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    • 专利摘要:
    FLAME RETARDANT COMPOSITION, FLAME RETARDANT SYNTHETIC RESIN COMPOSITION, AND MOLDED PRODUCT. The present invention provides a flame retardant composition having excellent heat resistance and reduced risk of corroding processing equipment at the time of resin preparation. Specifically, the invention provides a flame retardant composition comprising 20 to 50 parts by mass of component (A) described below, 50 to 80 parts by mass of component (B) described below (the total of component (A) and component ( B) is 100 parts by mass), and 0.01 to 5 parts by mass of component (C) described below: component (A): at least one type of melamine salt selected from melamine orthophosphate, melamine pyrophosphate, melamine polyphosphate, or a mixture including two or more types of melamine salts; component (B): at least one type of piperazine salt selected from piperazine orthophosphate, piperazine pyrophosphate, piperazine polyphosphate, or a mixture including two or more types of piperazine salts; and component (C): a hydrotalcite compound.
    公开号:BR112015029500B1
    申请号:R112015029500-2
    申请日:2014-07-18
    公开日:2022-02-01
    发明作者:Okamoto Yuri；Nakamura Michio；Kamimoto Tetsuo；Yonezawa Yutaka；Omori Kohei
    申请人:Adeka Corporation；
    IPC主号:
    专利说明:

    TECHNICAL FIELD
    [0001] The present invention relates to a flame retardant composition for synthetic resins and a flame retardant synthetic resin composition including the flame retardant composition. More specifically, the invention relates to a flame retardant composition which has excellent heat resistance and in which the risk of corrosion of processing machines at the time of obtaining the resin is reduced, and to a flame retardant synthetic resin composition which includes the aforementioned flame retardant composition and which has excellent weather resistance. FUNDAMENTALS
    [0002] Synthetic resins have conventionally been widely used, for example, for building materials, car parts, packaging materials, agricultural materials, housing materials for household appliances and toys because of their excellent chemical and mechanical characteristics. Unfortunately, many synthetic resins are flammable and therefore need to be fireproof for some applications. A widely known method of fire resistance is to use one or a combination of flame retardants, such as halogen-based flame retardants, red phosphorus-typified inorganic phosphorus-based flame retardants, and polyphosphate-based flame retardants. , such as ammonium polyphosphate, organophosphorus-based flame retardants typified by triaryl phosphate ester compounds, metal hydroxides and antimony oxide, and melamine compounds, which are flame retardant aids.
    [0003] Halogen based flame retardants, however, have a disadvantage in that they generate hazardous gases on combustion. Thus, attempts are being made to use the aforementioned phosphorus-based flame retardants that do not cause this problem.
    [0004] For example, Patent Literature 1 describes a flame retardant synthetic resin composition including ammonium polyphosphate, a compound containing a multivalent hydroxyl group, a triazine ring containing compound, and a metal hydroxide. Patent literatures 2 and 3 disclose flame retardant synthetic resin compositions including melamine polyphosphate and (penta to tripty) erythritol. Patent Literature 4 describes a flame retardant synthetic resin composition including polybutylene terephthalate (PBT), melamine pyrophosphate, and an aromatic phosphate oligomer. Patent Literatures 5 and 6 describe that melamine pyrophosphate and other phosphorus-containing compounds are effective in the fire resistance of polymers such as PBT.
    [0005] Among such flame retardants, intumescent flame retardants, - that is, flame retardants which include a polyphosphate salt as a main component and which form a surface swelling (swelling) layer on combustion, thereby obtaining flame retardancy by preventing diffusion of decomposition products and heat transfer - are known to have excellent flame retardancy. For example, Patent Literature 7 describes such a flame retardant. LIST OF QUOTATIONS
    [0006] Patent LiteraturePatent Literature 1: JP 8-176343 APatent Literature 2: US Patent 3936416Patent Literature 3: US Patent 4010137Patent Literature 4: US Patent 5814690Patent Literature 5: US Patent 4278591Patent Literature 6:US Patent 56137Patent Literature 6: US Patent 56137. Patent 7: US 2003088000 (A1) SUMMARY OF THE INVENTION TECHNICAL PROBLEM
    [0007] Unfortunately, polyphosphate salts - ie the main component of the aforementioned intumescent flame retardant - tend to produce strongly acidic salts due to, for example, side reactions at the time of production by heating and condensation. If a polyphosphate salt is used as a material for a flame retardant, the flame retardant may have a low heat resistance due to its acidity, or the flame retardant may corrode processing machinery at the time of obtaining the resins. Furthermore, if the flame retardant is mixed with a synthetic resin and made into a flame retardant synthetic resin composition, the flame retardant may affect the weather resistance of the synthetic resin composition over time.
