Flame retardant composition, flame retardant resin composition and molded article

Abstract

Provided are a flame retardant agent composition having excellent flame retardancy as well as an excellent balance of dust control and powder fluidity, a flame-retardant resin composition using the same, and a molded body thereof.　A flame retardant agent composition containing one or more of phosphate compounds represented by general formula (1) or (2). Taking the loose bulk density of the flame retardant agent composition as d (g / cm3), the cumulative 10% particle size of the flame retardant agent composition in a volume-based particle size distribution as D10 (μm), and the cumulative 50% particle size as D50 (μm), d, D10, and D50 satisfy 0.030 ≤ d / (D50 - D10) ≤ 0.110.

Description

[Technical Field]

[0001] The present invention relates to a flame retardant composition that not only has excellent flame retardancy but also has an excellent balance between dust suppression and powder flowability, a flame retardant resin composition using the same, and a molded article thereof. [Background technology]

[0002] Synthetic resins have excellent mechanical properties and are highly convenient, making them used in a wide range of fields and essential materials for modern life. However, many synthetic resins are flammable, and depending on the application, imparting flame retardancy is essential for improving safety. Various methods have been proposed to impart flame retardancy to synthetic resins, including, for example, a method of adding an intumescent flame retardant to a synthetic resin, as described in Patent Document 1.

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

[0004] [Patent Document 1] Japanese Patent Application Laid-Open No. 2003-026935 [Patent Document 2] International Publication No. 2016 / 125612 [Patent Document 3] International Publication No. 2019 / 009340 Summary of the Invention [Problem to be solved by the invention]

[0005] However, excessive suppression of dust generation causes a new problem of reduced powder fluidity. A decrease in the powder fluidity of a flame retardant composition increases concerns about reduced productivity due to clogging in the powder supply device of a processing machine, and performance degradation due to poor dispersion when mixed into a resin composition. Patent Documents 1 to 3 do not mention or suggest this issue, and conventional flame retardant compositions have room for improvement in terms of achieving both suppression of dust scattering and good powder fluidity.

[0006] Therefore, an object of the present invention is to provide a flame retardant composition that has 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. [Means for solving the problem]

[0007] As a result of intensive investigations to solve the above problems, the present inventors have found that, in a flame retardant composition using a predetermined phosphate compound, by setting the ratio of the loose bulk density to the particle size distribution width within a specific range, it is possible to achieve both excellent flame retardancy, suppression of dust scattering, and good powder fluidity, and have completed the present invention.

[0008] That is, according to the present invention, there is provided a flame retardant composition containing one or more phosphate compounds represented by the following general formula (1) or the following general formula (2), The loose bulk density of the flame retardant composition is d (g / cm 3 ) the cumulative 10% particle size in the volume-based particle size distribution of the flame retardant composition is D 10 (μm), cumulative 50% particle diameter is D 50 (μm), d, D 10 and D 50 However, there is provided a flame retardant composition that satisfies the following formula (I): 0.030≦d / (D 50 -D 10 )≦0.110 (I)

[0009] 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 represents a number satisfying 0 < p ≦ n1 + 2.

[0010] In general formula (1-A), Z 1 and Z 2 each independently represent a 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, and 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 methylol group.

[0011] In general formula (2), n2 represents a number from 1 to 100, and Y 1 represents [R 21 R 22 N(CH2) m NR 23 R 24 , piperazine, or a diamine containing a piperazine ring, and R 21 , R 22 , R 23 and R 24 each independently represent a hydrogen atom or a linear or branched alkyl group having 1 to 5 carbon atoms, m is an integer from 1 to 10, and q represents a number satisfying 0 < q ≦ n2 + 2.

[0012] In the flame retardant composition of the present invention, it is preferable that d satisfies the following formula (II). 0.20 ≦ d ≦ 0.80 ··· (II)

[0013] The flame retardant composition of the present invention is X 1It is preferable that the phosphate compound represented by the general formula (1) is melamine.

[0014] The flame retardant composition of the present invention also contains Y 1 It is preferable that the phosphate compound represented by the general formula (2) is piperazine.

[0015] Furthermore, the flame retardant composition of the present invention is 1 It is preferable that the phosphate compound represented by the general formula (1) contains ammonia.

[0016] Furthermore, the flame retardant composition of the present invention is 1 the phosphate compound represented by the general formula (1) in which Y is melamine; 1 It is also preferable that the phosphate compound represented by the general formula (2) contains piperazine.

[0017] Furthermore, the flame retardant composition of the present invention preferably contains the phosphate compound represented by general formula (1) in which n1 is 2, and the phosphate compound represented by general formula (2) in which n2 is 2.

[0018] The present invention also provides a flame-retardant resin composition containing the flame retardant composition and a thermoplastic resin.

[0019] In the flame-retardant resin composition of the present invention, the thermoplastic resin preferably contains a polyolefin resin.

[0020] Furthermore, according to the present invention, there is provided a molded article made using the above flame-retardant resin composition. [Effects of the Invention]

[0021] According to the present invention, it is possible to provide a flame retardant composition that has excellent flame retardancy and an excellent balance between dust suppression property and powder flowability, a flame-retardant resin composition using the same, and a molded article thereof. [Brief explanation of the drawings]

[0022] [Figure 1] It is an explanatory diagram showing an outline of an apparatus used for evaluating dust scattering property in an embodiment.

Mode for Carrying Out the Invention

[0023] Hereinafter, the present invention will be described in detail based on its preferred embodiments. <Flame Retardant Composition> The flame retardant composition of the present invention contains one or more of phosphate compounds represented by the following general formula (1) or the following general formula (2).

[0024] 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 represents a number satisfying 0 < p ≦ n1 + 2.

[0025] In general formula (1-A), Z 1 and Z 2 each independently represents a group selected from the group consisting of -NR 11 R 12 group, 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, and 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 methylol group.

[0026] In general formula (2), n2 represents a number from 1 to 100, and Y 1 is [R 21 R 22 N(CH2) m NR 23 R 24〕, piperazine, or a diamine containing a piperazine ring, and 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, and q represents a number satisfying 0 < q ≦ n2 + 2.

[0027] Z in the general formula (1-A) above 1 and Z 2 Examples of the linear or branched alkyl group 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, and the like. Further, examples of the linear or branched alkoxy group having 1 to 10 carbon atoms represented by Z 1 and Z 2 in the general formula (1-A) above include groups derived from the above alkyl groups. Furthermore, the -NR 1 and Z 2 that Z can take in the R 11 R 12 Examples of the linear or branched alkyl group having 1 to 6 carbon atoms represented by R 11 and R 12 in the group include those having 1 to 6 carbon atoms among the alkyl groups listed above.

[0028] Specific examples of the triazine derivative represented by the general formula (1-A) include melamine, acetoguanamine, 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, and 2-amino-4,6-dimercapto-1,3,5-triazine.

[0029] The compound represented by the general formula (1) may be a single compound or a mixture of two or more compounds having different degrees of condensation or different types of salts. 1 a phosphate compound represented by the above general formula (1), wherein X is melamine; and 1 It is preferable that the phosphate compound contains one or more of the phosphate compounds represented by the general formula (1) in which n1 is ammonia. Furthermore, it is preferable that the phosphate compound contains a pyrophosphate represented by the general formula (1) in which n1 is 2. When the phosphate compounds are used as a mixture, the higher the content of the pyrophosphate represented by the general formula (1) in which n1 is 2, the more preferable. This allows for stable improvement of heat resistance.

[0030] In the above general formula (2), Y 1 The compounds represented by [R 21 R 22 N(CH2) m NR 23 R 24 ], piperazine, or a diamine containing a piperazine ring. 21 ~R 24 may be the same or different and represent a hydrogen atom or a linear or branched alkyl group having 1 to 5 carbon atoms.

