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

Abstract

Provided are: a flame retardant composition that yields a flame-resistant synthetic resin composition having superior flame resistance and a superior balance between vertical and horizontal mold shrinkage; a flame-resistant synthetic resin composition in which said flame retardant composition is used; and a molded article thereof.　The flame retardant composition contains 0.005–5 parts by mass of component (B) per 100 parts by mass of component (A).　Component (A): A phosphate flame retardant.　Component (B): One or more types of compound having a structure represented by general formula (1). In the formula, R1–R4 each independently represents a hydrogen atom or an alkyl group comprising 1–8 carbon atoms, R5 represents a direct linkage or an alkanediyl group comprising 1–4 carbon atoms; and M1 represents any of an alkali metal, an alkaline earth metal, zinc, aluminum, and a hydrogen atom. When M1 is an alkali metal or a hydrogen atom, n is 1 and m is 0. When M1 is an alkaline earth metal or zinc, n is 2 and m is 0. When M1 is aluminum, n is 1, 2, or 3 and m is an integer represented by 3–n.

Description

[Technical field]

[0001] The present invention relates to a flame retardant composition capable of obtaining a flame retardant synthetic resin composition (hereinafter, also simply referred to as a "resin composition") having excellent flame retardancy and excellent shrinkage balance during molding, a flame retardant synthetic resin composition using the same, and a molded article thereof. [Background technology]

[0002] Synthetic resins have the advantages of being excellent in moldability, heat resistance, and mechanical properties, as well as low specific gravity and light weight, and therefore have traditionally been widely used in building materials, automobile parts, packaging materials, agricultural materials, housing materials for home appliances, toys, and the like.

[0003] However, many synthetic resins are flammable, and flame retardancy is essential depending on the application. In particular, highly flammable synthetic resins such as polyolefin resins are widely used in a wide range of fields, so it is essential to add flame retardants to these resins to make them flame-retardant.

[0004] There are various types of flame retardants for synthetic resins, and intumescent flame retardants, mainly composed of salts of polyphosphoric acid or pyrophosphoric acid and nitrogen-containing compounds, are known as excellent flame retardants that form a surface intumescent layer during combustion and suppress the diffusion and heat transfer of decomposition products, thereby making synthetic resins flame-retardant. Such flame retardants are described in Patent Document 1, for example.

[0005] In addition, in order to improve the powder characteristics and processability of this intumescent flame retardant, as well as the physical properties of the resin when it is blended with a resin, the addition of higher aliphatic carboxylic acid esters, silicone oils, silane coupling agents, and the like have been proposed (Patent Documents 2 to 4). [Prior art documents] [Patent documents]

[0006] [Patent Document 1] US Patent Publication No. 2003 / 0088000 [Patent Document 2] US Patent Publication No. 2005 / 0256234 [Patent Document 3] US Patent Publication No. 2007 / 0176154 [Patent Document 4] JP 2008-208269 A Summary of the Invention [Problem to be solved by the invention]

[0007] In the injection molding of synthetic resins, the volume of the molten resin filled inside the mold shrinks when it cools and solidifies. This molding shrinkage phenomenon is generally used to obtain a molded product of the desired dimensions by making the dimensions of the mold cavity slightly larger to accommodate the shrinkage.

[0008] However, when the above-mentioned flame retardant is blended with a synthetic resin and injection-molded, there is a problem that the mold shrinkage rate in the MD direction (the direction in which the resin flows in the mold) is larger than that in the TD direction (the direction perpendicular to the MD direction). Therefore, the balance of the vertical and horizontal mold shrinkage rates of a molded product containing the above-mentioned flame retardant is changed compared to a molded product not containing the above-mentioned flame retardant, and it is difficult to obtain a molded product with the shape as originally designed in the mold.

[0009] In order to solve the above problems, the present invention aims to provide a flame retardant composition which can give a flame-retardant synthetic resin composition having excellent longitudinal and transverse balance of flame retardancy and mold shrinkage rate, a flame-retardant synthetic resin composition using the same, and a molded article thereof. [Means for solving the problem]

[0010] The present inventors conducted extensive research to solve the above problems and have now completed the present invention.

[0011] That is, the flame retardant composition of the present invention contains the following component (B) in an amount of 0.005 to 5 parts by mass per 100 parts by mass of the following component (A): The component (A) contains the following components (A-1) and (A-2), and The mass ratio of the component (A-1) to the component (A-2) is 30:70 to 45:55. (A) Component: Phosphate-based flame retardant. Component (B): one or more compounds having a structure represented by the following general formula (1): TIFF0007671277000001.tif59157In the above general formula (1), R 1 , R 2 , R 3 and R 4 each independently represents a hydrogen atom or an alkyl group having 1 to 8 carbon atoms; R 5 represents a direct bond or an alkanediyl group having 1 to 4 carbon atoms; M 1 represents lithium or aluminum, M 1 For lithium, n is 1 and m is 0, and M 1 When is aluminum, n is 1, 2, or 3, and m is an integer expressed as 3-n. Component (A-1): one or more melamine salts selected from the group consisting of melamine orthophosphate, melamine pyrophosphate, and melamine polyphosphate. Component (A-2): at least one piperazine salt selected from the group consisting of piperazine orthophosphate, piperazine pyrophosphate, and piperazine polyphosphate.

[0012] In the flame retardant composition of the present invention, it is preferable that the component (A) further contains the following component (A-3). Component (A-3): one or more ammonium salts selected from the group consisting of ammonium orthophosphate, ammonium pyrophosphate, and ammonium polyphosphate.

[0013] The flame retardant composition of the present invention preferably further contains at least one selected from a filler, a fatty acid metal salt, and a hydrotalcite as component (C). In this case, it is more preferable that the fatty acid metal salt is a compound having a structure represented by the following general formula (2). TIFF0007671277000002.tif16157In the above general formula (2), R 4 represents a group introduced from a linear or branched aliphatic organic acid having 8 to 30 carbon atoms, M 2 is a metal atom or Al(OH) 3-p and p represents an integer of 1 to 3.

[0014] Furthermore, the flame retardant composition of the present invention preferably further contains, as component (E), at least one selected from the group consisting of silicone oil, epoxy coupling agents, and lubricants, in an amount of 0.01 to 5 parts by mass per 100 parts by mass of component (A).

[0015] The flame-retardant synthetic resin composition of the present invention is a flame-retardant synthetic resin composition containing a synthetic resin and the above-mentioned flame retardant composition, It is characterized by satisfying the relationships represented by the following formulas (i) and (ii). (i) 0.935≦ΔTD / ΔTD B ≦1.065 (ii) 0.860≦(ΔTD / ΔMD) / (ΔTD B / ΔMD B )≦1.140 In the above formula, ΔMD is the shrinkage rate of the molded article obtained by injection molding the flame-retardant synthetic resin composition in the MD direction, which is the direction in which the resin flows in the mold cavity during injection molding, and ΔTD is the shrinkage rate of the molded article obtained by injection molding the flame-retardant synthetic resin composition in the TD direction, which is the direction perpendicular to the MD direction. B is the shrinkage rate in the MD direction of a molded article obtained by injection molding a synthetic resin composition having a composition obtained by excluding the flame retardant composition from the flame retardant synthetic resin composition, and ΔTD Bis the shrinkage rate in the TD direction of a molded article obtained by injection molding the synthetic resin composition.

[0016] The molded article of the present invention is characterized by being obtained by molding the above-mentioned flame-retardant synthetic resin composition. Effect of the Invention

[0017] According to the present invention, it is possible to provide a flame retardant composition which can give a flame retardant synthetic resin composition having an excellent balance between flame retardancy and shrinkage during molding, a flame retardant synthetic resin composition using the same, and a molded article thereof. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0018] The present invention relates to a flame retardant composition, a flame retardant synthetic resin composition, and a molded article.

[0019] <Flame retardant composition> The flame retardant composition of the present invention contains as essential components a phosphate-based flame retardant as component (A) and one or more compounds having a structure represented by general formula (1) as component (B).

[0020] (Component (A)) The phosphate-based flame retardant used as component (A) in the flame retardant composition of the present invention contains phosphoric acids.

[0021] The phosphoric acid used in the phosphate-based flame retardant is not particularly limited, and examples thereof include various phosphoric acids such as orthophosphoric acid, pyrophosphoric acid, and polyphosphoric acid. In the present invention, the polyphosphoric acid is what is called condensed phosphoric acid, and examples thereof include linear polyphosphoric acid and cyclic polymetaphosphoric acid. The condensation degree of polyphosphoric acid is 3 or more.

[0022] Examples of the phosphate-based flame retardants include phosphates consisting of salts of the various phosphoric acids and at least one metal or compound selected from metals of Groups 1 to 14 of the periodic table, ammonia, aliphatic amines, and aromatic amines.

[0023] Examples of the metals in Groups 1 to 14 of the periodic table include lithium, sodium, calcium, barium, iron (II), iron (III), aluminum, and zinc.

[0024] Examples of the aliphatic amine include methylamine, ethylamine, diethylamine, triethylamine, ethylenediamine, and piperazine.

[0025] Furthermore, examples of the aromatic amine include pyridine, pyrazine, pyridazine, pyrimidine, triazine, melamine, melam, and melem.

[0026] The above-mentioned phosphate-based flame retardants may be subjected to a known water resistance improving treatment such as a silane coupling agent treatment or coating with a melamine resin, and may also be added with a known foaming assistant such as melamine, melamine cyanurate, or pentaerythritol.

[0027] Specific examples of the phosphate-based flame retardant include orthophosphate, pyrophosphate, polyphosphate, and the like.