    [0008] Thus, an object of the invention is to provide a flame retardant composition which has excellent heat resistance and in which the risk of corroding processing machines at the time of obtaining the resin is reduced and to provide a flame retardant synthetic resin composition which includes this flame retardant composition and which has excellent heat resistance and weather resistance. Also provided is a weather resistant flame retardant molded product which is obtained from the above mentioned flame retardant synthetic resin composition. SOLUTION TO THE PROBLEM
    [0009] In order to achieve the above object, the present inventors carried out intensive studies and came to the conclusion of the invention.
    [0010] The invention provides a flame retardant composition comprising from 20 to 50 parts by mass of component (A) described below, 50 to 80 parts by mass of component (B) described below (the total of component (A) and the component (B) is 100 parts by mass), and 0.01 to 5 parts by mass of component (C) described below: component (A): at least one type of melamine salt selected from melamine orthophosphate, melamine, melamine polyphosphate, or a mixture including two or more types of melamine salts; component (B): at least one type of piperazine salt selected from piperazine orthophosphate, piperazine pyrophosphate, piperazine polyphosphate, or a mixture including two or more types of piperazine salts; ecomponent (C): a hydrotalcite compound.
    [0011] The invention provides the flame retardant composition, wherein: at least one type of melamine salt selected as component (A) is a melamine salt obtained by subjecting melamine orthophosphate to heating and condensation; and at least one The type of piperazine salt selected as component (B) is a piperazine salt obtained by subjecting piperazine orthophosphate to heating and condensation.
    [0012] The invention provides the flame retardant composition, wherein a liquid obtained by dispersing the flame retardant composition in water in an amount that is 9 times the mass of the composition has a pH within a range of 3.0 to 5 .0 at 25°C.
    [0013] The invention provides a flame retardant synthetic resin composition obtained by mixing the flame retardant composition with a synthetic resin.
    [0014] The invention provides the flame retardant synthetic resin composition, wherein the synthetic resin is a polyolefin-based resin.
    [0015] The invention provides a molded product obtained from the flame retardant synthetic resin composition. ADVANTAGEOUS EFFECTS OF THE INVENTION
    [0016] According to the present invention, it is possible to provide a flame retardant composition which has excellent heat resistance and in which the risk of corroding processing machines at the time of obtaining the resin is reduced. Further in accordance with the present invention, it is possible to provide a synthetic resin composition which has excellent flame retardancy and weather resistance. Furthermore, according to the present invention, it is possible to provide a molded product having flame retardancy and weather resistance. DESCRIPTION OF MODALITIES
    [0017] The melamine salt used as component (A) in the flame retardant composition of the present invention is selected from melamine orthophosphate, melamine pyrophosphate and melamine polyphosphate; the salt can be used alone or it can be used as a mixture. Among the above, melamine pyrophosphate is preferable from the point of view of heat resistance, weather resistance, and low corrosion risk of processing machinery. In cases of using a blend, the higher the melamine pyrophosphate content ratio, the more preferable.
    [0018] The aforementioned salts of phosphoric acids and melamine can be obtained by reacting melamine with the corresponding phosphoric acid or phosphate. However, the melamine salt used as component (A) in the present invention is preferably melamine pyrophosphate or melamine polyphosphate obtained by subjecting melamine orthophosphate to heating and condensation, with melamine pyrophosphate being particularly preferable.
    [0019] Unreacted melamine pyrophosphate may include unreacted melamine orthophosphate, over-reacted melamine polyphosphate, or other by-products.
    [0020] In the heating and condensation reaction of melamine orthophosphate, melamine pyrophosphate or melamine polyphosphate can be produced by heating melamine orthophosphate and subjecting it to a dehydration condensation reaction.
    [0021] It is preferable to conduct the heating and condensation reaction of melamine orthophosphate in a solid phase state; however, the reaction can be conducted in a molten state or in a slurry state in which a small amount of water is included. Of course, a solvent can be used for the reaction, but this is not preferable considering, for example, the time and difficulty of removing the solvent.