[0031] Above R 21~R 24 Examples of the linear or branched alkyl group having 1 to 5 carbon atoms represented by the formula (I) include the above-mentioned Z 1 and Z 2 Among the alkyl groups given above as specific examples of the alkyl group represented by the formula, those having 1 to 5 carbon atoms can be mentioned.

[0032] Examples of the diamine containing a piperazine ring include a compound in which one or more of the 2-, 3-, 5-, and 6-positions of piperazine are substituted with alkyl groups (preferably having 1 to 5 carbon atoms); and a compound in which the amino groups at the 1- and / or 4-positions of piperazine are substituted with alkyl groups (preferably having 1 to 5 carbon atoms).

[0033] Y in the above general formula (2) 1 Specific examples of the compound represented by the formula (I) 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-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, and 1,4-bis(3-aminopropyl)piperazine.

[0034] The compound represented by the general formula (2) may be a single compound or a mixture of two or more compounds having different degrees of condensation or different types of salt. 1It is preferable that the phosphate compound contains a phosphate compound represented by the general formula (2) in which n2 is piperazine. Furthermore, it is preferable that the phosphate compound contains a pyrophosphate represented by the general formula (2) in which n2 is 2. When the phosphate compounds are used as a mixture, the higher the content of the pyrophosphate in which n2 is 2, the more preferable. This allows for stable improvement of heat resistance.

[0035] 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 a desired ratio, adding hydrochloric acid to cause a reaction, and neutralizing with sodium hydroxide. Furthermore, for example, a salt of a phosphoric acid and piperazine can be easily obtained as a poorly water-soluble precipitate by reacting a phosphoric acid and piperazine in a desired ratio in water or aqueous methanol solution. The composition of the raw phosphoric acid is not particularly limited. Furthermore, a phosphate compound in which n1 or n2 in the above general formula (1) or (2) is 2 or greater may be obtained by thermal condensation of an orthophosphate in which n1 or n2 is 1.

[0036] The above-mentioned phosphate compounds are obtained by the above steps. These may be used alone or in combination of two or more. The flame retardant composition containing such a phosphate compound can impart excellent flame retardancy to a resin material.

[0037] From the viewpoint of flame retardancy, the flame retardant composition of the present invention preferably contains both the phosphate compound represented by the above general formula (1) and the phosphate compound represented by the above general formula (2).

[0038] In particular, X 1 a phosphate compound represented by the above general formula (1) in which Y is melamine; 1 It is preferable to use a phosphate compound represented by the above general formula (1) in which n1 is 2 in combination with a phosphate compound represented by the above general formula (2) in which n2 is 2 in combination. It is also preferable to use a phosphate compound represented by the above general formula (1) in which n1 is 2 in combination with a phosphate compound represented by the above general formula (2) in which n2 is 2.

[0039] 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 mass 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, from the viewpoint of flame retardancy.

[0040] Furthermore, as described above, the inventors have found through their investigations that the bulk density of the flame retardant composition affects the dust scattering property.

[0041] Generally, it is believed that the lower the bulk density of a powder, the higher its dust scattering tendency. However, as a result of studies by the present inventors, it was surprisingly found that the opposite result was observed in the flame retardant composition of the present invention containing the above-mentioned specific phosphate compound. That is, it was found that when the loose bulk density of the flame retardant composition is high, the dust scattering tendency of the flame retardant composition increases.

[0042] Based on this finding, the present inventors have conducted further intensive studies and found that by setting the ratio of the loose bulk density to the particle size distribution width of the flame retardant composition to a predetermined value or more and a predetermined value or less, it is possible to achieve both 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 concern of adversely affecting the powder fluidity, but as a result of the studies of the present inventors, it has been found that by appropriately setting the ratio of the loose bulk density to the particle size distribution width, it is possible to achieve both suppression of dust scattering and good powder fluidity.

[0043] Therefore, the flame retardant composition of the present invention can suppress dust scattering and prevent deterioration of the working environment due to dust. Furthermore, the flame retardant composition of the present invention exhibits good powder flowability, so that it is less likely to have an adverse effect on productivity and dispersibility when mixed with a resin material.

[0044] The flame retardant composition of the present invention has a loose bulk density of d (g / cm3 ), and the cumulative 10% particle size in the volume-based particle size distribution is D 10 (μm), cumulative 50% particle diameter is D 50 (μm), d, D 10 and D 50 satisfies the following formula (I). 0.030≦d / (D 50 -D 10 )≦0.110 (I)

[0045] In the above formula (I), d / (D 50 -D 10 The lower limit of d / (D) is 0.030 or more, preferably 0.035 or more, and more preferably 0.040 or more. This can improve the powder flowability. On the other hand, in the above formula (I), 50 -D 10 ) is 0.110 or less, preferably 0.107 or less, and more preferably 0.103 or less. This makes it possible to prevent excessive dust scattering.

[0046] Here, the loose bulk density d is the packing density of the powder when it is allowed to fall naturally. The loose bulk density is measured, for example, by 3 A suitable amount of the powder composition was dropped into a cylindrical container from the upper open end of the container to loosely fill it, and the mass (g) of the filled powder composition was measured and the volume (cm 3 ) and take a reading of the volume (cm 3 The loose bulk density can be determined by calculating the mass (g) of the powder composition per 1000g of powder. The loose bulk density may be measured using a commercially available powder property measuring device.

[0047] In addition, the cumulative 10% particle size D in the volume-based particle size distribution of the flame retardant composition 10 and cumulative 50% particle diameter D 50 can be determined, for example, by dispersing the flame retardant composition in methanol, subjecting the dispersion to ultrasonic treatment, and measuring the dispersion using a laser diffraction / scattering particle size distribution analyzer.

[0048] 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). 0.20≦d≦0.80 (II)

[0049] In the above formula (II), the lower limit of d is 0.20 or more, preferably 0.25 or more, and more preferably 0.30 or more. This can improve powder fluidity. 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 scattering.

[0050] The loose bulk density d and cumulative 10% particle diameter D 10 and cumulative 50% particle diameter D 50 can be controlled by appropriately selecting the preparation method such as pulverization, classification, etc. Among these, for example, appropriate selection of pulverization conditions such as pulverization method and pulverization time, classification conditions such as removal of coarse particles, blending conditions, etc. can be used to control the above d and D. 10 and D 50 are factors for setting the desired numerical range. 10 and D 50 The surface roughness can be controlled by appropriately selecting the surface treatment or not and the surface treatment agent, etc. Examples of such surface treatment agents include the surface treatment agents, dust suppressants, lubricants, etc., which will be described later.

[0051] Examples of the grinding means for the grinding include a mortar, ball mill, rod mill, tube mill, conical mill, vibration ball mill, high swing ball mill, roller mill, pin mill, hammer mill, attrition mill, jet mill, jetmizer, micronizer, nanomizer, Majack mill, microatomizer, colloid mill, premier colloid mill, micron mill, Shallotte colloid mill, rotary cutter, dry media stirring mill, impact type ultrafine grinder, planetary mill, bead mill, microbead mill, attritor, crushing roll, etc. These grinding means can be used alone or in combination of two or more.

[0052] Examples of the classification method include dry classification such as sieving classification, inertial classification, and centrifugal classification, and wet classification such as sedimentation classification, etc. Pulverization and classification may be carried out simultaneously using a pulverizer with a built-in classification function.

[0053] When the flame retardant composition of the present invention is a mixture of multiple components, the components may be mixed after undergoing a preparation step such as pulverization or classification, or the components may be mixed and then subjected to a preparation step such as pulverization or classification.

[0054] The flame retardant composition of the present invention may contain a co-agent.