[0028] Examples of the orthophosphate salt include, but are not limited to, ammonium salts such as ammonium phosphate, ammonium dihydrogen phosphate, and diammonium hydrogen phosphate; sodium salts such as monosodium phosphate, disodium phosphate, trisodium phosphate, monosodium phosphite, disodium phosphite, and sodium hypophosphite; potassium salts such as monopotassium phosphate, dipotassium phosphate, tripotassium phosphate, monopotassium phosphite, dipotassium phosphite, and potassium hypophosphite; lithium salts such as monolithium phosphate, dilithium phosphate, trilithium phosphate, monolithium phosphite, dilithium phosphite, and lithium hypophosphite; barium salts such as barium dihydrogen phosphate, barium hydrogen phosphate, tribarium phosphate, and barium hypophosphite; magnesium salts such as monohydrogen magnesium phosphate, magnesium hydrogen phosphate, trimagnesium phosphate, and magnesium hypophosphite; calcium salts such as calcium dihydrogen phosphate, calcium hydrogen phosphate, tricalcium phosphate, and calcium hypophosphite; zinc salts such as zinc phosphate, zinc phosphite, and zinc hypophosphite; and amine salts such as piperazine phosphate and melamine phosphate.

[0029] The pyrophosphate salt is not particularly limited, but examples thereof include ammonium pyrophosphate, piperazine pyrophosphate, melamine pyrophosphate, and aluminum pyrophosphate.

[0030] Furthermore, the polyphosphate salt is not particularly limited, but examples thereof include ammonium polyphosphate, piperazine polyphosphate, melamine polyphosphate, aluminum polyphosphate, and the like.

[0031] The above phosphate-based flame retardants may be used alone or in combination of two or more.

[0032] From the viewpoints of flame retardancy and heat resistance, the phosphate-based flame retardant of the component (A) preferably contains at least one of the following components (A-1), (A-2) and (A-3). Component (A-1): one or more melamine salts selected from the group consisting of melamine orthophosphate, melamine pyrophosphate, and melamine polyphosphate. Component (A-2): at least one piperazine salt selected from the group consisting of piperazine orthophosphate, piperazine pyrophosphate, and piperazine polyphosphate. Component (A-3): one or more ammonium salts selected from the group consisting of ammonium orthophosphate, ammonium pyrophosphate, and ammonium polyphosphate.

[0033] In the component (A) according to the present invention, the melamine salt used as the component (A-1) is selected from the group consisting of melamine orthophosphate, melamine pyrophosphate, and melamine polyphosphate, which may be used alone or in a mixture. Among these, from the viewpoints of flame retardancy, handling properties, and storage stability, melamine pyrophosphate or melamine polyphosphate is preferred, and melamine pyrophosphate is particularly preferred. When using these in a mixture, the higher the content of melamine pyrophosphate, the more preferred.

[0034] These salts of phosphoric acids and melamine can also be obtained by reacting the corresponding phosphoric acids or salts of phosphoric acids with melamine, but the melamine salt used as component (A-1) in the present invention is preferably melamine pyrophosphate or melamine polyphosphate obtained by thermal condensation of melamine orthophosphate, and in particular, melamine pyrophosphate is preferred.

[0035] In the (A) component of the present invention, the piperazine salt used as the (A-2) component is selected from the group consisting of piperazine orthophosphate, piperazine pyrophosphate and piperazine polyphosphate, and these may be used alone or in a mixture. Among these, from the viewpoints of flame retardancy, handling and storage stability, piperazine pyrophosphate is preferred, and when used in a mixture, the higher the content of piperazine pyrophosphate, the more preferred.

[0036] These salts of phosphoric acids and piperazine can be obtained by reacting the corresponding phosphoric acids or salts of phosphoric acids with piperazine, respectively. However, the piperazine salt used as component (A-2) according to the present invention is preferably piperazine pyrophosphate or piperazine polyphosphate obtained by thermal condensation of piperazine diphosphate, and particularly preferably piperazine pyrophosphate.

[0037] In the component (A) according to the present invention, the ammonium salt used as component (A-3) is selected from the group consisting of ammonium orthophosphate, ammonium pyrophosphate, and ammonium polyphosphate, which may be used alone or in combination.

[0038] In addition, since the above-mentioned ammonium salt alone is easily hydrolyzed, it is also possible to suitably use the above-mentioned ammonium salt coated or microencapsulated with a thermosetting resin, or the above-mentioned ammonium salt particles coated with a melamine monomer or other nitrogen-containing organic compounds, or to use ammonium salts treated with a surfactant, a silane coupling agent, or a silicon compound such as silicone oil, or ammonium salts made insoluble by adding melamine or the like during the production process of the above-mentioned ammonium salt.

[0039] From the standpoint of flame retardancy, the component (A) according to the present invention particularly preferably contains the components (A-1) and (A-2).

[0040] When the component (A) according to the present invention contains the components (A-1) and (A-2), the content ratio of the components (A-1) and (A-2) in terms of mass ratio of the components (A-1) and (A-2) is preferably from 20:80 to 50:50, and more preferably from 30:70 to 45:55, from the viewpoint of flame retardancy.

[0041] ((B) component) The component (B) in the flame retardant composition of the present invention is a compound having a structure represented by the following general formula (1). TIFF0007671277000003.tif59157In the above general formula (1), R 1 , R2 , R 3 and R 4 each independently represents a hydrogen atom or an alkyl group having 1 to 8 carbon atoms; R 5 represents a direct bond or an alkanediyl group having 1 to 4 carbon atoms; M 1 represents any one of an alkali metal, an alkaline earth metal, zinc, aluminum, and a hydrogen atom; M 1 is an alkali metal or hydrogen atom, n is 1 and m is 0, and M 1 is an alkaline earth metal or zinc, n is 2 and m is 0, and M 1 When is aluminum, n is 1, 2, or 3, and m is an integer expressed as 3-n.

[0042] In the above general formula (1), R 1 , R 2 , R 3 and R 4 Examples of the alkyl group having 1 to 8 carbon atoms represented by the formula (1) include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, a sec-butyl group, a tert-butyl group, a pentyl group, a tert-pentyl group, a hexyl group, a heptyl group, an octyl group, a 2-ethylhexyl group, a tert-octyl group, etc. Among these, from the viewpoint of the effects of the present invention, an alkyl group having 1 to 5 carbon atoms is preferred, and a tert-butyl group is particularly preferred.

[0043] In the above general formula (1), R 5 Examples of the alkanediyl group having 1 to 4 carbon atoms represented by the formula (1) include a methanediyl group, an ethane-1,1-diyl group, a propane-1,1-diyl group, a propane-2,2-diyl group, a butane-1,1-diyl group, a butane-2,2-diyl group, etc. Among these, from the viewpoint of the effects of the present invention, a methanediyl group or an ethane-1,1-diyl group is preferred.

[0044] In the above general formula (1), M 1represents any one of an alkali metal, an alkaline earth metal, zinc, aluminum, and a hydrogen atom, and examples of the alkali metal include sodium, potassium, and lithium, and examples of the alkaline earth metal include magnesium, calcium, strontium, barium, etc. Among these, from the viewpoint of the effects of the present invention, sodium, lithium, magnesium, calcium, or aluminum is preferred, and sodium, lithium, or aluminum is particularly preferred.

[0045] The component (B) according to the present invention may use one type alone or two or more types in combination.

[0046] In the component (B) according to the present invention, M in the above general formula (1) 1 Specific examples of when is an alkali metal include the following compounds No. 1 to No. 8. However, the component (B) according to the present invention is not limited to these compounds.

[0047] TIFF0007671277000004.tif96166

[0048] In addition, M in the above general formula (1) 1 Specific examples of compounds in which is an alkaline earth metal include the following compounds No. 9 to No. 12. However, the component (B) according to the present invention is not limited to these compounds.

[0049] TIFF0007671277000005.tif48166TIFF0007671277000006.tif49161

[0050] Furthermore, M in the above general formula (1) 1 Specific examples of compounds in which is aluminum include the following compounds No. 13 to No. 17. However, the component (B) according to the present invention is not limited to these compounds.

[0051] TIFF0007671277000007.tif97166

[0052] Furthermore, M in the above general formula (1) 1 Specific examples of compounds in which is a hydrogen atom include the following compounds No. 18 to No. 20. However, the component (B) of the present invention is not limited to these compounds.

[0053] TIFF0007671277000008.tif49161

[0054] The component (B) according to the present invention has the effect of bringing the ratio of the longitudinal / lateral balance of the molding shrinkage rate between the flow direction (MD) of the resin and the direction perpendicular to the flow direction (TD) during injection molding of the resin composition closer to 1, thereby suppressing warping and deformation of the molded article.

[0055] From the viewpoint of the balance between flame retardancy and shrinkage during molding, the content of the (B) component in the flame retardant composition of the present invention is preferably 0.005 to 5 parts by mass, more preferably 0.01 to 3 parts by mass, and even more preferably 0.05 to 1 part by mass, relative to 100 parts by mass of the (A) component.

[0056] ((C) component) From the viewpoint of further improving the effects of the present invention, the flame retardant composition of the present invention preferably further contains, as component (C), at least one selected from fillers, fatty acid metal salts, and hydrotalcites.

[0057] Examples of the filler 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, silica, alumina, potassium titanate whisker, wollastonite, fibrous magnesium oxysulfate, and hydrotalcite, and the particle size, and in the case of fibrous form, the fiber diameter, fiber length, and aspect ratio can be appropriately selected and used. These may be used alone or in combination of two or more. In addition, the filler may be surface-treated as necessary.

[0058] When a filler is added, the amount added can be adjusted to be preferably 1 to 80 parts by mass, more preferably 3 to 50 parts by mass, and even more preferably 5 to 40 parts by mass, per 100 parts by mass of the synthetic resin.

[0059] The fatty acid metal salt may be a compound having a structure represented by the following general formula (2). TIFF0007671277000009.tif16157In the above general formula (2), R 4 represents a group introduced from a linear or branched aliphatic organic acid having 8 to 30 carbon atoms, M 2 is a metal atom or Al(OH) 3-p and p represents an integer of 1 to 3.