    [0022] Melamine pyrophosphate obtained by subjecting melamine orthophosphate to a heating and condensation reaction in a solid phase state can be used as such without refining.
    [0023] From the point of view of the purity of the obtained melamine pyrophosphate and production efficiency, the temperature to obtain melamine pyrophosphate by subjecting melamine orthophosphate to a heating and condensation reaction in a solid phase state is preferably 150°C to 300°C, more preferably 160 to 280°C. If the temperature is below 150°C, pyrophosphorylation cannot progress sufficiently, whereas temperatures above 300°C tend to produce a triphosphate salt or other polyphosphates that have undergone another dehydration condensation reaction.
    [0024] Reaction time is not particularly limited; the reaction can be conducted as appropriate depending on the temperature conditions until the dehydration condensation reaction of melamine orthophosphate to melamine pyrophosphate is completed.
    [0025] The piperazine salt used as component (B) in the flame retardant composition of the invention is selected from piperazine orthophosphate, piperazine pyrophosphate, and piperazine polyphosphate; the salt can be used alone or it can be used as a mixture. Among the above, piperazine pyrophosphate is preferable from the point of view of heat resistance, weather resistance and low risk of corrosion of processing machinery. In case of using a mixture, the higher the piperazine pyrophosphate content ratio, the more preferable.
    [0026] The aforementioned salts of phosphoric acids and piperazine can be obtained by reacting piperazine with corresponding phosphoric acid or phosphate. However, the piperazine salt used as component (B) in the present invention is preferably piperazine pyrophosphate or piperazine polyphosphate obtained by subjecting piperazine orthophosphate to heating and condensation, with piperazine pyrophosphate being particularly preferable.
    [0027] Piperazine pyrophosphate may include unreacted piperazine orthophosphate, piperazine polyphosphate produced by over-reaction, or other by-products.
    [0028] In the heating and condensation reaction of piperazine orthophosphate, piperazine pyrophosphate or piperazine polyphosphate can be produced by heating piperazine orthophosphate and subjecting it to a dehydration condensation reaction.
    [0029] It is preferable to conduct the heating and condensation reaction of piperazine orthophosphate in a solid phase state; however, the reaction can be conducted in a molten state or in a slurry state in which a small amount of water is included. Of course, a solvent can be used for the reaction, but this is not preferable considering, for example, the time and difficulty of removing the solvent.
    [0030] Piperazine pyrophosphate obtained by subjecting piperazine orthophosphate to a heating and condensation reaction in a solid phase state can be used as such without refining.
    [0031] From the point of view of the purity of the piperazine pyrophosphate obtained and the production efficiency, the temperature to obtain piperazine pyrophosphate by subjecting the piperazine orthophosphate to a heating and condensation reaction in a solid phase state is preferably 170°C to 320°C, more preferably 180 to 300°C. If the temperature is below 170°C, pyrophosphorylation cannot progress sufficiently, while temperatures above 320°C tend to produce a triphosphate salt or other polyphosphates that have undergone another dehydration condensation reaction.
    [0032] Reaction time is not particularly limited; the reaction can be conducted as appropriate depending on temperature conditions until the dehydration condensation reaction from piperazine orthophosphate to piperazine pyrophosphate is complete.
    [0033] The contents of component (A) and component (B) in the flame retardant composition of the invention, when the total content of component (A) and component (B) is 100 parts by mass are: 20 to 50 parts by component mass (A); and 50 to 80 parts by weight of component (B).
    [0034] In the following, component (C) of the present invention is described.
    [0035] In the present invention, a hydrotalcite compound is used as component (C). In the present invention, a hydrotalcite compound refers to a double salt compound of aluminum magnesium and/or zinc carbonate. The hydrotalcite compound can be a naturally occurring product or a synthetic product. Examples of methods for synthesizing such synthetics include known methods described, for example, in JP-B-46-2280, JP-B-50-30039, JP-B-51-29129, and JP-A-61-174270 . In the present invention, various hydrotalcite compounds can be used without regard to crystal structure, crystal grain diameter, presence/absence of water of crystallization, its amount, etc.
    [0036] The hydrotalcite compound can be treated with perchloric acid. Also, it is possible to use a hydrotalcite compound whose surface is covered with, for example, a higher fatty acid, such as stearic acid, a metal salt of a higher fatty acid, such as an alkali metal salt of oleic acid, a metal salt of of organic sulfonic acid, such as an alkali metal salt of dodecylbenzenesulfonic acid, a higher fatty acid amide, a higher fatty acid ester, or a wax.