[0055] Examples of the auxiliary agent include a flame retardant auxiliary agent, an anti-drip auxiliary agent, and a processing auxiliary agent.

[0056] The flame retardant aid may contain a metal oxide or a polyhydric alcohol compound, which can improve the flame retardancy of the resin.

[0057] Examples of the metal oxide 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 alone or in combination of two or more. 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 viewpoint of flame retardancy.

[0058] The zinc oxide may be surface-treated or may not be surface-treated. Specific examples of the zinc oxide that can be used include commercially available products such as zinc oxide type 1 (manufactured by Mitsui Smelting & Industrial Co., Ltd.), partially coated zinc oxide (manufactured by Mitsui Smelting & Industrial Co., Ltd.), Nanofine 50 (ultrafine zinc oxide particles having an average particle size of 0.02 μm: manufactured by Sakai Chemical Industry Co., Ltd.), and Nanofine K (ultrafine zinc oxide particles coated with zinc silicate having an average particle size of 0.02 μm: manufactured by Sakai Chemical Industry Co., Ltd.).

[0059] The polyhydric alcohol compound is a compound having a plurality of hydroxy 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, glycerin, diglycerin, mannitol, maltitol, lactitol, sorbitol, erythritol, xylitol, xylose, sucrose, trehalose, inositol, fructose, maltose, and lactose. Among these polyhydric alcohol compounds, one or more selected from the group consisting of pentaerythritol and pentaerythritol condensates, such as pentaerythritol, dipentaerythritol, tripentaerythritol, and polypentaerythritol, are preferred, with dipentaerythritol and pentaerythritol condensates being particularly preferred, and dipentaerythritol being the most preferred. Furthermore, THEIC and sorbitol can also be suitably used. These may be used alone or in combination of two or more.

[0060] Examples of the anti-drip aid include layered silicates, fluorine-based anti-drip aids, and silicone rubbers, which can suppress dripping during resin combustion.

[0061] The layered silicate is a layered silicate mineral, and may be either natural or synthetic, and is not particularly limited. Examples of the layered silicate include smectite clay minerals such as montmorillonite, saponite, hectorite, beidellite, stevensite, and nontronite, as well as vermiculite, halloysite, swelling mica, and talc. These may be used alone or in combination of two or more. Among the layered silicates, saponite or talc are preferred from the viewpoint of preventing dripping, and talc is particularly preferred from the viewpoint of cost and other economical aspects.

[0062] The layered silicate may have cations between layers, which may be metal ions, or some or all of which may be cations other than metal ions, such as organic cations, (quaternary) ammonium cations, or phosphonium cations.

[0063] Examples of the metal ions include sodium ions, potassium ions, calcium ions, magnesium ions, lithium ions, nickel ions, copper ions, and zinc ions.

[0064] Examples of the organic cation or quaternary ammonium cation include lauryltrimethylammonium cation, stearyltrimethylammonium cation, trioctylmethylammonium cation, distearyldimethylammonium cation, di-hardened beef tallow dimethylammonium cation, distearyldibenzylammonium cation, etc. These may be used alone or in combination of two or more.

[0065] Specific examples of the fluorine-based drip prevention aid include fluorine-based resins such as polytetrafluoroethylene, polyvinylidene fluoride, and polyhexafluoropropylene, as well as alkali metal salt compounds of perfluoroalkanesulfonic acid or alkaline earth metal salts of perfluoroalkanesulfonic acid, such as sodium perfluoromethanesulfonate, potassium perfluoro-n-butanesulfonate, potassium perfluoro-t-butanesulfonate, sodium perfluorooctanesulfonate, and calcium perfluoro-2-ethylhexanesulfonate. Among these, polytetrafluoroethylene is preferred from the viewpoint of drip prevention. These may be used alone or in combination of two or more.

[0066] The processing aid can be appropriately selected from known processing aids, and may include an acrylic acid-based processing aid.

[0067] Examples of the acrylic acid-based processing aid include homopolymers or copolymers of alkyl methacrylates such as methyl methacrylate, ethyl methacrylate, and butyl methacrylate; copolymers of the alkyl methacrylates with alkyl acrylates such as methyl acrylate, ethyl acrylate, and butyl acrylate; copolymers of the alkyl methacrylates with aromatic vinyl compounds such as styrene, α-methylstyrene, and vinyltoluene; and copolymers of the alkyl methacrylates with vinyl cyan compounds such as acrylonitrile and methacrylonitrile. These may be used alone or in combination of two or more.

[0068] The flame retardant composition may contain a surface treatment agent.

[0069] Examples of the surface treatment agent include silicone oil and silane coupling agents. The use of silicone oil can prevent aggregation of the powdered flame retardant composition, improve storage stability, and improve dispersibility in synthetic resins. It can also improve water resistance.

[0070] The silicone oil can be any known silicone oil having a polysiloxane skeleton, without any particular limitation. The silicone oil may be a polymer having a linear polysiloxane skeleton, and the polysiloxane side chains may all be methyl groups, or some of the side chains may have phenyl groups, or some of the side chains may have hydrogen.

[0071] Examples of silicone oil include dimethyl silicone oil, in which the side chain and terminal of polysiloxane are all methyl groups; methylphenyl silicone oil, in which the side chain and terminal of polysiloxane are methyl groups and part of the side chain is phenyl group; methylhydrogen silicone oil, in which the side chain and terminal of polysiloxane are methyl groups and part of the side chain is hydrogen, and copolymers thereof.These silicone oils can be partially modified by epoxy modification, amino modification, carboxy modification, etc.These can be used alone or in combination of two or more.

[0072] Among the silicone oils, dimethyl silicone oil and methyl hydrogen silicone oil are preferred, and methyl hydrogen silicone oil is more preferred, from the viewpoints of preventing aggregation of the powdery flame retardant composition, improving storage stability, and improving dispersibility in synthetic resins.

[0073] Examples of the silane coupling agent include silane coupling agents having an alkenyl group, such as vinyltrimethoxysilane, vinyltriethoxysilane, vinyltriacetoxysilane, vinyltris(2-methoxyethoxy)silane, vinylmethyldimethoxysilane, octenyltrimethoxysilane, allyltrimethoxysilane, and p-styryltrimethoxysilane; silane coupling agents having an acrylic group, such as 3-acryloxypropyltrimethoxysilane and 3-acryloxypropyltriethoxysilane; and silane coupling agents having a methacryl group, such as 3-methacryloxypropylmethyldimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropylmethyldiethoxysilane, 3-methacryloxypropyltriethoxysilane, and methacryloxyoctyltrimethoxysilane. Examples of silane coupling agents having an epoxy group include 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, 3-glycidoxypropyltriethoxysilane, and glycidoxyoctyltrimethoxysilane. Examples of silane coupling agents having an amino group include 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, N,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 ureido group include silane coupling agents having an isocyanurate group, tris-(trimethoxysilylpropyl)isocyanurate. Examples of silane coupling agents having an isocyanurate group include 3-mercaptopropylmethyldimethoxysilane, 3-mercaptopropyltrimethoxysilane, and 3-mercaptopropyltriethoxysilane. Examples of silane coupling agents include 3-ureidopropyltrimethoxysilane and 3-ureidopropyltriethoxysilane. 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.

[0074] Among these silane coupling agents, silane coupling agents having an epoxy group are preferred from the viewpoints of improving flame retardancy and ease of handling, and further preventing aggregation of the powdery 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.

[0075] Examples of the method for adding the surface treatment agent include a method of mixing the powdery flame retardant composition with the surface treatment agent, a method of spray-drying the surface treatment agent and adding and mixing it, etc. The surface treatment agent may also be added to the flame retardant composition by surface-treating some of the components that constitute the flame retardant composition.