[0060] In the above general formula (2), R 4 Examples of the group introduced from an aliphatic organic acid having 8 to 30 carbon atoms, represented by the formula (1), include hydrocarbon groups such as an alkyl group having 7 to 29 carbon atoms, an alkenyl group, and an alkyl group having two or more unsaturated bonds introduced therein. These may be substituted with a hydroxyl group, and may be linear or branched.

[0061] Specific examples of the fatty acid metal salt include metal salts of saturated fatty acids such as caprylic acid, 2-ethylhexanoic acid, pelargonic acid, capric acid, undecylic acid, lauric acid, tridecylic acid, myristic acid, pentadecylic acid, palmitic acid, margaric acid, stearic acid, nonadecylic acid, arachidic acid, heicosyl acid, behenic acid, tricosyl acid, lignoceric acid, cerotic acid, montanic acid, melissic acid, and 12-hydroxystearic acid; metal salts of linear unsaturated fatty acids such as 4-decenoic acid, 4-dodecenoic acid, palmitoleic acid, α-linolenic acid, linoleic acid, γ-linolenic acid, stearidonic acid, petroselinic acid, oleic acid, elaidic acid, vaccenic acid, eicosapentaenoic acid, docosapentaenoic acid, and docosahexaenoic acid; and metal salts of aromatic fatty acids such as trimesic acid. In the flame retardant composition of the present invention, the fatty acid metal salt may be R 4The hydrocarbon group represented by the formula (I) preferably has 9 to 21 carbon atoms, and in particular, metal salts of saturated fatty acids such as lauric acid, myristic acid, stearic acid, palmitic acid, and 12-hydroxystearic acid are preferred because they provide a remarkable effect to the composition of the present invention.

[0062] In the above general formula (2), M 2 Examples of the metal atom represented by the formula (I) include an alkali metal atom, an alkaline earth metal atom, a transition metal atom, and a base metal atom. In the composition of the present invention, an alkali metal atom such as sodium, lithium, or potassium is preferred because it enhances the effect of the present invention.

[0063] When a fatty acid metal salt is added, the amount is preferably adjusted to 0.0005 to 5 parts by mass, and particularly 0.001 to 3 parts by mass, per 100 parts by mass of the synthetic resin.

[0064] The hydrotalcites are known as natural or synthetic compounds, and are complex salt compounds consisting of magnesium, aluminum, hydroxyl groups, carbonate groups, and any water of crystallization. Examples of the hydrotalcites include those in which a part of the magnesium or aluminum is replaced with other metals such as alkali metals or zinc, and those in which the hydroxyl groups and carbonate groups are replaced with other anion groups. Specific examples of the hydrotalcites include those in which the metal of the hydrotalcite having the structure represented by the following general formula (3) is replaced with an alkali metal. In addition, compounds having the structure represented by the following general formula (4) can also be used as Al-Li hydrotalcites.

[0065] In the above general formula (3), x1 and x2 are each represented by the following formula: 0≦x2 / x1<10, 2≦x1+x2≦20 represents the number that satisfies the condition expressed by, and q represents 0 or a positive number.

[0066] TIFF0007671277000011.tif11161In the above general formula (4), A r-represents an anion with a valence of r, and q represents 0 or a positive number.

[0067] In addition, the carbonate anions in these hydrotalcites may be partially substituted with other anions.

[0068] The hydrotalcites may be those from which water of crystallization has been dehydrated, or may be those coated with a higher fatty acid such as stearic acid, a higher fatty acid metal salt such as an alkali metal salt of oleic acid, an organic sulfonic acid metal salt such as an alkali metal salt of dodecylbenzenesulfonic acid, a higher fatty acid amide, a higher fatty acid ester, a wax, or the like.

[0069] The hydrotalcites may be natural products or synthetic products. Methods for synthesizing hydrotalcites include known methods described in JP-B-46-2280, JP-B-50-30039, JP-B-51-29129, JP-B-3-36839, JP-A-61-174270, and JP-A-5-179052. Hydrotalcites can be used without being limited by their crystal structure or crystal particles. These may be used alone or in combination of two or more.

[0070] When hydrotalcites are blended, the blending amount is preferably adjusted to 0.001 to 5 parts by mass, particularly 0.01 to 3 parts by mass, per 100 parts by mass of the synthetic resin.

[0071] ((D) component) It is preferable that the flame retardant composition of the present invention further contains zinc oxide as component (D).

[0072] The zinc oxide functions as a flame retardant auxiliary. The zinc oxide may be surface-treated. As the zinc oxide, a commercially available product may be used, such as zinc oxide type 1 (manufactured by Mitsui Mining & Smelting Co., Ltd.), partially coated zinc oxide (manufactured by Mitsui Mining & Smelting Co., Ltd.), Nanofine 50 (ultrafine zinc oxide particles having an average particle size of 0.02 μm: manufactured by Sakai Chemical Industry Co., Ltd.), 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.), etc.

[0073] In the flame retardant composition of the present invention, the content of zinc oxide as the above component (D) is preferably 0.01 to 30 parts by mass, more preferably 0.5 to 10 parts by mass, and even more preferably 1 to 5 parts by mass, relative to 100 parts by mass of the component (A) from the viewpoint of flame retardancy. By setting the content of zinc oxide to 0.01 parts by mass or more, the flame retardancy becomes better. On the other hand, by setting the content of zinc oxide to 30 parts by mass or less, it is difficult to cause an adverse effect on processability.

[0074] ((E) component) It is preferable that the flame retardant composition of the present invention further contains, as component (E), at least one selected from the group consisting of silicone oil, epoxy coupling agents, and lubricants.

[0075] By including the above component (E) in the flame retardant composition of the present invention, aggregation of the flame retardant powder can be suppressed, and improvement in storage stability, dispersibility in synthetic resins, and flame retardancy can be expected.

[0076] Examples of the silicone oil include dimethyl silicone oil in which the side chains and ends of the polysiloxane are all methyl groups, methylphenyl silicone oil in which the side chains and ends of the polysiloxane are methyl groups and part of the side chains are phenyl groups, methylhydrogen silicone oil in which the side chains and ends of the polysiloxane are methyl groups and part of the side chains are hydrogen, and copolymers of these. In addition, modified silicone oils that have been amine-modified, epoxy-modified, alicyclic epoxy-modified, carboxyl-modified, carbinol-modified, mercapto-modified, polyether-modified, long-chain alkyl-modified, fluoroalkyl-modified, higher fatty acid ester-modified, higher fatty acid amide-modified, silanol-modified, diol-modified, phenol-modified and / or aralkyl-modified, in which organic groups have been introduced into part of the side chains and / or ends of these, can also be used.

[0077] Specific examples of the silicone oil include dimethyl silicone oils such as KF-96 (Shin-Etsu Chemical Co., Ltd.), KF-965 (Shin-Etsu Chemical Co., Ltd.), and KF-968 (Shin-Etsu Chemical Co., Ltd.), methyl hydrogen silicone oils such as KF-99 (Shin-Etsu Chemical Co., Ltd.), KF-9901 (Shin-Etsu Chemical Co., Ltd.), HMS-151 (Gelest Co., Ltd.), HMS-071 (Gelest Co., Ltd.), HMS-301 (Gelest Co., Ltd.), and DMS-H21 (Gelest Co., Ltd.), and examples of methyl phenyl silicone oils such as KF-50 (Shin-Etsu Chemical Co., Ltd.), KF-53 (Shin-Etsu Chemical Co., Ltd.), K Examples of the epoxy-modified products include X-22-343 (Shin-Etsu Chemical Co., Ltd.), X-22-2000 (Shin-Etsu Chemical Co., Ltd.), KF-101 (Shin-Etsu Chemical Co., Ltd.), KF-102 (Shin-Etsu Chemical Co., Ltd.), and KF-1001 (Shin-Etsu Chemical Co., Ltd.). Examples of the carboxyl-modified products include X-22-3701E (Shin-Etsu Chemical Co., Ltd.). Examples of the carbinol-modified products include X-22-4039 (Shin-Etsu Chemical Co., Ltd.) and X-22-4015 (Shin-Etsu Chemical Co., Ltd.). Examples of the amine-modified products include KF-393 (Shin-Etsu Chemical Co., Ltd.).

[0078] In the flame retardant composition of the present invention, among the silicone oils, methyl hydrogen silicone oil is preferred since it can prevent aggregation of the flame retardant powder and improve storage stability and dispersibility in synthetic resins.

[0079] The epoxy-based coupling agent has the functions of suppressing aggregation of the flame retardant powder, improving storage stability, and imparting water resistance and heat resistance. Examples of the epoxy-based coupling agent include those represented by the general formula A-(CH 2 ) k -Si(OR) 3 and a compound having an epoxy group, represented by the formula: where A is an epoxy group, k is an integer of 1 to 3, and R is a methyl group or an ethyl group. Examples of the epoxy group include a glycidoxy group and a 3,4-epoxycyclohexyl group.

[0080] Specific examples of the epoxy coupling agent include silane coupling agents having an epoxy group, such as 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, 3-glycidoxypropyltriethoxysilane, and glycidoxyoctyltrimethoxysilane.

[0081] Examples of the lubricant 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 wax); 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 and polyglycerols, silicone oils, mineral oils, etc. The lubricants can be used alone or in combination of two or more.

[0082] When the flame retardant composition of the present invention contains the above-mentioned (E) component, from the viewpoint of effectively exerting the effect of containing the (E) component, the content of the (E) component in the flame retardant composition of the present invention is preferably 0.01 to 5 parts by mass, and more preferably 0.01 to 3 parts by mass, per 100 parts by mass of the above-mentioned (A) component.

[0083] In particular, when silicone oil is contained in the flame retardant composition of the present invention, the content of the silicone oil is preferably 0.01 to 3 parts by mass, and more preferably 0.1 to 1 part by mass, per 100 parts by mass of the component (A) above, in order to enhance the above-mentioned effects due to the inclusion of the silicone oil.