    [0037] Preferably, the hydrotalcite compound is a compound represented by the following general formula (4).MgxiZnX2Al2(OH)2(xi+x2)+4CO3 IT1H2O... (4)(wherein, x1 and x2 each represent a number meeting the conditions represented by the following expressions, and represents a real number: 0<x2/x1 <10; and 2<x1+x2<20.)
    [0038] Commercially available products can be used for the hydrotalcite compound, with examples including DHT-4 (hydrotalcite; product of Kyowa Chemical Industry Co., Ltd), DHT-4A (hydrotalcite; product of Kyowa Chemical Industry Co., Ltd.) ), Magceler 1 (hydrotalcite; product of Kyowa Chemical Industry Co., Ltd.), Alcamizer 1 (hydrotalcite; product of Kyowa Chemical Industry Co., Ltd.), Alcamizer 2 (hydrotalcite; product of Kyowa Chemical Industry Co., Ltd. .), Alcamizer 4 (Alcamizer P-93) (zinc-modified hydrotalcite; product of Kyowa Chemical Industry Co., Ltd.), Alcamizer 7 (zinc-modified hydrotalcite; product of Kyowa Chemical Industry Co., Ltd.), and Alcamizer 5 (perchloric acid treated hydrotalcite; product of Kyowa Chemical Industry Co., Ltd.), wherein DHT-4A (hydrotalcite; product of Kyowa Chemical Industry Co., Ltd.) is particularly preferred.
    [0039] The content of component (C) in the flame retardant composition of the present invention is 0.01 to 5 parts by mass with respect to 100 parts by mass in total of component (A) and component (B). From the point of view of heat resistance, weather resistance, and low risk of corrosion of processing machines, the content in the flame retardant composition of the present invention is preferably from 0.05 to 4 parts by mass, more preferably from 0.1 to 2 parts by mass, with respect to 100 parts by mass in total of component (A) and component (B).
    [0040] The flame retardant composition of the present invention may further include zinc oxide, which serves as a flame retardant auxiliary. Zinc oxide can be surface treated. Commercially available zinc oxide products can be used and usable examples include type 1 zinc oxide (product of Mitsui Mining and Smelting Co., Ltd.), partially coated zinc oxide (product of Mitsui Mining and Smelting Co., Ltd. ), Nanofine 50 (ultrafine particles of zinc oxide; average particle size: 0.02 μm; product of Sakai Chemical Industry Co., Ltd ), and Nanofine K (ultrafine particles of zinc oxide coated with zinc silicate; size particle average: 0.02 μm; product of Sakai Chemical Industry Co., Ltd).
    [0041] The zinc oxide content in the flame retardant composition of the present invention is preferably from 0.5 to 10 parts by mass, more preferably from 1.2 to 5 parts by mass, with respect to 100 parts by mass of total of component (A) and component (B).
    [0042] In addition, the flame retardant composition of the present invention may include an anti-drip agent to prevent dripping at the time of combustion. Examples of anti-drip agents include fluorine-based anti-drip agents, silicone rubbers, and phyllosilicates. Among the above, fluorine-based anti-drip agents are preferred.
    [0043] Specific examples of fluorine-based anti-drip agents include: fluorine-based resins, such as polytetrafluoroethylene, polyvinylidene fluoride, and polyhexafluoropropylene; and compounds of alkali metal salt of perfluoroalkane sulfonic acids or alkaline earth metal salts of perfluoroalkane sulfonic acids, such as perfluoromethane sulfonic acid, sodium salt, perfluoro-n-butane sulfonic acid, potassium salt, perfluoro-t-butane sulfonic acid, potassium salt, perfluorooctane sulfonic acid sodium salt, perfluoro-2-ethyl-hexane acid calcium salt. Among the above anti-drip agents, polytetrafluoroethylene is most preferred from the point of view of ability to prevent dripping.
    [0044] In case of using a phyllosilicate as the anti-drip agent, examples of usable phyllosilicates include smectite-based clay minerals such as montmorillonite, saponite, hectorite, beidelite, stevensite and nontronite; and vermiculite, halloysite, intumescent mica and talc. Organic cations, quaternary ammonium cations or phosphonium cations can be intercalated between the layers.