[0076] The flame retardant composition may include a dust suppressant.

[0077] Examples of the dust suppressant include an aliphatic dicarboxylic acid ether ester compound and the above-mentioned silane coupling agent.

[0078] The aliphatic dicarboxylic acid ether ester compound may contain a compound represented by the following general formula (3). This can suppress dust from the particulate flame retardant composition. These compounds may be used alone or in combination of two or more.

[0079] TIFF0007813724000007.tif19153In general formula (3), n3 represents an integer of 1 to 3, m3 represents an integer of 2 to 6, and R 3 represents an alkyl group having 1 to 6 carbon atoms.

[0080] In the above general formula (3), R 3 The alkyl group having 1 to 6 carbon atoms represented by the formula (I) may be a straight-chain alkyl group or a branched alkyl group, and examples thereof include methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl, tert-butyl, amyl, isoamyl, tert-amyl, and hexyl groups. 3 As the alkyl group, a butyl group is preferred from the viewpoint of flame retardancy, and particularly from the viewpoint of handling properties and storage stability.

[0081] In addition, in the above general formula (3), n3 is preferably 2 from the viewpoints of flame retardancy, particularly ease of handling and storage stability. Furthermore, in the above general formula (3), m3 is preferably 4 from the viewpoints of flame retardancy, particularly ease of handling and storage stability.

[0082] The flame retardant composition may contain other components as long as the effects of the present invention are not impaired. Examples of other components include additives typically used to modify thermoplastic resins, such as antioxidants, light stabilizers, ultraviolet absorbers, crystal nucleating agents, clarifying agents, plasticizers, lubricants, flame retardants other than the phosphate compound of the present invention, reinforcing materials, crosslinking agents, antistatic agents, metal soaps, fillers, antifogging agents, antiplateout agents, fluorescent agents, antifungal agents, bactericides, foaming agents, metal deactivators, release agents, pigments, and dyes. These may be used alone or in combination of two or more.

[0083] Examples of antioxidants include phenol-based antioxidants, phosphite-based antioxidants, thioether-based antioxidants, and other antioxidants.

[0084] Examples of phenolic antioxidants 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)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)isocyanurate, 1,3,5-tris(3,5-di-tert-butyl-4-hydroxybenzyl)isocyanurate, 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] oxyphenyl)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,Examples of such phenolic antioxidants include 10-tetraoxaspiro[5,5]undecane and triethylene glycol bis[(3-tert-butyl-4-hydroxy-5-methylphenyl)propionate]. These phenolic antioxidants can be used alone or in combination of two or more.

[0085] Examples of phosphite antioxidants include trisnonylphenyl phosphite, tris[2-tert-butyl-4-(3-tert-butyl-4-hydroxy-5-methylphenylthio)-5-methylphenyl]phosphite, tridecyl phosphite, octyldiphenyl 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)isopropylidenediphenol diphosphite, and 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)butane triphosphite, tetrakis(2,4-di-tert-butylphenyl)biphenylene diphosphonite, 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, 2,2'-methylenebis(4,6-tert-butylphenyl)-2-ethylhexyl phosphite, Examples include 2,2'-methylenebis(4,6-tert-butylphenyl)-octadecyl phosphite, 2,2'-ethylidenebis(4,6-di-tert-butylphenyl)fluorophosphite, tris(2-[(2,4,8,10-tetrakis-tert-butyldibenzo[d,f][1,3,2]dioxaphosphepin-6-yl)oxy]ethyl)amine, and phosphite of 2-ethyl-2-butylpropylene glycol and 2,4,6-tri-tert-butylphenol. These phosphite antioxidants can be used alone or in combination of two or more.

[0086] Examples of thioether antioxidants include 3,3'-thiodipropionic acid, alkyl (C12-14) thiopropionic acid, di(lauryl)-3,3'-thiodipropionate, ditridecyl 3,3'-thiobispropionate, di(myristyl)-3,3'-thiodipropionate, di(stearyl)-3,3'-thiodipropionate, di(octadecyl)-3,3'-thiodipropionate, laurylstearylthiodipropionate, tetrakis[methyl thiodiethylenebis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)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), bis(4,6- Examples of the thioether antioxidants include 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 antioxidants can be used alone or in combination of two or more.

[0087] Other antioxidants include, for example, nitrone compounds such as N-benzyl-α-phenyl nitrone, N-ethyl-α-methyl nitrone, N-octyl-α-heptyl nitrone, N-lauryl-α-undecyl nitrone, N-tetradecyl-α-tridecyl nitrone, N-hexadecyl-α-pentadecyl nitrone, N-octyl-α-heptadecyl nitrone, N-hexadecyl-α-heptadecyl nitrone, N-octadecyl-α-pentadecyl nitrone, N-heptadecyl-α-heptadecyl nitrone, and N-octadecyl-α-heptadecyl nitrone; 3-arylbenzofuran-2(3H)-one, 3-(alkoxyphenyl)benzofuran-2-one, 3-(acyloxyphenyl)benzofuran-2(3H)-one; Examples of the benzofuran compounds include ert-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, and 5-di-tert-butyl-3-(4-((15-hydroxy-3,6,9,13-tetraoxapentadecyl)oxy)phenyl)benzofuran-2(3H)-one. These other antioxidants can be used alone or in combination of two or more.

[0088] Examples of light stabilizers 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-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) 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) Polycondensation product of 1,6-bis(2,2,6,6-tetramethyl-4-piperidinol / diethyl succinate, polycondensation product of 1,6-bis(2,2,6,6-tetramethyl-4-piperidylamino)hexane / 2,4-dichloro-6-morpholino-s-triazine, polycondensation product of 1,6-bis(2,2,6,6-tetramethyl-4-piperidylamino)hexane / 2,4-dichloro-6-tert-octylamino-s-triazine, polycondensation product of 1,5,8,12-tetrakis[2,4-bis(N-butyl-N-(2,2,6,6-tetramethyl-4-piperidyl)amino)- 1,6,11-Tris[2,4-bis(N-butyl-N-(2,2,6,6-tetramethyl-4-piperidyl)amino)-s-triazin-6-yl]aminoundecane, 1,6,11-Tris[2,4-bis(N-butyl-N-(1,2,2,6,6-tetramethyl-4-piperidyl)amino]-s-triazin-6-yl]aminoundecane, 1,6,11-Tris[2,4-bis(N-butyl-N-(1,2,2,6,6-pentamethyl-4-piperidyl)amino)-s-triazin-6-yl)aminoundecane, bis(2,2,6,6-tetramethyl-1-octyloxy-4-piperidyl)decanedioate, 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, polymers with 2,2-bis(hydroxymethyl)-1,3-propanediol and 3-hydroxy-2,2-dimethylpropanal, 1,2,2,6,6-pentamethyl Examples of such light stabilizers include 2,4-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, 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 can be used alone or in combination of two or more.

[0089] Examples of the ultraviolet absorber include 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'-hydroxy-5'-methylphenyl)benzotriazole, 2-(2'-hydroxy-3',5'-di-tert-butylphenyl)-5-chlorobenzotriazole, and 2-(2'-hydroxy-3',5'-tert-butylphenyl)-5-chlorobenzotriazole. 2-(2'-hydroxyphenyl)benzotriazoles such as 2-(2'-hydroxy-5'-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; phenyl salicylate Benzoates such as 2,4-di-tert-butylphenyl-3,5-di-tert-butyl-4-hydroxybenzoate, 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; ethyl-α-cyano-β,β-diphenylacrylate, methyl and 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 can be used alone or in combination of two or more.