[0084] In particular, when an epoxy coupling agent is contained in the flame retardant composition of the present invention, the content of the epoxy coupling agent is preferably 0.01 to 3 parts by mass, and more preferably 0.1 to 1 part by mass, relative to 100 parts by mass of the component (A) above, in order to enhance the above-mentioned effects due to the inclusion of the epoxy coupling agent.

[0085] In particular, when a lubricant is contained in the flame retardant composition of the present invention, the content of the lubricant is preferably 0.01 to 3 parts by mass, and more preferably 0.1 to 0.5 parts by mass, relative to 100 parts by mass of the component (A), in order to enhance the above-mentioned effects due to the inclusion of the lubricant.

[0086] In addition, the flame retardant composition of the present invention may contain any known resin additives within the range that does not significantly impair the effects of the present invention. As such resin additives, for example, one or more selected from phenol-based antioxidants, phosphorus-based antioxidants, thioether-based antioxidants, other antioxidants, hindered amine-based light stabilizers, ultraviolet absorbers, plasticizers, crystal nucleating agents, flame retardants other than the component (A) of the present invention, flame retardant assistants, drip prevention agents, acrylic processing assistants, antistatic agents, pigments, and dyes are used. These resin additives may be blended in advance with the flame retardant composition of the present invention, or may be blended during the preparation of the flame-retardant synthetic resin composition described below.

[0087] Examples of the phenol-based antioxidant include 2,6-di-tert-butyl-p-cresol, 2,6-diphenyl-4-octadecyloxyphenol, stearyl (3,5-di-tert-butyl-4-hydroxyphenyl)propionate, distearyl (3,5-di-tert-butyl-4-hydroxybenzyl)phosphonate, tridecyl 3,5-di-tert-butyl-4-hydroxybenzylthioacetate, thiodiethylenebis[(3,5-di-tert-butyl-4-hydroxyphenyl)propionate], 4,4'-thio Bis(6-tert-butyl-m-cresol), 2-octylthio-4,6-bis(3,5-di-tert-butyl-4-hydroxyphenoxy)-s-triazine, 2,2'-methylenebis(4-methyl-6-tert-butylphenol), ethylene bis[3,3-bis(4-hydroxy-3-tert-butylphenyl)butyrate], 4,4'-butylidenebis(2-tert-butyl-5-methylphenol), 2,2'-ethylidenebis(4,6-di-tert-butylphenol), 1,1,3-tris(2-methyl-4-hydroxy -5-tert-butylphenyl)butane, bis[2-tert-butyl-4-methyl-6-(2-hydroxy-3-tert-butyl-5-methylbenzyl)phenyl]terephthalate, 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, 1,3,5-tris[( 3,5-di-tert-butyl-4-hydroxyphenyl)propionyloxyethyl]isocyanurate, tetrakis[methylene-3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate]methane, 2-tert-butyl-4-methyl-6-(2-acryloyloxy-3-tert-butyl-5-methylbenzyl)phenol, 3,9-bis[2-{3-(3-tert-butyl-4-hydroxy-5-methylphenyl)propanoyloxy}-1,1-dimethylethyl]-2,4,8,10-tetraoxaspiro[5.5] undecane, triethylene glycol bis [β-(3-tert-butyl-4-hydroxy-5-methylphenyl) propionate], etc. These phenolic antioxidants may be used alone or in combination of two or more.

[0088] The content of the phenolic antioxidant in the flame retardant composition of the present invention can be within a range that does not impair the effects of the present invention, but the content is preferably 0.01 to 1 part by mass, and more preferably 0.03 to 0.8 parts by mass, relative to 100 parts by mass of the synthetic resin contained in the resin composition containing the flame retardant composition of the present invention.

[0089] Examples of the phosphorus-based antioxidant include triphenyl phosphite, diisooctyl phosphite, heptakis(dipropylene glycol)triphosphite, triisodecyl phosphite, diphenyl isooctyl phosphite, diisooctylphenyl phosphite, diphenyl tridecyl phosphite, triisooctyl phosphite, trilauryl phosphite, diphenyl phosphite, tris(dipropylene glycol)phosphite, diisodecyl pentaerythritol diphosphite, dioleyl hydrogen phosphite, trilauric acid phosphite, and the like. aryl trithiophosphite, bis(tridecyl)phosphite, tris(tridecyl)phosphite, diphenyldecyl phosphite, dinonylphenyl bis(nonylphenyl)phosphite, poly(dipropylene glycol)phenyl phosphite, tetraphenyl dipropylene glycol diphosphite, tris(nonylphenyl)phosphite, tris(2,4-di-tert-butylphenyl)phosphite, tris(2,4-di-tert-butyl-5-methylphenyl)phosphite, tris[2-tert-butyl-4-(3-tert-butyl butyl-4-hydroxy-5-methylphenylthio)-5-methylphenyl] phosphite, tridecyl phosphite, octyl diphenyl phosphite, didecyl monophenyl phosphite, distearyl pentaerythritol diphosphite, a mixture of distearyl pentaerythritol diphosphite and calcium stearate, 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, tetraphenyltetrakis(tridecyl)pentaerythritol tetraphosphite, bis(2,4-di-tert-butyl-6-methylphenyl)ethyl phosphite, tetrakis(tridecyl)isopropylidenediphenol diphosphite, tetrakis(tridecyl)-4,4'-n-butylidenebis(2-tert-butyl-5-methylphenol)diphosphite, hexakis(tridecyl)-1,1,3-tris(2-methyl-5-tert-butylphenyl)butane triphosphite, tetrakis(2,4-di-tert-butylphenyl)biphenylene diphosphonite, 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, (1-methyl-1-propenyl-3-ylidene)tris(1,1-dimethylethyl)-5-methyl-4,1-phenylene)hexakis(tridecyl)phosphite, 2,2'-methylenebis(4,6-di-tert-butylphenyl)-2-ethylhexyl phosphite, 2,2'-methylenebis(4,6-di-tert-butylphenyl)-2-ethylhexyl phosphite butylphenyl)octadecyl phosphite, 2,2'-ethylidenebis(4,6-di-tert-butylphenyl)fluorophosphite, 4,4'-butylidenebis(2-tert-butyl-5-methylphenyl)tetratridecyl bisphosphite, tris(2-[(2,4,8,10-tetrakis-tert-butyldibenzo[d,f][1,3,2]dioxaphosphepin-6-yl)oxy]ethyl)amine, 3,9-bis(4-nonylphenoxy)-2,4,8,10-tetraoxa-3,9-diphosphespiro[5,5]undecane, 2,4,6-tri-tert-butylphenyl-2-butyl-2-ethyl-1,3-propanediol phosphite, 4,4'-isopropylidenediphenol C, 10 Alcohol phosphite, 4,4'-isopropylidenediphenol C 12-15 Alcohol phosphite, etc. These phosphorus-based antioxidants may be used alone or in combination of two or more.

[0090] The content of the phosphorus-based antioxidant in the flame retardant composition of the present invention can be within a range that does not impair the effects of the present invention, but an amount of 0.01 to 1 part by mass, and more preferably 0.03 to 0.8 parts by mass, per 100 parts by mass of the synthetic resin contained in the resin composition containing the flame retardant composition of the present invention.

[0091] Examples of the thioether-based antioxidant include tetrakis[methylene-3-(laurylthio)propionate]methane, bis(methyl-4-[3-n-alkyl(C12 / C14)thiopropionyloxy]5-tert-butylphenyl)sulfide, bis(tridecyl)-3,3'-thiodipropionate, dilauryl-3,3'-thiodipropionate, dimyristyl-3,3'-thiodipropionate, distearyl-3,3'-thiodipropionate, lauryl / stearyl thiodipropionate, 4,4'-thiobis(6-tert-butyl-m-cresol), 2,2'-thiobis(6-tert-butyl-p-cresol), and distearyl disulfide. These thioether-based antioxidants may be used alone or in combination of two or more.

[0092] The content of the thioether-based antioxidant in the flame retardant composition of the present invention can be within a range that does not impair the effects of the present invention, but the content is preferably 0.001 to 10 parts by mass, more preferably 0.005 to 5 parts by mass, relative to 100 parts by mass of the synthetic resin contained in the resin composition containing the flame retardant composition of the present invention.

[0093] Examples of the hindered amine-based light stabilizer include 2,2,6,6-tetramethyl-4-piperidyl stearate, 1,2,2,6,6-pentamethyl-4-piperidyl stearate, 2,2,6,6-tetramethyl-4-piperidyl benzoate, bis(2,2,6,6-tetramethyl-4-piperidyl)sebacate, tetrakis(2,2,6,6-tetramethyl-4-piperidyl)-1,2,3,4-butanetetracarboxylate, and tetrakis(1,2,2,6,6-pentamethyl-4-piperidyl)-1,2,3,4-butanetetracarbohydrate. xylates, bis(2,2,6,6-tetramethyl-4-piperidyl)·bis(tridecyl)-1,2,3,4-butanetetracarboxylate, bis(1,2,2,6,6-pentamethyl-4-piperidyl)·di(tridecyl)-1,2,3,4-butanetetracarboxylate, bis(1,2,2,4,4-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 polycondensation 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-(2,2,6,6-tetramethyl-4-piperidyl)amino)-s-triazine-6-yl]- rakis[2,4-bis(N-butyl-N-(1,2,2,6,6-pentamethyl-4-piperidyl)amino)-s-triazin-6-yl]-1,5,8-12-tetraazadodecane, 1,6,11-tris[2,4-bis(N-butyl-N-(2,2,6,6-tetramethyl-4-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, and TINUVIN NOR 371 manufactured by Ciba Specialty Chemicals. These hindered amine light stabilizers may be used alone or in combination of two or more.