    [0045] The content of the anti-drip agent in the flame retardant composition of the invention with respect to 100 parts by mass of total component (A) and component (B) is preferably 0.01 to 5 parts by mass, more preferably from 0.05 to 3 parts by mass, even more preferably from 0.1 to 1 part by mass. If the content of anti-drip agent is less than 0.01 parts by mass, the drip prevention effect may not be sufficient, and if the content exceeds 5 parts by mass, the resin characteristics may deteriorate.
    [0046] The flame retardant composition of the present invention may include a silicone oil in order to suppress secondary coagulation at the time of mixing and improve water resistance. Examples of silicone oils include: dimethyl silicone oils in which the side and end chains of a polysiloxane are all methyl groups; methylphenyl silicone oils wherein some of the side chains of a polysiloxane include phenyl groups; methyl hydrogen silicone oils, where some of the polysiloxane side chains include hydrogen; and copolymers of the above. It is also possible to use modified silicone oils, such as amine modified, epoxy modified, alicyclic epoxy modified, carboxyl modified, carbinol modified, mercapto modified, polyether modified, long chain alkyl modified, fluoroalkyl modified, higher fatty acid modified, higher fatty acid amide modified, silanol modified, diol modified, phenol modified, and/or aralkyl modified - in which organic groups are introduced into some part of the side and/or terminal chains.
    [0047] Specific examples of silicone oil are listed below. Examples of dimethyl silicone oils include KF-96 (product of Shin-Etsu Chemical Co., Ltd.), KF-965 (product of Shin-Etsu Chemical Co., Ltd.), and KF-968 (product of Shin-Etsu Chemical Co., Ltd.), and KF-968 (product of Shin-Etsu Chemical Co., Ltd.). Etsu Chemical Co., Ltd.). Examples of methyl hydrogen silicone oils or silicone oils having a methyl hydrogen polysiloxane backbone include KF-99 (product of Shin-Etsu Chemical Co., Ltd.), KF-9901 (product of Shin-Etsu Chemical Co., Ltd.), HMS-151 (product of Gelest Inc.), HMS-071 (product of Gelest Inc.), HMS-301 (product of Gelest Inc.), and DMS-H21 (product of Gelest Inc.). Examples of methylphenyl silicone oils include KF-50 (product of Shin-Etsu Chemical Co., Ltd.), KF-53 (product of Shin-Etsu Chemical Co., Ltd.), KF-54 (product of Shin-Etsu Chemical Co., Ltd. Chemical Co., Ltd.), and KF-56 (product of Shin-Etsu Chemical Co., Ltd.). Examples of epoxy-modified products include X-22-343 (product of Shin-Etsu Chemical Co., Ltd.), X-22-2000 (product of Shin-Etsu Chemical Co., Ltd.), KF-101 (product of from Shin-Etsu Chemical Co., Ltd.), KF-102 (product from Shin-Etsu Chemical Co., Ltd.), and KF-1001 (product from Shin-Etsu Chemical Co., Ltd.). An example of one of the carboxyl-modified products includes X-22-3701E (product of Shin-Etsu Chemical Co., Ltd.). Examples of carbinol-modified products include X-22-4039 (product of Shin-Etsu Chemical Co., Ltd.) and X-22-4015 (product of Shin-Etsu Chemical Co., Ltd.). An example of an amine-modified product includes KF-393 (product of Shin-Etsu Chemical Co., Ltd.).
    [0048] The flame retardant composition of the invention may include a silane coupling agent. A silane coupling agent is a compound that includes an organic functional group and a hydrolytic group, being represented, for example, by the general formula A-(CH2)k-Si(OR)3, where A represents an organic functional group , k represents a number from 1 to 3, and R represents a methyl group or an ethyl group. Examples of the organic group A include an epoxy group, a vinyl group, a methacrylic group, an amino group, and a mercapto group. A silane coupling agent including an epoxy group is particularly preferable for the silane coupling agent used in the present invention.
    [0049] It is also preferred that the flame retardant composition of the invention include a slip additive, as required. Examples of slip additives include: purely hydrocarbon based slip additives such as liquid paraffin, natural paraffin, microwax, synthetic paraffin, low molecular weight polyethylene, and polyethylene wax; halogenated hydrocarbon slip additives; fatty acid based slip additives such as higher fatty acids and oxyfatty acids; fatty acid amide-based slip additives, such as fatty acid amides and fatty acid bis-amides; ester-type slip additives such as lower alcohol esters of fatty acids, polyol esters of fatty acids such as glycerides, polyglycol esters of fatty acids, esters of fatty alcohols and fatty acids (ester waxes); metal soap, fatty alcohols, polyols, polyglycols, polyglycerols, partial esters of fatty acids and polyols, partial ester slip additives of fatty acids and polyglycols or polyglycerols, (meth)acrylic ester-based copolymers, silicone oils and oils minerals.