[0090] Examples of the crystal nucleating agent include metal salts of carboxylic acids such as sodium benzoate, aluminum 4-tert-butylbenzoate, sodium adipate, and disodium bicyclo[2.2.1]heptane-2,3-dicarboxylate; metal salts of phosphates 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; dibenzylidene sorbitol, bis(methylbenzylidene)sorbitol, bis(3,4-dimethylbenzylidene)sorbitol, bis(p-ethylbenzylidene)sorbitol, and bis(dimethylbenzyl) sorbitol. Examples of suitable crystal nucleating agents 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 (dibenzylidenesorbitol); 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(dimethylisopropoylamino)benzene. These crystal nucleating agents can be used alone or in combination of two or more.

[0091] 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 polyhydric alcohols, and polycondensates of polycarboxylic acids and polyhydric alcohols, polyether ester-based plasticizers such as polycondensates of dicarboxylic acids, polyhydric alcohols, and alkylene glycols, polycondensates of dicarboxylic acids, polyhydric alcohols, and arylene glycols, polycondensates of polycarboxylic acids, polyhydric alcohols, and alkylene glycols, and polycondensates of polycarboxylic acids, polyhydric alcohols, and arylene glycols, aliphatic ester-based plasticizers such as adipates and succinates, and aromatic ester-based plasticizers such as phthalates, terephthalates, trimellitates, pyromellitates, and benzoates. These plasticizers can be used alone or in combination of two or more.

[0092] Examples of lubricants include pure hydrocarbon lubricants such as liquid 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 oxyfatty acids; fatty acid amide lubricants such as fatty acid amides and bisfatty 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 of fatty acids (ester waxes); lubricants based on metal soaps, fatty alcohols, polyhydric alcohols, polyglycols, polyglycerols, partial esters of fatty acids and polyhydric alcohols, partial esters of fatty acids and polyglycols or polyglycerols, silicone oils, mineral oils, etc. These lubricants can be used alone or in combination of two or more.

[0093] Examples of flame retardants other than the phosphate compounds according to the present invention include triphenyl phosphate, tricresyl phosphate, trixylenyl phosphate, cresyl diphenyl phosphate, cresyl-2,6-dixylenyl phosphate, resorcinol bis(diphenyl phosphate), (1-methylethylidene)-4,1-phenylenetetraphenyl diphosphate, 1,3-phenylenetetrakis(2,6-dimethylphenyl)phosphate, and ADEKA STAB FP (trade name) manufactured by ADEKA Corporation. aromatic phosphate esters such as "ADK STAB FP-500", "ADK STAB FP-600", "ADK STAB FP-800", and "ADK STAB FP-900L", phosphonate esters such as divinyl phenylphosphonate, diallyl phenylphosphonate, and 1-butenyl phenylphosphonate, phosphinate esters such as phenyl diphenylphosphinate, methyl diphenylphosphinate, and 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide derivatives, aluminum diethylphosphinate, diethylphosphinate, and Dialkyl phosphinates such as zinc phosphinate, phosphazene compounds such as bis(2-allylphenoxy)phosphazene and dicresylphosphazene, inorganic phosphorus flame retardants such as red phosphorus, metal hydroxides such as magnesium hydroxide and aluminum hydroxide, brominated bisphenol A type epoxy resins, brominated phenol novolac type epoxy resins, hexabromobenzene, pentabromotoluene, ethylene bis(pentabromophenyl), ethylene bistetrabromophthalimide, 1,2-dibromo-4-(1,2-dibromoethylene) Examples of suitable flame retardants include brominated flame retardants such as 2,4,6-tris(tribromophenoxy)-1,3,5-triazine, tribromophenylmaleimide, tribromophenyl acrylate, tribromophenyl methacrylate, tetrabromobisphenol A dimethacrylate, pentabromobenzyl acrylate, and brominated styrene. These other flame retardants can be used alone or in combination of two or more.

[0094] 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 polyoxyethylene alkyl allyl ethers, and amphoteric antistatic agents such as amphoteric alkyl betaines such as alkyl dimethylaminoacetic acid betaine and imidazoline-type amphoteric surfactants. These antistatic agents can be used alone or in combination of two or more.

[0095] 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, wollastonite, fibrous magnesium oxysulfate, and montmorillonite, and the particle size (fiber diameter, fiber length, and aspect ratio in the case of fibrous fillers) can be appropriately selected and used. These fillers can be used alone or in combination of two or more. Furthermore, fillers that have been surface-treated can be used as needed.

[0096] Examples of pigments 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, 201, 202, 203, 204, 205, 206, 207, 208, 209, 210, 211, 212, 213, 214, 215, 216, 217, 218, 219, 220, 221, 222, 223, 224, 225, 226, 227, 228, 229, 230, 231, 232, 233, 234, 235, 236, 237, 238, 239, 240, 241, 242, 243, 244, 245, 246, 247, 248, 249, 250, 251, 252, 253, 254, 255, 256, 257, 258, 259, 260, 261, 262, 263, 264, 265, 266, 267, 268, 269, 170, 1 02, 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, 1 4, 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, 1 75, 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 can be used alone or in combination of two or more.

[0097] Examples of dyes include azo dyes, anthraquinone dyes, indigoid dyes, triarylmethane dyes, xanthene dyes, alizarin dyes, acridine dyes, stilbene dyes, thiazole dyes, naphthol dyes, quinoline dyes, nitro dyes, indamine dyes, oxazine dyes, phthalocyanine dyes, cyanine dyes, etc. These dyes can be used alone or in combination of two or more.

[0098] One or more of the above-mentioned auxiliaries, surface treatment agents, dust suppressants, and other components may be blended into the flame retardant composition, or may be blended into a flame retardant resin composition containing the flame retardant composition and a thermoplastic resin.

[0099] The flame retardant composition of the present invention can be obtained by mixing one or more phosphate compounds represented by general formula (1) or general formula (2) with other optional components as needed, provided that the above formula (I) is satisfied. Various mixers can be used for mixing. Heat may be applied during mixing. Mixers that can be used include, but are not limited to, a tumbler mixer, a Henschel mixer, a ribbon blender, a V-type mixer, a W-type mixer, a Super mixer, a Nauta mixer, etc.

[0100] Furthermore, 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 pulverizing with a pulverizer, etc.

[0101] <Flame-retardant resin composition> The flame-retardant resin composition of the present invention contains the above-mentioned flame retardant composition and a thermoplastic resin.

[0102] The content of the flame retardant composition is usually 10 to 400 parts by mass, preferably 15 to 200 parts by mass, and more preferably 20 to 70 parts by mass, relative to 100 parts by mass of the thermoplastic resin, which can sufficiently improve the flame retardancy of the thermoplastic resin.

[0103] 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. These may be used alone or in combination of two or more.

[0104] Further examples of the thermoplastic resin include petroleum resin, coumarone resin, polyvinyl acetate, acrylic resin, polymethyl methacrylate, polyvinyl alcohol, polyvinyl formal, polyvinyl butyral, polyphenylene sulfide, polyurethane, cellulose resin, polyimide resin, polysulfone, liquid crystal polymer, and other thermoplastic resins, as well as blends thereof.

[0105] The 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, or these may be used in combination.

[0106] Specific examples of the thermoplastic resin include, but are not limited to, polyolefin-based resins such as α-olefin polymers such as polypropylene, high-density polyethylene, low-density polyethylene, linear low-density polyethylene, polybutene-1, poly3-methylpentene, poly4-methylpentene, and ethylene / propylene block or random copolymers; thermoplastic linear polyester-based resins such as polyethylene terephthalate, polybutylene terephthalate, and polyhexamethylene terephthalate; polysulfide-based resins such as polyphenylene sulfide; polylactic acid-based resins such as polycaprolactone; linear polyamide-based resins such as polyhexamethylene adipamide; and crystalline polystyrene-based resins such as syndiotactic polystyrene.