[0094] The content of these hindered amine-based light stabilizers can be within a range that does not impair the effects of the present invention, but the content is preferably 0.001 to 10 parts by mass, and more preferably 0.005 to 1 part by mass, relative to 100 parts by mass of the synthetic resin contained in the resin composition containing the flame retardant composition of the present invention.

[0095] Examples of the ultraviolet absorber include 2-hydroxybenzophenones such as 2,4-dihydroxybenzophenone and 5,5′-methylenebis(2-hydroxy-4-methoxybenzophenone);2-(2-hydroxy-5-methylphenyl)benzotriazole, 2-(2-hydroxy-5-tert-octylphenyl)benzotriazole, 2-(2-hydroxy-3,5-di-tert-butylphenyl)-5-chlorobenzotriazole, 2-(2-hydroxy-3-tert-butyl-5-methylphenyl)-5-chlorobenzotriazole, 2-(2-hydroxy-3,5-dicumylphenyl)benzotriazole, 2,2'-methylenebis(4-tert-octyl-6-benzotriazole), 2-[2-hydroxy-3-(2-methacryloyloxyethyl)-5-tert-butylphenyl]benzotriazole, 2-[2-hydroxy-3-(2-methacryloyloxyethyl)-5-tert-octyl ... 2-[2-hydroxy-3-(2-methacryloyloxyethyl)phenyl]benzotriazole, 2-[2-hydroxy-3-tert-butyl-5-(2-methacryloyloxyethyl)phenyl]benzotriazole, 2-[2-hydroxy-3-tert-butyl-5-(2-methacryloyloxyethyl)phenyl]benzotriazole, 2-[2-hydroxy-3-tert-amyl-5-(2-methacryloyloxyethyl)phenyl]benzotriazole, 2-[2-hydroxy-3-tert-amyl-5-(2-methacryloyloxyethyl)phenyl]benzotriazole, 2-(2-hydroxyphenyl)benzotriazoles such as 2-[2-hydroxy-4-(2-methacryloyloxymethyl)phenyl]benzotriazole, 2-[2-hydroxy-4-(3-methacryloyloxy-2-hydroxypropyl)phenyl]benzotriazole, and 2-[2-hydroxy-4-(3-methacryloyloxypropyl)phenyl]benzotriazole;Phenyl salicylate, resorcinol monobenzoate, 2,4-di-tert-butylphenyl-3,5-di-tert-butyl-4-hydroxybenzoate, octyl (3,5-di-tert-butyl-4-hydroxy)benzoate, dodecyl (3,5-di-tert-butyl-4-hydroxy)benzoate, tetradecyl (3,5-di-tert-butyl-4-hydroxy)benzoate, hexadecyl (3,5-di-tert-butyl-4-hydroxy)benzoate, octadecyl (3,5-di-tert benzoates such as 2-ethyl-2'-ethoxyoxanilide and 2-ethoxy-4'-dodecyloxanilide; cyanoacrylates such as ethyl-α-cyano-β,β-diphenylacrylate and methyl-2-cyano-3-methyl-3-(p-methoxyphenyl)acrylate; and various metal salts or metal chelates, particularly nickel and chromium salts or chelates. These ultraviolet absorbents may be used alone or in combination of two or more kinds.

[0096] The content of the ultraviolet absorber in the flame retardant composition of the present invention can be within a range that does not impair the effects of the present invention, but the content is preferably 0.001 to 10 parts by mass, and more preferably 0.005 to 1 part by mass, relative to 100 parts by mass of the synthetic resin contained in the resin composition containing the flame retardant composition of the present invention.

[0097] Examples of the plasticizer include phthalic acid plasticizers such as dibutyl phthalate, butyl benzyl phthalate, butyl hexyl phthalate, diheptyl phthalate, dioctyl phthalate, bis(2-ethylhexyl) phthalate, diisooctyl phthalate, diisononyl phthalate, diisodecyl phthalate, dilauryl phthalate, dicyclohexyl phthalate, dioctyl terephthalate, and bis(2-ethylhexyl) terephthalate; adipic acid plasticizers such as dioctyl adipate, bis(2-ethylhexyl) adipate, diisononyl adipate, diisodecyl adipate, and bis(butyl diglycol) adipate; triphenyl phosphate, tricresyl phosphate, trixylenyl phosphate, tris(isopropylphenyl) phosphate, triethyl phosphate, tributyl phosphate, tris(isopropylphenyl) phosphate, triethyl phosphate, tributyl phosphate, triethyl ... phosphate-based plasticizers such as rioctyl phosphate, tris(butoxyethyl) phosphate, and octyl diphenyl phosphate; polyester-based plasticizers using polyhydric alcohols such as ethylene glycol, diethylene glycol, triethylene glycol, 1,2-propanediol, 1,3-propanediol, 2-methyl-1,3-propanediol, 1,3-butanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, neopentyl glycol, and trimethylolpropane, and dibasic acids such as oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, phthalic acid, isophthalic acid, terephthalic acid, and cinnamic acid, and using monohydric alcohols, monocarboxylic acids (acetic acid, lauric acid, aromatic acids, and the like) as stoppers as necessary;Epoxidized soybean oil, epoxidized linseed oil, epoxidized tung oil, epoxidized fish oil, epoxidized beef tallow oil, epoxidized castor oil, epoxidized safflower oil, epoxidized methyl stearate, epoxidized butyl stearate, epoxidized 2-ethylhexyl stearate, epoxidized stearyl stearate, epoxidized polybutadiene, tris(epoxypropyl)isocyanurate, epoxidized tall oil fatty acid ester, epoxidized linseed oil fatty acid ester, bisphenol A diglycidyl ether, vinylcyclohexene diepoxide, dicyclohexene diepoxide, 3,4-epoxycyclohex Examples of the plasticizer include epoxy-based plasticizers such as silmethyl and epoxycyclohexane carboxylate, and other tetrahydrophthalic acid-based plasticizers, azelaic acid-based plasticizers, sebacic acid-based plasticizers such as bis(2-ethylhexyl)sebacate and dibutyl sebacate, stearic acid-based plasticizers, citric acid-based plasticizers, trimellitic acid-based plasticizers, pyromellitic acid-based plasticizers, biphenylene polycarboxylic acid-based plasticizers, trimethylolpropane tribenzoate, diethylene glycol dibenzoate, dipropylene glycol dibenzoate, (2-ethylhexyl)benzoate, and aromatic acid ester-based plasticizers such as isodecyl benzoate. Preferred are polyester-based plasticizers, phthalic acid-based plasticizers, trimellitic acid-based plasticizers, adipic acid-based plasticizers, sebacic acid-based plasticizers, and epoxy-based plasticizers. These plasticizers may be used alone or in combination of two or more.;

[0098] The content of the plasticizer in the flame retardant composition of the present invention can be within a range that does not impair the effects of the present invention, but the content is preferably 1 to 90 parts by mass, and more preferably 10 to 80 parts by mass, relative to 100 parts by mass of the synthetic resin contained in the resin composition containing the flame retardant composition of the present invention.

[0099] Examples of the crystal nucleating agent include metal salts of carboxylates 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; polyhydric alcohol derivatives such as dibenzylidene sorbitol, bis(methylbenzylidene)sorbitol, bis(p-ethylbenzylidene)sorbitol, bis(dimethylbenzylidene)sorbitol, and 1,2,3-trideoxy-4,6:5,7-O-bis(4-propylbenzylidene)nonitol; N,N',N"-tris[2-methylcyclohexyl]-1,2,3-propanetricarboxamide (RIKACLEAR Examples of the crystal nucleating agent include amide compounds such as PC1), N,N',N"-tricyclohexyl-1,3,5-benzenetricarboxamide, N,N'-dicyclohexyl-naphthalenedicarboxamide, and 1,3,5-tris(dimethylisopropoylamino)benzene. These crystal nucleating agents may be used alone or in combination of two or more.

[0100] The content of the crystal nucleating agent in the flame retardant composition of the present invention can be within a range that does not impair the effects of the present invention, but an amount of 0.001 to 10 parts by mass, and more preferably 0.01 to 5 parts by mass, per 100 parts by mass of the synthetic resin contained in the resin composition containing the flame retardant composition of the present invention.

[0101] Examples of the flame retardant other than the component (A) 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-phenylene tetraphenyl diphosphate, 1,3-phenylene tetrakis(2,6-dimethylphenyl) phosphate, and amide phosphate sold under the trade name " 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; Phosphazene compounds such as (2-allylphenoxy)phosphazene and dicresylphosphazene, phosphorus-based 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-dibromoethyl)cyclohexane, tetrabromobenzene ... Examples of the flame retardants include tribromocyclooctane, hexabromocyclododecane, bis(tribromophenoxy)ethane, brominated polyphenylene ether, brominated polystyrene, and 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 flame retardants may be used alone or in combination of two or more.

[0102] The content of the flame retardant other than the component (A) according to the present invention in the flame retardant composition of the present invention can be within a range that does not impair the effects of the present invention, but the content is preferably 1 to 90 parts by mass, more preferably 3 to 80 parts by mass, per 100 parts by mass of the synthetic resin contained in the resin composition containing the flame retardant composition of the present invention.

[0103] Examples of the flame retardant auxiliary include inorganic flame retardant auxiliary such as titanium oxide, aluminum oxide, magnesium oxide, hydrotalcite, talc, montmorillonite, and other inorganic compounds, and surface-treated products thereof. Examples of the inorganic flame retardant auxiliary include TIPAQUE R-680 (titanium oxide: manufactured by Ishihara Sangyo Kaisha), Kyowamag 150 (magnesium oxide: manufactured by Kyowa Chemical Industry Co., Ltd.), DHT-4A (hydrotalcite: manufactured by Kyowa Chemical Industry Co., Ltd.), and Alcamizer 4 (zinc-modified hydrotalcite: manufactured by Kyowa Chemical Industry Co., Ltd.). Examples of organic flame retardant aids include polyhydric alcohol compounds such as 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 (sucrose), trehalose, inositol, fructose, maltose, lactose, etc. Among these polyhydric alcohol compounds, one or more selected from the group of pentaerythritol and pentaerythritol condensates such as pentaerythritol, dipentaerythritol, tripentaerythritol, polypentaerythritol, etc. are preferred, dipentaerythritol and pentaerythritol condensates are particularly preferred, and dipentaerythritol is the most preferred. In addition, THEIC and sorbitol can also be suitably used. These flame retardant synergists may be used alone or in combination of two or more.