    [0050] It is also preferred that the flame retardant composition of the invention includes a polyol compound as a flame retardant auxiliary. A polyol compound is a compound in which a plurality of hydroxyl groups are attached, and examples include pentaerythritol, dipentaerythritol, tripentaerythritol, polypentaerythritol, neopentyl glycol, trimethylol propane, ditrimethylol propane, 1,3,5-tris(2-hydroxyethyl)isocyanurate , polyethylene glycol, glycerol, diglycerol, mannitol, maltitol, lactitol, sorbitol, erythritol, xylitol, xylose, sucrose, trehalose, inositol, fructose, maltose and lactose. Among the above polyol compounds, one or more types of compounds selected from the group consisting of pentaerythritol and pentaerythritol condensates - such as pentaerythritol, dipentaerythritol, tripentaerythritol, and polypentaerythritol - are preferred, dipentaerythritol and pentaerythritol condensates are more preferred, and dipentaerythritol is the most preferred.
    [0051] The pentaerythritol condensate may be a mixture of pentaerythritol and various pentaerythritol condensates (in the present invention, this is referred to as a (poly)pentaerythritol mixture. In the mixture of (poly)pentaerythritol, if n represents the degree of condensation of pentaerythritol, the total content of pentaerythritol and condensates thereof with n = 1 to 3 is 5 to 40% by mass with respect to the total amount of the mixture of (poly) pentaerythritol. (Note that the total content of pentaerythritol and condensates thereof with n = 1 to 3 and pentaerythritol condensates with amounts from n>4 to 100% by mass.) It should be noted that n = 1 indicates pentaerythritol, n = 2 indicates dipentaerythritol.
    [0052] As for the mixture of (poly)pentaerythritol, from the point of view of flame retardancy, if n represents the degree of condensation of pentaerythritol, a mixture in which the total content of pentaerythritol and condensates thereof with n = 1 to 3 is 10 to 30% by mass for the total amount of mixture is preferred; a mixture wherein the content of n = 1 pentaerythritol is 0 to 10% by mass and the total content of pentaerythritol and condensates thereof with n = 1 to 3 and 5 to 30% by mass, is more preferred; and a mixture wherein the content of n=1 pentaerythritol is 0 to 5% by mass and the total content of pentaerythritol and condensates thereof with n=1 to 3 is 10 to 30% by mass is most preferred.
    [0053] An example of the aforementioned pentaerythritol and condensates thereof is a compound represented by the following general formula (5).
    (where, t is an integer of 1 or greater.)
    [0054] The mixture of (poly)pentaerythritol may include, for example: compounds resulting from intramolecular etherification within a single pentaerythritol condensate shown in the above general formula (5), compounds resulting from the intermediate methylol group(s) forming ether(s) bonds with another(s) molecule(s), compounds that have bonded together in a mesh-like fashion, and large sized compounds formed by another bond between molecules, forming macrocyclic ether structures in several portions.
    [0055] The mixture of (poly)pentaerythritol can be produced according to known methods without limitation. For example, the mixture can be produced by a thermal dehydration condensation reaction of pentaerythritol and/or pentaerythritol condensates as such or in the presence of an appropriate catalyst and solvent.
    [0056] Examples of useful catalysts for producing the (poly)pentaerythritol mixture include inorganic acids and organic acids which are generally used for the dehydration condensation reaction of alcohols. Examples of inorganic acids include mineral acids such as phosphoric acid and sulfuric acid; acidic salts of such mineral acids; and solid acid catalysts such as clay minerals (eg montmorillonite), silica, alumina and zeolite. Examples of organic acids include formic acid and para-toluenesulfonic acid.
    [0057] There is no particular limitation on the amount of catalyst to be used. In case of using a water-soluble acid catalyst, it will be sufficient if the amount used can keep the pH of the reaction system during the reaction below 7, and preferably at or below 5. In case of using a solid acid catalyst , it will generally be sufficient if the amount used is from 0.1 to 100% by mass with respect to pentaerythritol.