[0107] These thermoplastic resins can be used regardless of the molecular weight, degree of polymerization, density, softening point, proportion of insoluble matter in a solvent, degree of stereoregularity, presence or absence of catalyst residue, types and blending ratios of raw material monomers, type of polymerization catalyst (e.g., Ziegler catalyst, metallocene catalyst, etc.), etc.

[0108] Among these thermoplastic resins, one or more selected from the group consisting of polyolefin resins, polystyrene resins, and copolymers thereof are preferred, from the viewpoint of being able to impart excellent flame retardancy, and polyolefin resins are more preferred, with polypropylene, high-density polyethylene, low-density polyethylene, and linear low-density polyethylene being even more preferred, and it is also preferred to use these resins in combination with a thermoplastic elastomer.

[0109] In addition to the flame retardant composition, the flame-retardant resin composition may contain, as necessary, one or more additives selected from the above-mentioned auxiliaries, surface treatment agents, dust suppressants, and other components, which may be used alone or in combination of two or more.

[0110] The content of the additives (excluding fillers and flame retardants other than the phosphate compound according to the present invention) in the flame-retardant resin composition 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 the content within such a range, the effect of the additives can be improved.

[0111] When a filler is blended into the flame-retardant resin composition, the content thereof 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, relative to 100 parts by mass of the thermoplastic resin.

[0112] When a flame retardant other than the phosphate compound according to the present invention is blended into 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, relative to 100 parts by mass of the thermoplastic resin.

[0113] When a polyolefin resin or an olefin elastomer is used as the thermoplastic resin in the flame-retardant resin composition, the flame-retardant resin composition preferably contains a known neutralizing agent to neutralize catalyst residues in the resin, within a range that does not impair the effects of the present invention. Examples of neutralizing agents include fatty acid metal salts such as calcium stearate, lithium stearate, sodium stearate, and magnesium stearate; fatty acid amide compounds such as ethylene bis(stearamide), ethylene bis(12-hydroxystearamide), and stearamide; and inorganic compounds such as hydrotalcite. These neutralizing agents can 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, more preferably 0.01 to 1 part by mass, per 100 parts by mass of the thermoplastic resin.

[0114] Next, a method for producing the flame-retardant resin composition will be described.

[0115] The flame-retardant resin composition can be obtained by mixing the flame-retardant composition with a thermoplastic resin. If necessary, the additives may be mixed in. The additives may be mixed in the flame-retardant composition or in a mixture of the flame-retardant composition and the thermoplastic resin.

[0116] As a mixing method, a commonly used known method can be applied as it is, for example, a method of mixing the flame retardant composition, the thermoplastic resin, and, if necessary, the additives in a mixer such as a general blender or mixer, a method of melt-kneading in an extruder, a method of mixing together with a solvent and then solution-casting, etc.

[0117] The flame-retardant resin composition can be used in various forms, for example, pellets, granules, or powder, with pellets being preferred from the viewpoint of ease of handling.

[0118] <Molded body> The molded article of the present invention is produced using the flame-retardant resin composition. A molded article can be produced by molding the flame-retardant resin composition.

[0119] The molding method is not particularly limited, and examples thereof include injection molding, extrusion molding, blow molding, rotational molding, vacuum molding, inflation molding, calendar molding, slush molding, dip molding, foam molding, additive manufacturing, etc. Among these, injection molding, extrusion molding, and blow molding are preferred.

[0120] This allows the production of molded articles of various shapes, such as resin plates, sheets, films, and irregularly shaped articles.

[0121] Molded articles made using the flame-retardant resin composition can be used in a variety of applications, including, for example, electrical and electronic parts, mechanical parts, optical instruments, building materials, automobile parts, and daily necessities, etc. Among these, from the viewpoint of flame retardancy, the composition is preferably used for electrical and electronic parts and building materials.

[0122] The flame-retardant resin composition and molded articles thereof can be used in a wide range of industrial fields, such as electricity, electronics, and communications, agriculture, forestry, and fisheries, mining, construction, food, textiles, clothing, medicine, coal, petroleum, rubber, leather, automobiles, precision instruments, 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 automation equipment such as printers, personal computers, word processors, keyboards, PDAs (personal digital assistants), telephones, copiers, facsimiles, ECRs (electronic cash registers), calculators, electronic organizers, cards, holders, and stationery; home appliances such as washing machines, refrigerators, vacuum cleaners, microwave ovens, lighting fixtures, game consoles, irons, and kotatsu tables; audio-visual equipment such as TVs, VTRs, video cameras, radio-cassette players, tape recorders, minidiscs, CD players, speakers, and liquid crystal displays; and electrical and electronic components and communication equipment such as connectors, relays, capacitors, switches, printed circuit boards, coil bobbins, semiconductor encapsulating materials, LED encapsulating materials, electric wires, cables, transformers, deflection yokes, distribution boards, and clocks.

[0123] The flame-retardant resin composition and its molded article can be used in, for example, seats (padding, upholstery, etc.), belts, ceiling coverings, convertible tops, armrests, door trims, rear package trays, carpets, mats, sun visors, wheel covers, mattress covers, airbags, insulating materials, hand straps, hand straps, wire covering materials, electrical insulating materials, paints, coating materials, covering materials, flooring materials, corner walls, carpets, wallpaper, wall covering materials, exterior materials, interior materials, roofing materials, deck materials, wall materials, and pillars. It can be used in a variety of fields, including materials for automobiles, vehicles, ships, aircraft, buildings, houses, etc., such as lumber, floor boards, fence materials, frames and moldings, window and door profiles, shingles, paneling, terraces, balconies, soundproofing boards, heat insulating boards, window materials, construction materials and civil engineering materials, clothing, curtains, sheets, plywood, synthetic fiber boards, carpets, entrance mats, sheets, buckets, hoses, containers, eyeglasses, bags, cases, goggles, skis, rackets, tents, musical instruments, and other daily necessities and sporting goods.

[0124] Although the embodiments of the present invention have been described above, these are merely examples of the present invention, and various other configurations may be adopted. Furthermore, the present invention is not limited to the above-described embodiments, and modifications and improvements within the scope of achieving the object of the present invention are included in the present invention. [Example]

[0125] The present invention will be described in detail below with reference to examples, but the present invention is not limited to the descriptions of these examples.

[0126] <Production of melamine salt> Melamine orthophosphate was subjected to a solid-state thermal condensation reaction at 220°C for 6 hours to produce a melamine salt containing melamine pyrophosphate as the main component. The melamine salt was used as is without purification. The purity of the melamine pyrophosphate in the melamine salt was 98.5%.

[0127] <Production of Piperazine Salt> Piperazine diphosphate was subjected to a solid-state thermal 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 as is without purification. The purity of piperazine pyrophosphate in the piperazine salt was 99.0%.

[0128] The purity of the melamine salt and 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 an electric conductivity detector.

[0129] <Preparation of Composition A1> 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 pulverized using a compact jet mill pulverizer (Cojet System α-mkIII, manufactured by Seishin Enterprise Co., Ltd.) under 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 input 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 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 A1.

[0130] <Preparation of Composition A2> 35 parts by mass of the melamine salt, 5 parts by mass of melamine polyphosphate (PMP100, manufactured by Nissan Chemical Industries, Ltd.), 60 parts by mass of the piperazine salt, and 5 parts by mass of zinc oxide type 1 (manufactured by Mitsui Mining & Smelting Co., Ltd.) were pulverized using a compact jet mill pulverizer (Cojet System α-mkIII, manufactured by Seishin Enterprise Co., Ltd.) under 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 input 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 mixer and heated to 150 °C in a heating oven. After allowing to cool to room temperature, 0.3 parts by mass of butyl stearate was mixed using a food mixer to obtain Composition A2.