[0104] The content of the flame retardant auxiliary in the flame retardant composition of the present invention can be within a range that does not impair the effects of the present invention, but the content is preferably 0.01 to 20 parts by mass, and more preferably 0.1 to 10 parts by mass, relative to 100 parts by mass of the synthetic resin contained in the resin composition containing the flame retardant composition of the present invention.

[0105] Examples of the drip prevention agent include fluorine-based drip prevention agents, silicone rubbers, and layered silicates. Examples of the fluorine-based drip prevention agent include fluorine-based resins such as polytetrafluoroethylene, polyvinylidene fluoride, and polyhexafluoropropylene, and perfluoroalkanesulfonic acid alkali metal salt compounds or perfluoroalkanesulfonic acid alkaline earth metal salts such as sodium perfluoromethanesulfonate, potassium perfluoro-n-butanesulfonate, potassium perfluoro-t-butanesulfonate, sodium perfluorooctane sulfonate, and calcium perfluoro-2-ethylhexanesulfonate. Examples of layered silicates include smectite clay minerals such as montmorillonite, saponite, hectorite, beidellite, stevensite, and nontronite, vermiculite, halloysite, swelling mica, and talc, and organic cations, quaternary ammonium cations, and phosphonium cations may be intercalated between the layers. These drip prevention agents may be used alone or in combination of two or more. Among the drip prevention agents, fluorine-based drip prevention agents are particularly preferred from the viewpoint of drip prevention, and polytetrafluoroethylene is most preferred.

[0106] The content of the anti-drip agent in the flame retardant composition of the present invention can be within a range that does not impair the effects of the present invention, but is preferably 0.005 to 5 parts by mass, more preferably 0.01 to 5 parts by mass, even more preferably 0.05 to 3 parts by mass, and even more preferably 0.1 to 1 part by mass, relative to 100 parts by mass of the component (A) of the present invention. By making it 0.005 parts by mass or more, it is possible to obtain a sufficient drip prevention effect, and by making it 5 parts by mass or less, the properties of the resin are not deteriorated.

[0107] As the acrylic processing aid, one type of (meth)acrylic acid ester can be polymerized or two or more types of (meth)acrylic acid esters can be copolymerized. Examples of (meth)acrylic acid esters to be polymerized or copolymerized include (meth)acrylic acid esters such as methyl acrylate, methyl methacrylate, ethyl acrylate, ethyl methacrylate, n-propyl acrylate, isopropyl acrylate, n-propyl methacrylate, isopropyl methacrylate, n-butyl acrylate, isobutyl acrylate, t-butyl methacrylate, n-hexyl acrylate, n-hexyl methacrylate, 2-ethylhexyl acrylate, 2-ethylhexyl methacrylate, dodecyl methacrylate, and tridecyl methacrylate. In addition to the above, (meth)acrylic acid and (meth)acrylic acid esters containing a hydroxyl group can also be used.

[0108] The content of the acrylic processing aid in the flame retardant composition of the present invention can be within a range that does not impair the effects of the present invention, but an amount of 0.01 to 10 parts by mass, and more preferably 0.03 to 1 part by mass, per 100 parts by mass of the synthetic resin contained in the resin composition containing the flame retardant composition of the present invention is preferably 0.01 to 10 parts by mass.

[0109] Examples of the antistatic agent include cationic antistatic agents such as fatty acid quaternary ammonium ion salts and polyamine quaternary salts; anionic antistatic agents such as higher alcohol phosphate salts, higher alcohol EO adducts, polyethylene glycol fatty acid esters, anionic alkylsulfonates, higher alcohol sulfate salts, higher alcohol ethylene oxide adduct sulfate salts, and higher alcohol ethylene oxide adduct phosphate 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 dimethylamino acetate betaines and imidazoline amphoteric surfactants. These antistatic agents may be used alone or in combination of two or more.

[0110] The content of the antistatic agent in the flame retardant composition of the present invention can be within a range that does not impair the effects of the present invention, but the content is preferably 0.01 to 20 parts by mass, and more preferably 0.03 to 10 parts by mass, relative to 100 parts by mass of the synthetic resin contained in the resin composition containing the flame retardant composition of the present invention.

[0111] As the pigment, commercially available pigments can be used. 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, 1 85, 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, 1 68, 175, 180, 185; Pigment Green 7, 10, 36; Pigment Blue 15, 15:1, 15:2, 15:3, 15:4, 15:5, 15:6, 22, 24, 56, 60, 61, 62, 64; Pigment Violet 1, 19, 23, 27, 29, 30, 32, 37, 40, 50, etc. These pigments may be used alone or in combination of two or more kinds.

[0112] The content of the pigment in the flame retardant composition of the present invention can be within a range that does not impair the effects of the present invention, but an amount of 0.001 to 5 parts by mass, and more preferably 0.003 to 3 parts by mass, per 100 parts by mass of the synthetic resin contained in the resin composition containing the flame retardant composition of the present invention.

[0113] Examples of the 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 may be used alone or in combination of two or more.

[0114] The content of the dye in the flame retardant composition of the present invention can be within a range that does not impair the effects of the present invention, but the content is preferably 0.001 to 5 parts by mass, and more preferably 0.003 to 3 parts by mass, relative to 100 parts by mass of the synthetic resin contained in the resin composition containing the flame retardant composition of the present invention.

[0115] In addition, the flame retardant composition of the present invention may contain additives that are usually used in synthetic resins, such as crosslinking agents, antifogging agents, plate-out inhibitors, surface treatment agents, fluorescent agents, antifungal agents, bactericides, foaming agents, metal deactivators, release agents, processing aids other than acrylic processing aids, etc., as necessary, within the range that does not significantly impair the effects of the present invention. These components may be blended in advance with the flame retardant composition of the present invention, or may be blended during the preparation of the flame-retardant synthetic resin composition described below.

[0116] To obtain the flame retardant composition of the present invention, the (A) component and the (B) component may be mixed with other optional components as necessary, and various mixers may be used for mixing. Heat may be applied during mixing. Examples of mixers that can be used include a tumbler mixer, a Henschel mixer, a ribbon blender, a V-type mixer, a W-type mixer, a super mixer, and a Nauta mixer.

[0117] The flame retardant composition of the present invention can be blended with a synthetic resin, particularly preferably a thermoplastic resin, and used as a flame retardant synthetic resin composition.

[0118] <Flame-retardant synthetic resin composition> The flame-retardant synthetic resin composition of the present invention contains at least one synthetic resin and at least one flame retardant composition of the present invention.

[0119] Specific examples of the synthetic resin include α-olefin polymers such as polypropylene, high density polyethylene, low density polyethylene, linear low density polyethylene, crosslinked polyethylene, ultra-high molecular weight polyethylene, polybutene-1, poly-3-methylpentene, and poly-4-methylpentene, and polyolefin resins such as ethylene-vinyl acetate copolymer, ethylene-ethyl acrylate copolymer, and ethylene-propylene copolymer, and copolymers thereof; halogen-containing resins such as polyvinyl chloride, polyvinylidene chloride, chlorinated polyethylene, chlorinated polypropylene, polyvinylidene fluoride, chlorinated rubber, vinyl chloride-vinyl acetate copolymer, vinyl chloride-ethylene copolymer, vinyl chloride-vinylidene chloride copolymer, vinyl chloride-vinylidene chloride-vinyl acetate terpolymer, vinyl chloride-acrylic acid ester copolymer, vinyl chloride-maleic acid ester copolymer, and vinyl chloride-cyclohexylmaleimide copolymer; petroleum resin, coumarone resin, polystyrene, polyvinyl acetate, acrylic resin, styrene, and / or the like. or copolymers of α-methylstyrene with other monomers (e.g., maleic anhydride, phenylmaleimide, methyl methacrylate, butadiene, acrylonitrile, etc.) (e.g., AS resin, ABS (acrylonitrile-butadiene-styrene copolymer) resin, ACS resin, SBS resin, MBS resin, heat-resistant ABS resin, etc.); polymethyl methacrylate, polyvinyl alcohol, polyvinyl formal, polyvinyl butyral; aromatic polyesters such as polyalkylene terephthalates such as polyethylene terephthalate, polybutylene terephthalate, and polycyclohexane dimethylene terephthalate, polyalkylene naphthalates such as polyethylene naphthalate and polybutylene naphthalate, and linear polyesters such as polytetramethylene terephthalate; degradable aliphatic polyesters such as polyhydroxybutyrate, polycaprolactone, polybutylene succinate, polyethylene succinate, polylactic acid, polymalic acid, polyglycolic acid, polydioxane, and poly(2-oxetanone);Examples of the synthetic resin include polyamides such as polyphenylene oxide, polycaprolactam, and polyhexamethylene adipamide, polycarbonate, polycarbonate / ABS resin, branched polycarbonate, polyacetal, polyphenylene sulfide, polyurethane, cellulose resin, polyimide resin, polysulfone, polyphenylene ether, polyether ketone, polyether ether ketone, and liquid crystal polymer, and blends thereof. The synthetic resin may be an elastomer such as isoprene rubber, butadiene rubber, acrylonitrile-butadiene copolymer rubber, styrene-butadiene copolymer rubber, fluororubber, silicone rubber, polyolefin thermoplastic elastomer, styrene thermoplastic elastomer, polyester thermoplastic elastomer, nitrile thermoplastic elastomer, nylon thermoplastic elastomer, vinyl chloride thermoplastic elastomer, polyamide thermoplastic elastomer, and polyurethane thermoplastic elastomer. In the present invention, these synthetic resins may be used alone or in combination of two or more. The synthetic resin may be alloyed.