    [0058] Examples of usable solvents for producing the (poly)pentaerythritol mixture include: hydrocarbons such as benzene, xylene, decalin, and tetralin; ethers such as dioxane, tetrahydrofuran, ethyl ether, anisole, phenyl ether, diglyme, tetraglyme, and 18-crown-6; methyl acetate, ethyl butyrate, and methyl benzoate; ketones such as γ-butyrolactone; N-substituted amides, such as N-methylpyrrolidinone, N,N-dimethylacetamide, N-methylpiperidone, and hexamethylphosphoric triamide; tertiary amines such as N,N-diethylaniline, N-methylmorpholine, pyridine, and quinoline; sulfones such as sulfolane; sulfoxides such as dimethyl sulfoxide; urea derivatives such as 1,3-dimethyl-2-imidazolidinone; phosphine oxides such as tributylphosphine oxide; and silicone oil. These solvents can be dehydrated or they can be hydrated.
    [0059] The temperature range for the thermal dehydration condensation reaction in the production of (poly)pentaerythritol mixture is generally about 100 to 280°C, more preferably 150 to 240°C. Reaction temperatures below 100°C can result in a slow reaction, while temperatures above 280°C can make the condensation reaction difficult to control.
    [0060] In cases of mixing the above-mentioned compound(s) for the flame retardant composition of the present invention, the amount that should be mixed with respect to 100 parts by mass in total of component (A) and component (B) is preferably from 0.5 to 15 parts by mass, more preferably from 2 to 12 parts by mass, and even more preferably from 5 to 10 parts by mass.
    [0061] In the flame retardant composition of the present invention, it is possible to use one or more types of non-halogen containing organic/inorganic flame retardants or flame retardant auxiliaries, if necessary, in amounts that do not affect the effects of the present invention. Examples of such flame retardants/flame retardant aids include triazine ring containing compounds, metal hydroxides, phosphoric ester based flame retardants, condensed phosphoric ester based flame retardants, phosphate based flame retardants, flame retardants based on inorganic phosphorus, salts of dialkylphosphinates, flame retardants based on silicone, metal oxides, boric acid compounds, intumescent graphite, other inorganic flame retardant auxiliaries, and other organic flame retardants.
    [0062] Examples of the triazine ring-containing compounds include melamine, ameline, benzoguanamine, acetoguanamine, phthalodiguanamine, melamine cyanide, butylene diguanamine, norbornene diguanamine, methylene diguanamine, ethylene dimelamine, trimethylene dimelamine, tetramethylene dimelamine, hexamethylene dimelamine, and 1,3- hexylene dimelamine.
    [0063] Examples of the metal hydroxides include magnesium hydroxide, aluminum hydroxide, calcium hydroxide, barium hydroxide, zinc hydroxide and Kisuma 5A (trade name magnesium hydroxide; product of Kyowa Chemical Industry Co., Ltd.) .
    [0064] Examples of phosphoric ester based flame retardants include trimethyl phosphate, triethyl phosphate, tributyl phosphate, tributexyethyl phosphate, trischloroethyl phosphate, trisdichloropropyl phosphate, triphenyl phosphate, tricresyl phosphate, cresyl diphenyl phosphate, trixylenyl phosphate, octyl diphenyl phosphate, xylenyl diphenyl phosphate, triisopropylphenyl phosphate, 2-ethylhexyl diphenyl phosphate, t-butylphenyl diphenyl phosphate, bis-(t-butylphenyl) phenyl phosphate, tris-(t-butylphenyl) phosphate, isopropylphenyl diphenyl phosphate, bis-(isopropylphenyl) diphenyl phosphate, and tris-(isopropylphenyl)phosphate.
    [0065] Examples of condensed phosphoric ester based flame retardants include 1,3-phenylene bis(diphenyl phosphate), 1,3-phenylene bis(dixylenyl phosphate) and bisphenol A, bis(diphenyl phosphate).
    [0066] An example of inorganic phosphorus-based flame retardant includes red phosphorus.
    [0067] Examples of the dialkylphosphinate salts include aluminum diethylphosphinate and zinc diethylphosphinate.
    [0068] Examples of other inorganic flame retardant aids include inorganic compounds such as titanium oxide, aluminum oxide and magnesium oxide, and products treated on the surface thereof. As specific examples thereof, you can use various commercially available products, such as Tipaque R-680 (trade name titanium oxide; product of Ishihara Sangyo Kaisha, Ltd.) and Kyowa Mag 150 (trade name magnesium oxide; product of Kyowa Chemical Industry Co., Ltd.).