[0131] <Preparation of Composition A3> 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 pulverized using a compact jet mill pulverizer (Cojet System α-mkIII, manufactured by Seishin Enterprise Co., Ltd.) under 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 input 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 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.

[0132] <Preparation of Composition A4> 40 parts by weight of the melamine salt, 60 parts by weight of the piperazine salt, and 5 parts by weight of zinc oxide type 1 (manufactured by Mitsui Mining & Smelting Co., Ltd.) were pulverized using a compact jet mill pulverizer (Cojet System α-mkIII, manufactured by Seishin Enterprise Co., Ltd.) under 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 input rate of 100 g / h. This mixture was mixed with 1 part by weight 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. After allowing to cool to room temperature, 0.2 parts by weight of bis[2-(2-butoxyethoxy)ethyl] adipate was mixed using a food mixer to obtain Composition A4.

[0133] <Preparation of Composition A5> 40 parts by mass of the melamine salt and 60 parts by mass of the piperazine salt were pulverized using a compact jet mill pulverizer (Cojet System α-mkIII, manufactured by Seishin Enterprise Co., Ltd.) under 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 input rate of 100 g / h. This mixture was mixed with 1 part by mass of 3-glycidoxypropyltrimethoxysilane (KBM-403, manufactured by Shin-Etsu Chemical Co., Ltd.) using a food mixer and heated to 150°C in a heating oven. After allowing to cool to room temperature, 0.2 parts by mass of bis[2-(2-butoxyethoxy)ethyl] adipate was mixed using a food mixer to obtain Composition A5.

[0134] <Preparation of Composition A6> 40 parts by mass of the melamine salt, 60 parts by mass of the piperazine salt, and 5 parts by mass of zinc oxide type 1 (manufactured by Mitsui Mining & Smelting Co., Ltd.) were pulverized using a compact jet mill pulverizer (Cojet System α-mkIII, manufactured by Seishin Enterprise Co., Ltd.) under 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 input rate of 100 g / h. This mixture was then mixed with 1 part by mass of 3-glycidoxypropyltrimethoxysilane (KBM-403, manufactured by Shin-Etsu Chemical Co., Ltd.) using a food mixer and heated to 150°C in a heating oven. After allowing to cool to room temperature, 0.2 parts by mass of polyethylene glycol (300) dioctylate was mixed using a food mixer to obtain Composition A6.

[0135] <Preparation of Composition A7> 35 parts by weight of the melamine salt, 5 parts by weight of melamine polyphosphate (PMP100, manufactured by Nissan Chemical Co., Ltd.), and 60 parts by weight of the piperazine salt were pulverized using a compact jet mill pulverizer (Cojet System α-mkIII, manufactured by Seishin Enterprise Co., Ltd.) under 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 input rate of 100 g / h. This mixture was then mixed with 1 part by weight 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. After allowing to cool to room temperature, 0.2 parts by weight of polyethylene glycol (300) dioctylate was mixed using a food mixer to obtain Composition A7.

[0136] <Preparation of Composition A8> 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 (for 2 minutes) using a food mixer to obtain Composition A8.

[0137] <Preparation of Composition A9> Composition A9 was obtained by mixing and pulverizing (for 2 minutes) using a food mixer 60 parts by weight of ammonium polyphosphate (Exolit AP422, manufactured by Clariant), 20 parts by weight of aluminum diethylphosphinate (Exolit OP1230, manufactured by Clariant), 20 parts by weight of poly-[2,4-(piperazin-1,4-yl)-6-(morpholin-4-yl)-1,3,5-triazine], and 0.2 parts by weight of stearic acid.

[0138] <Preparation of Composition A10> 60 parts by mass of the above piperazine salt and 40 parts by mass of melamine polyphosphate (PMP100, manufactured by Nissan Chemical Industries, Ltd.) were pulverized using a compact jet mill pulverizer (Cojet System α-mkIII, manufactured by Seishin Enterprise Co., Ltd.) under 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 input rate of 100 g / h, and 0.2 parts by mass of stearic acid were mixed using a food mixer to obtain composition A10.

[0139] <Preparation of Composition A11> 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 pulverized using a compact jet mill pulverizer (Cojet System α-mkIII, manufactured by Seishin Enterprise Co., Ltd.) under 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, and 0.2 parts by mass of stearic acid were mixed using a food mixer to obtain composition A11.

[0140] <Preparation of Composition B1> 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 pulverized using a compact jet mill pulverizer (Cojet System α-mkIII, manufactured by Seishin Enterprise Co., Ltd.) under 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 input 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 mixer and heated to 150°C in a heating oven to obtain composition B1.

[0141] <Preparation of Composition B2> 35 parts by mass of the above melamine salt, 5 parts by mass of melamine polyphosphate (PMP100, manufactured by Nissan Chemical Industries, Ltd.), 60 parts by mass of the above piperazine salt, and 5 parts by mass of zinc oxide type 1 (manufactured by Mitsui Mining and Smelting Co., Ltd.) were pulverized using a compact jet mill pulverizer (Cojet System α-mkIII, manufactured by Seishin Enterprise Co., Ltd.) under 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 input 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 mixer and heated to 150°C in a heating oven to obtain composition B2.

[0142] <Preparation of Composition B3> 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 pulverized using a compact jet mill pulverizer (Cojet System α-mkIII, manufactured by Seishin Enterprise Co., Ltd.) under 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 input 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 mixer and heated to 150°C in a heating oven to obtain composition B3.

[0143] <Preparation of Composition B4> 40 parts by mass of the melamine salt, 60 parts by mass of the piperazine salt, and 5 parts by mass of zinc oxide type 1 (manufactured by Mitsui Mining & Smelting Co., Ltd.) were pulverized using a compact jet mill pulverizer (Cojet System α-mkIII, manufactured by Seishin Enterprise Co., Ltd.) under 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 input 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 mixer, and the mixture was heated to 150°C in a heating oven to obtain composition B4.

[0144] <Preparation of Composition B5> 40 parts by mass of the melamine salt and 60 parts by mass of the piperazine salt were pulverized using a compact jet mill pulverizer (Cojet System α-mkIII, manufactured by Seishin Enterprise Co., Ltd.) under 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 input 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 mixer and heated to 150°C in a heating oven to obtain composition B5.

[0145] <Preparation of Composition B6> 40 parts by mass of the melamine salt, 60 parts by mass of the piperazine salt, and 5 parts by mass of zinc oxide type 1 (manufactured by Mitsui Mining & Smelting Co., Ltd.) were pulverized using a compact jet mill pulverizer (Cojet System α-mkIII, manufactured by Seishin Enterprise Co., Ltd.) under 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 input 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 mixer and heated to 150°C in a heating oven to obtain composition B6.

[0146] <Preparation of Composition B7> 35 parts by mass of the above melamine salt, 5 parts by mass of melamine polyphosphate (PMP100, manufactured by Nissan Chemical Industries, Ltd.), and 60 parts by mass of the above piperazine salt were pulverized using a compact jet mill pulverizer (Cojet System α-mkIII, manufactured by Seishin Enterprise Co., Ltd.) under 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 input 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 mixer, and the mixture was heated to 150°C in a heating oven to obtain composition B7.

[0147] <Preparation of Composition B8> 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.

[0148] <Preparation of Composition B9> 40 parts by mass of the melamine salt and 60 parts by mass of the piperazine salt were ground for 2 minutes using a food mixer, and then 1 part by mass of 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane (Sila-Ace S530, manufactured by JNC Corporation) was mixed using a food mixer, and the mixture was heated to 150° C. in a heating oven. After allowing to cool to room temperature, 0.3 parts by mass of bis[2-(2-butoxyethoxy)ethyl] adipate was mixed using a food mixer to obtain composition B9.