[0120] These synthetic resins can be used regardless of molecular weight, degree of polymerization, density, softening point, proportion of insoluble matter in solvent, degree of stereoregularity, presence or absence of catalyst residue, types and blending ratios of monomers used as raw materials, types of polymerization catalysts (e.g., Ziegler catalyst, metallocene catalyst, etc.), etc. Among these synthetic resins, one or more selected from the group consisting of polyolefin resins, polystyrene resins, and copolymers thereof are preferred because they can impart excellent flame retardancy, and it is also preferred to use them in combination with a thermoplastic elastomer.

[0121] In addition, the synthetic resin may contain any known resin additives as long as the effect of the present invention is not significantly impaired. As such resin additives, for example, one or more selected from the group consisting of phenol-based antioxidants, phosphorus-based antioxidants, thioether-based antioxidants, other antioxidants, hindered amine-based light stabilizers, ultraviolet absorbers, plasticizers, crystal nucleating agents, flame retardants other than the component (A) according to the present invention, flame retardant assistants, drip prevention agents, acrylic processing assistants, antistatic agents, pigments and dyes are used, and specific examples thereof include the same resin additives that can be contained in the above-mentioned flame retardant composition. These resin additives may be blended in advance in the synthetic resin, or may be blended during the preparation of the flame-retardant synthetic resin composition.

[0122] In addition, when a polyolefin resin is used as the thermoplastic resin, it is preferable to further add a known neutralizing agent to neutralize the residual catalyst in the polyolefin resin as necessary within a range that does not impair the effects of the present invention. Examples of the neutralizing agent include fatty acid metal salts such as calcium stearate, lithium stearate, and sodium stearate, fatty acid amide compounds such as ethylene bis(stearic acid amide), ethylene bis(12-hydroxystearic acid amide), and stearic acid amide, and inorganic compounds such as hydrotalcite, and these neutralizing agents may be used in combination. The amount of these neutralizing agents used is preferably 0.001 to 3 mass %, more preferably 0.01 to 1 mass %, in the flame-retardant synthetic resin composition when blended with the synthetic resin.

[0123] The content of the flame retardant composition in the flame-retardant synthetic resin composition of the present invention is preferably 10 to 400 parts by mass, more preferably 10 to 300 parts by mass, further preferably 10 to 150 parts by mass, and particularly preferably 20 to 120 parts by mass, relative to 100 parts by mass of the synthetic resin. By making the content of the flame retardant composition 10 parts by mass or more relative to 100 parts by mass of the synthetic resin, sufficient flame retardancy can be exhibited, and by making it 400 parts by mass or less, the inherent physical properties of the resin are not impaired.

[0124] The method of blending the flame retardant composition of the present invention with a synthetic resin is not particularly limited, and any known method can be used. Specific blending methods include a method of mixing with a normal blender, mixer, etc., a method of melt-kneading with an extruder, etc., a method of mixing with a solvent and then solution casting, etc.

[0125] Moreover, the flame-retardant synthetic resin composition of the present invention satisfies the relationships represented by the following formulas (i) and (ii). (i) 0.935≦ΔTD / ΔTD B ≦1.065 (ii) 0.860≦(ΔTD / ΔMD) / (ΔTD B / ΔMD B )≦1.140

[0126] In the above formula, ΔMD is the shrinkage rate (%) in the MD direction of the molded article obtained by injection molding the flame-retardant synthetic resin composition, and ΔTD is the shrinkage rate (%) in the TD direction of the molded article obtained by injection molding the flame-retardant synthetic resin composition. Here, the MD direction is the flow direction of the resin in the mold cavity during injection molding, and the TD direction is the direction perpendicular to the MD direction. In addition, ΔMD B is the shrinkage rate in the MD direction of the molded body obtained by injection molding the base resin, and ΔTD B is the shrinkage rate in the TD direction of a molded body obtained by injection molding a base resin, and the base resin means a synthetic resin composition consisting of a composition obtained by excluding the flame retardant composition from the flame-retardant synthetic resin composition.

[0127] The shrinkage rates ΔMD and ΔTD are respectively expressed by the following formulas. ΔMD(%)=[(MD 0 -MD 1 ) / MD 0 ] x 100 ΔTD(%)=[(TD 0 -TD 1 ) / TD 0 ] x 100

[0128] In the above formula, MD 0 is the dimension of the mold cavity used for injection molding in the MD direction, and TD0 is the dimension of the mold cavity used for injection molding in the TD direction, and MD 1 is the dimension in the MD direction of the molded body obtained by injection molding using the above mold, and TD 1 is the dimension in the TD direction of the molded body injection molded using the above mold.

[0129] In the above formula (ii), ΔTD / ΔMD represents the balance of the molding shrinkage rate of the flame-retardant synthetic resin composition in the vertical and horizontal directions, and ΔTD B / ΔMD B represents the balance of the molding shrinkage rate of the base resin in the vertical and horizontal directions. Satisfying the above formula (ii) means that the ΔTD / ΔMD of the flame-retardant synthetic resin composition is B / ΔMD B The closer these ratios are to 1, the closer the balance between the length and width in terms of molding shrinkage rate between the flame-retardant synthetic resin composition and the base resin is, and the easier it is to obtain a molded product with an aspect ratio as intended at the time of mold design.

[0130] In addition, satisfying the above formula (i) means that ΔTD of the flame-retardant synthetic resin composition is B The closer this ratio is to 1, the closer the molding shrinkage rates of the flame-retardant synthetic resin composition and the base resin are, and the easier it is to obtain a molded article with the dimensions intended at the time of mold design.

[0131] In other words, satisfying the above formulas (i) and (ii) simultaneously means that even when the flame-retardant synthetic resin composition of the present invention is molded using a mold designed for molding the base resin, a molded article having a shape similar to that of a molded article made of the base resin can be obtained.

[0132] In order to obtain the effects of the present invention satisfactorily, ΔTD / ΔTD in the above formula (i) B The lower limit of ΔTD / ΔTD in the above formula (i) is required to be 0.935, preferably 0.940, and more preferably 0.945. B The upper limit of the ratio must be 1.065, is preferably 1.060, and is more preferably 1.055. In order to obtain the effects of the present invention satisfactorily, (ΔTD / ΔMD) / (ΔTD B / ΔMD B The lower limit of (ΔTD / ΔMD) / (ΔTD in the above formula (ii) must be 0.860, preferably 0.865, and more preferably 0.870. B / ΔMD B The upper limit of the above must be 1.140, preferably 1.135, and more preferably 1.130.

[0133] The dimensions of the molded body and the mold cavity can be measured using measuring instruments such as calipers, rulers, digital length measuring instruments, image measuring instruments, etc. The dimensions of the molded body and the mold cavity are preferably measured at room temperature (20 to 25° C.).

[0134] The shape of the mold cavity used for injection molding of the flame-retardant synthetic resin composition is not particularly limited, and examples of the shape include a square, circular, elliptical, polygonal, cylindrical, conical, irregular shape, etc., but from the viewpoint of accurately measuring the length in the MD and TD directions, a symmetrical shape is preferable.

[0135] The molding shrinkage rate and the longitudinal and lateral balance of a molded article made from the flame-retardant synthetic resin composition of the present invention are close to those of a molded article made from a base resin, and therefore even when the flame-retardant synthetic resin composition of the present invention is molded using a mold designed for molding the base resin, a molded article close in shape to the article made from the base resin can be obtained.

[0136] <Molded body> The molded article of the present invention is obtained by molding the flame-retardant synthetic resin composition of the present invention, preferably a flame-retardant synthetic resin composition using a thermoplastic resin. There is no particular restriction on the molding method and molding conditions, and known molding methods and molding conditions can be used. Specific molding methods include extrusion processing, calendar processing, injection molding, rolling, vacuum molding, pressure molding, compression molding, blow molding, rotational molding, etc., and from the viewpoint of the effects of the present invention, molding by injection molding is preferable. The shape of the molded article of the present invention includes various shapes such as resin plates, sheets, films, bottles, fibers, and irregular shapes.

[0137] The flame-retardant synthetic resin composition of the present invention and its molded article can be used in a wide range of industrial fields, including electricity, electronics, communications, agriculture, forestry, fisheries, mining, construction, food, textiles, clothing, medicine, coal, petroleum, rubber, leather, automobiles, precision instruments, wood, building materials, civil engineering, furniture, printing, and musical instruments. More specifically, they are used in office and office 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, stationery, etc., home appliances such as washing machines, refrigerators, vacuum cleaners, microwave ovens, lighting fixtures, game consoles, irons, kotatsu (heated table with heated tables), audio-visual equipment such as TVs, VTRs, video cameras, radio cassette players, tape recorders, minidiscs, CD players, speakers, LCD displays, etc., electric and electronic components and communication equipment such as connectors, relays, capacitors, switches, printed circuit boards, coil bobbins, semiconductor encapsulation materials, LED encapsulation materials, electric wires, cables, transformers, deflection yokes, distribution boards, clocks, etc., housings (frames, enclosures, covers, exteriors) and parts for office equipment, etc., and interior and exterior materials for automobiles.

[0138] Furthermore, the flame-retardant synthetic resin composition of the present invention and its molded article can be used for seats (padding, outer material, etc.), belts, ceiling coverings, convertible tops, armrests, door trims, rear package trays, carpets, mats, sun visors, wheel covers, mattress covers, airbags, insulation materials, hanging handles, hanging handle straps, wire covering materials, electrical insulation 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 pillar materials. They are used for a variety of purposes, including materials for automobiles, hybrid cars, electric cars, vehicles, ships, aircraft, buildings, houses and construction, such as floor boards, fence materials, frames and moldings, window and door shapes, shingles, paneling, terraces, balconies, soundproofing boards, heat insulating boards, window materials, etc., as well as civil engineering materials, clothing, curtains, sheets, plywood, synthetic fiber boards, carpets, entrance mats, sheets, buckets, hoses, containers, glasses, bags, cases, goggles, skis, rackets, tents, musical instruments and other daily necessities and sporting goods. EXAMPLES

[0139] The present invention will be described in detail below with reference to examples. However, the present invention is not limited to the following examples. In the following examples, the blending amounts of the components are based on parts by mass unless otherwise specified.

[0140] [Examples 1 to 6, Reference Examples 1 and 2, and Comparative Examples 1 to 7] Resin compositions containing the flame retardant composition of the present invention (Examples 1 to 6, Reference Examples 1 and 2) and comparative resin compositions (Comparative Examples 1 to 7) were produced by the following method.

[0141] <Preparation of Impact Copolymer Resin Composition Pellets> To an impact copolymer polypropylene resin (Prime Polypro J-754HP, manufactured by Prime Polymer Co., Ltd., melt flow rate 14 g / 10 min) in an amount adjusted so that the total amount of the resin composition was 100 parts by mass, 0.1 parts by mass of a phenol-based antioxidant (tetrakis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionyloxymethyl]methane, manufactured by ADEKA Corporation under the trade name "ADK STAB AO-60"), 0.1 parts by mass of a phosphorus-based antioxidant (tris(2,4-di-tert-butylphenyl)phosphite, manufactured by ADEKA Corporation under the trade name "ADK STAB 2112"), 0.1 parts by mass of a neutralizing agent (calcium stearate), and each compound in the blending amounts shown in the table below were added and mixed, and the mixture was melt-kneaded in a twin-screw extruder (apparatus: manufactured by The Japan Steel Works, Ltd., TEX25αIII, extrusion temperature: 220° C., screw rotation speed: 150 rpm) to prepare pellets. The pellets thus obtained were dried at 60° C. for 8 hours, and then evaluated for flame retardancy and shrink isotropy according to the test methods described below. The results are shown in the following table.

[0142] <Flame retardancy UL-94V test> The pellets obtained by the above procedure were injection molded using an injection molding machine (EC60NII-1.5A; manufactured by Toshiba Machine Co., Ltd.) under conditions of a resin temperature of 220°C and a mold temperature of 50°C to prepare a test piece with a length of 127 mm, a width of 12.7 mm, and a thickness of 1.6 mm. The test piece was fixed vertically, and a burner flame was applied to the lower end for 10 seconds, after which the flame was removed and the time it took for the fire to go out was measured. Next, as soon as the fire went out, the second flame was applied for 10 seconds and the time it took for the fire to go out was measured in the same way as the first time. In addition, it was also evaluated whether the cotton under the test piece would ignite due to the falling fire.

[0143] Flame ranks were assigned according to the UL-94V standard based on factors such as the burning time after the first and second exposure to flame, and whether the cotton ignited. V-0 is the highest flammability rank, with flame retardancy decreasing as the ranks progress to V-1 and V-2. Items that do not fall into any of the V-0 to V-2 ranks are rated NR (No Rating).

[0144] <Evaluation of shrinkage balance during molding> The pellets obtained by the above procedure were injection molded under the following conditions using an injection molding machine (EC60NII-1.5A; manufactured by Toshiba Machine Co., Ltd.) to prepare test pieces. Resin temperature: 220℃. Mold temperature: 50℃. Injection time: 15 seconds. Cooling time: 25 seconds. Filling speed: 25mm / s. Holding pressure: 20MPa.

[0145] The test piece was left to stand in an incubator at 23°C and 50% humidity for 48 hours, after which the dimensions in the MD and TD directions were measured at three points each, and the average was taken as the MD dimension of the test piece (MD 1 ) and TD direction dimension (TD 1 For the measurements, we used the Mitutoyo Quick Vision ELF image measuring instrument.

[0146] The mold cavity used for molding is rectangular, and the dimensions in the MD direction (MD 0 ) is 60.02 mm, and the dimension in the TD direction (TD 0 ) was 60.03 mm and the thickness was 2.0 mm. A vernier caliper was used to measure the length of the mold cavity in the MD and TD directions.

[0147] The shrinkage rates ΔMD and ΔTD of the test pieces were calculated according to the following formulas. ΔMD(%)=[(MD 0 -MD 1 ) / MD 0 ] x 100 ΔTD(%)=[(TD 0 -TD 1 ) / TD 0 ] x 100

[0148] The shrinkage ratios ΔMD and ΔTD of the base resin (Comparative Example 1) not containing the flame retardant composition of the present invention are respectively B and ΔTD BFrom the evaluation results of Comparative Example 1, ΔMD B =1.72, ΔTD B =1.78.

[0149] The obtained ΔTD was compared with the measured value ΔTD for a base resin (Comparative Example 1) that did not contain the flame retardant composition of the present invention. B is normalized to 1. This normalized value is ΔTD / ΔTD B This is expressed as:

[0150] The obtained ΔMD and ΔTD were substituted into the following formula to calculate the shrinkage isotropy. Shrinkage isotropy = ΔTD / ΔMD

[0151] The obtained value of shrinkage isotropy, ΔTD / ΔMD, was compared with the value of shrinkage isotropy, ΔTD, of the base resin (Comparative Example 1) not containing the flame retardant composition of the present invention. B / ΔMD B was normalized to 1. This normalized value is (ΔTD / ΔMD) / (ΔTD B / ΔMD B )

[0152] [Table 1]

[0153] [Table 2]

[0154] As shown in the above table, the compositions of Examples 1 to 6 and Reference Examples 1 and 2 maintained the flame retardancy evaluation rank compared to the compositions not containing the (B) component (Comparative Examples 2 to 4), while improving the ratio of the shrinkage rate ΔTD to the base resin (ΔTD / ΔTD B ), and the ratio of ΔTD / ΔMD to the base resin ((ΔTD / ΔMD) / (ΔTD B / ΔMD B )) was close to 1, indicating that the longitudinal and lateral balance of the mold shrinkage during injection molding was good.

[0155] Furthermore, in the compositions not containing the component (A) (Comparative Examples 1, 5 to 7), the evaluation rank in the flame retardancy test was rated as NR, which resulted in impaired flame retardancy compared to the compositions of the Examples.

[0156] From the above, it has been confirmed that the flame retardant composition of the present invention can impart excellent flame retardancy to a synthetic resin, and that a molded article using the flame retardant resin composition has a good balance of the longitudinal and lateral mold shrinkage rates compared to a molded article made of a base resin, and therefore the flame retardant composition of the present invention can be suitably used as a flame retardant for resins.

Claims

1. The composition contains 0.005 to 5 parts by mass of the following component (B) relative to 100 parts by mass of the following component (A), The component (A) contains the following components (A-1) and (A-2), and A flame retardant composition, characterized in that the mass ratio of the component (A-1) to the component (A-2) is 30:70 to 45:

55. Component (A): Phosphate-based flame retardant. Component (B): one or more compounds having a structure represented by the following general formula (1): In the above general formula (1), R １ , R ２ , R ３ and R ４ each independently represents a hydrogen atom or an alkyl group having 1 to 8 carbon atoms; R ５ represents a direct bond or an alkanediyl group having 1 to 4 carbon atoms; M １ represents lithium or aluminum, M １ When M 1 is lithium, n is 1 and m is 0; when M 1 is aluminum, n is 1, 2, or 3, and m is an integer represented by 3−n. Component (A-1): one or more melamine salts selected from the group consisting of melamine orthophosphate, melamine pyrophosphate, and melamine polyphosphate. Component (A-2): at least one piperazine salt selected from the group consisting of piperazine orthophosphate, piperazine pyrophosphate, and piperazine polyphosphate.

2. The flame retardant composition according to claim 1, wherein the component (A) further contains the following component (A-3): Component (A-3): one or more ammonium salts selected from the group consisting of ammonium orthophosphate, ammonium pyrophosphate, and ammonium polyphosphate.

3. 2. The flame retardant composition according to claim 1, further comprising, as component (C), at least one selected from the group consisting of fillers, fatty acid metal salts and hydrotalcites.

4. 4. The flame retardant composition according to claim 3, wherein the fatty acid metal salt is a compound having a structure represented by the following general formula (2): In the above general formula (2), R ４ represents a group introduced from a linear or branched aliphatic organic acid having 8 to 30 carbon atoms; M ２ is a metal atom or Al(OH) ３－ｐ and p represents an integer of 1 to 3.

5. The flame retardant composition according to claim 1, further comprising, as a component (E), 0.01 to 5 parts by mass of at least one selected from the group consisting of silicone oil, epoxy coupling agents, and lubricants, relative to 100 parts by mass of the component (A).

6. A flame-retardant synthetic resin composition comprising a synthetic resin and the flame retardant composition according to claim 1, A flame-retardant synthetic resin composition, characterized by satisfying the relationships represented by the following formulas (i) and (ii): (i)0.935≦ΔTD / ΔTD Ｂ ≦1.065 (ii)0.860≦(ΔTD / ΔMD) / (ΔTD Ｂ / ΔMD Ｂ )≦1.140 In the above formula, ΔMD is the shrinkage rate in the MD direction, which is the direction of resin flow in the mold cavity during injection molding, of the molded article obtained by injection molding the flame-retardant synthetic resin composition, ΔTD is the shrinkage rate in the TD direction, which is the direction perpendicular to the MD direction, of the molded article obtained by injection molding the flame-retardant synthetic resin composition, and ΔMD Ｂ is the shrinkage rate in the MD direction of a molded body obtained by injection molding a synthetic resin composition consisting of a composition obtained by excluding the flame retardant composition from the flame retardant synthetic resin composition, and ΔTD Ｂ is the shrinkage rate in the TD direction of a molded article obtained by injection molding the synthetic resin composition.

7. A molded article produced by molding the flame-retardant synthetic resin composition according to claim 6.

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