[0149] <Preparation of Composition B10> 100 parts by mass of composition B1 was pulverized using a compact jet mill pulverizer (Cojet System α-mkIII, manufactured by Seishin Enterprise Co., Ltd.) under 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 input 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 mixer, and the mixture was heated to 150°C in a heating oven to obtain composition B10.

[0150] The flame retardant composition obtained as above was measured for the following measurement items. The measurement results and values ​​calculated from the measurement results based on formula (I) are shown in Tables 1 to 3.

[0151] <Loose bulk density measurement> Using a powder property evaluation device (Multitester MT-02, manufactured by Seishin Enterprise Co., Ltd.), a powder with a diameter of 5 cm and a volume of 100 cm was measured. 3 The loose bulk density of the resulting flame retardant composition was measured using a cylindrical container.

[0152] The sample was gently filled into the container until it was heaped up, and the excess sample above the container surface was scraped off, and the weight of the sample loosely packed in the container was measured. At this time, the loose bulk density (g / cm 3 ) is calculated by dividing the weight of the sample loosely packed in the container (g) by 100 (cm 3 ) was calculated.

[0153] <Measurement of particle size distribution> Cumulative 10% particle size 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 ultrasonically, and the particle size distribution was measured under wet conditions using a laser diffraction / scattering particle size distribution analyzer (Microtrac MT3000II, manufactured by Microtrac Bell Co., Ltd.).

[0154] The flame retardant compositions thus obtained were evaluated for the following items. The evaluation results are shown in Tables 1 to 3.

[0155] <Evaluation of dust scattering> As shown in Figure 1, a transparent acrylic cylinder 10 (outer diameter: 110 mm, inner diameter: 98 mm, length: 500 mm) with only one open end was erected so that the top was open, and three sides were surrounded by black acrylic plates 11. 10 g of the flame retardant composition obtained above was weighed and allowed to fall freely from the opening at the top of the cylinder 10, and the scattered dust was captured with a video camera. An image was taken from the captured video 5 seconds after the powder contacted the bottom, and the luminance, as defined by the HLS color space, of a portion 12 approximately 150 mm from the bottom of the cylinder was extracted from the image. Furthermore, the luminance when a standard white plate (X 94.62, Y 99.79, Z 106.92 (SCI method)) was placed in portion 12 was also extracted, along with the luminance before the flame retardant composition was dropped. The degree of dust scattering was calculated using the following formula (III).

[0156] TIFF0007813724000008.tif15153In formula (III), (Sample) represents the luminance of part 12 when the flame retardant composition is dropped, (White) represents the luminance of part 12 when a standard white plate is placed on part 12, and (Black) represents the luminance of part 12 before the flame retardant composition is dropped.

[0157] The smaller the value calculated by formula (III), the smaller the dust scattering property of the flame retardant composition. If this value is 30 or more, the dust will adversely affect the working environment when the flame retardant composition is supplied to a mixer or a processing machine. These values ​​are shown in Tables 1 to 3 as evaluation values ​​of dust scattering property.

[0158] <Evaluation of angle of repose> The flame retardant composition was poured onto a disk using a funnel, and the angle at which it remained stable without spontaneously collapsing was measured as the angle of repose (°). The lower this value, the better the flowability of the flame retardant composition.

[0159] If the angle of repose is 60° or more, clogging of the hopper or feeder when processing the flame retardant composition is likely to occur, which is undesirable.

[0160] <Preparation of test specimens for flame retardancy evaluation> A flame-retardant resin composition was obtained by blending 100 parts by weight of polypropylene (melt flow rate (JIS K7210, load 2.16 kg, temperature 230°C) = 14 g / 10 min) with 0.1 parts by weight of calcium stearate (neutralizer), 0.1 parts by weight of tetrakis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)methylpropionate]methane (phenolic antioxidant), and 0.1 parts by weight of tris(2,4-di-tert-butylphenyl)phosphite (phosphorus antioxidant). 54 parts by weight of the flame retardant compositions (A1 to A11, B1 to B10) were blended with this polypropylene resin composition. The resulting flame-retardant resin composition was melt-kneaded in a twin-screw extruder (TEX28V, manufactured by The Japan Steel Works, Ltd.) at a cylinder 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 in an injection molding machine (EC60NII-1.5A, manufactured by Toshiba Machine Co., Ltd.) under conditions of a cylinder temperature of 220°C and a mold temperature of 40°C to obtain test pieces measuring 127mm x 12.7mm x 1.6mm.

[0161] <Flame retardancy evaluation> The obtained test pieces were subjected to a flame retardancy evaluation test in accordance with the UL-94V standard.

[0162] 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 edge for 10 seconds. The flame was then removed and the time for the flame to extinguish on the test specimen was measured. Next, as soon as the flame went out, a second flame application was started for 10 seconds, and the time for the flame to extinguish was measured in the same manner as the first. At the same time, an evaluation was also made to see whether the cotton underneath the test specimen would ignite due to the falling embers.

[0163] Flammability ratings were assigned according to the UL-94V standard based on factors such as the first and second burning times and whether or not the cotton ignited. V-0 is the highest flammability rating, with V-1 and V-2 representing decreasing flame retardancy. However, items that did not fall into any of the V-0 to V-2 ratings were rated NR.

[0164] [Table 1]

[0165] [Table 2]

[0166] [Table 3]

[0167] With regard to flame retardancy, all of Examples 1 to 11 and Comparative Examples 1 to 10 were good.

[0168] 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 ​​higher than 30, which was found to be at a level that would adversely affect the working environment.

[0169] Furthermore, in the evaluation of the angle of repose, Examples 1 to 11 were good, but Comparative Examples 8 to 10 showed values ​​higher than 60°, indicating that they were poor in terms of powder fluidity.

[0170] From the above, it has been demonstrated that the flame retardant composition of the present invention has good powder flowability, little dust scattering, and exhibits good flame retardant performance. [Explanation of symbols]

[0171] 10 tubes 11 Acrylic board 12. The area approximately 150 mm from the bottom of the tube

Claims

1. A flame retardant composition containing one or more phosphate compounds represented by the following general formula (1) or the following general formula (2): The loose bulk density of the flame retardant composition is d (g / cm ３ ), The cumulative 10% particle size in the volume-based particle size distribution of the flame retardant composition is D １０ (μm), cumulative 50% particle diameter is D ５０ (μm), d, D １０ and D ５０ A flame retardant composition characterized in that the following formula (I) is satisfied: 0.030≦d / (D ５０ -D １０ )≦0.110 ・・・(I) In the 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 represents a number satisfying 0<p≦n1+2. In general formula (1-A), Z １ and Z ２ are each independently -NR １１ R １２ R represents 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; １１ and R １２ each independently represents a hydrogen atom, a linear or branched alkyl group having 1 to 6 carbon atoms, or a methylol group. In the general formula (2), n2 represents a number from 1 to 100, and Y １ is [R ２１ R ２２ N (CH ２ ) 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, and q is a number satisfying 0<q≦n2+2.

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

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

4. Y １ 3. The flame retardant composition according to claim 1, wherein the phosphate compound represented by the general formula (2) is piperazine.

5. X １ 3. The flame retardant composition according to claim 1, wherein the phosphate compound represented by the general formula (1) is ammonia.

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

7. the phosphate compound represented by the general formula (1) in which n1 is 2; the phosphate compound represented by the general formula (2) in which n2 is 2; The flame retardant composition according to any one of claims 1 to 6, comprising:

8. The flame retardant composition according to any one of claims 1 to 7, A thermoplastic resin, A flame-retardant resin composition comprising:

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

10. A molded article obtained by using the flame-retardant resin composition according to claim 9.

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