    [0069] The flame retardant composition used in the present invention may include, if necessary, a phenol-based antioxidant, a phosphorus-based antioxidant, a thioether-based antioxidant, a UV absorber, a light stabilizer based on of hindered amine, an anti-aging agent, and the like. These components may be mixed beforehand into the flame retardant composition of the invention, or they may be mixed with a synthetic resin at the time of mixing the flame retardant composition of the invention with the synthetic resin. It is preferable to stabilize the synthetic resin by mixing these components.
    [0070] Examples of the phenol-based antioxidant include 2,6-di-tert-butyl-p-cresol, 2,6-diphenyl-4-octadesyloxyphenol, distearyl (3,5-di-tert-butyl-4-hydroxybenzyl )phosphonate, 1,6-hexamethylene-bis[(3,5-di-tert-butyl-4-hydroxyphenyl)propionic acid amide], 4,4'-thio-bis(6-tert-butyl-m-cresol ), 2,2'-methylene-bis(4-methyl-6-tert-butylphenol), 2,2'-methylene-bis(4-ethyl-6-tert-butylphenol), 4,4'-butylidene-bis (6-tert-butyl-m-cresol), 2,2'-ethylidene-bis(4,6-di-tert-butylphenol), 2,2'-ethylidene-bis(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-hyd roxybenzyl)-2,4,6-trimethylbenzene, 2-tert-butyl-4-methyl-6-(2-acryloyloxy-3-tert-butyl-5-methylbenzyl)phenol, stearyl(3,5-di-tert- butyl-4-hydroxyphenyl)propionate, tetrakis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)methylpropionate]methane, thiodiethylene glycol col bis[(3,5-di-tert-butyl-4-hydroxyphenyl)propionate], 1,6-hexamethylene-bis[(3,5-di-tert-butyl-4-hydroxyphenyl)propionate], glycol ester bis[3,3-bis(4-hydroxy-3-tert-butylphenyl)butyric acid], bis[2-tert-butyl-4-methyl-6-(2-hydroxy-3-tert-butyl-5- methylbenzyl)phenyl]terephthalate, 1,3,5-tris[(3,5-di-tert-butyl-4-hydroxyphenyl)propionyloxyethyl]isocyanurate, 3,9-bis[1,1-dimethyl-2-{(3 -tert-butyl-4-hydroxy-5-methylphenyl)propionyloxy}ethyl]-2,4,8,10-tetraoxaspiro[5,5]undecane, and bis[(3-tert-butyl-4-hydroxy-5- methylphenyl)propionate] triethylene glycol
    [0071] The amount of the phenol-based antioxidant(s) used when mixed with a synthetic resin is preferably 0.001 to 5% by mass, more preferably 0.05 to 3% by mass, in the resin composition synthetic.
    [0072] Examples of the phosphorus-based antioxidant include trisnonylphenyl phosphite, tris[2-tert-butyl-4-(3-tert-butyl-4-hydroxy-5-methylphenylthio)-5-methylphenyl] phosphite, tridecyl phosphite, octyldiphenyl phosphite, di(decyl)monophenyl phosphite, di(tridecyl)pentaerythritol diphosphite, di(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, tetra(tridecyl)isopropylidenediphenol diphosphite, tetra(tridecyl)-4,4 '-n-butylidene bis(2-tert-butyl-5-methylphenol) diphosphite, hexa(tridecyl)-1,1,3-tris(2-methyl-4-hydroxy-5-tert-butylphenyl)butane triphosphite, tetrakis(2,4-di-tert-butylphenyl)biphenylene diphosphonite, 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, 2,2'-methylene-bis(4,6-tert-butylphenyl) -2-ethylhexyl phosphite, 2,2'-methylene-bis(4,6-tert-butylphenyl)-octadecyl phosphite, 2,2'-ethylidene-bis(4,6-di-tert-but ylphenyl) fluorophosphite, tris(2-[(2,4,8,10-tetrakis-tert-butyldibenzo[d,f][1,3,2]dioxaphosphopin-6-yl)oxy]ethyl)amine, and a phosphite of 2-ethyl-2-butylpropylene glycol and 2,4,6-tri-tert-butylphenol. The amount of the phosphorus-based antioxidant(s) used when mixed with a synthetic resin is preferably from 0.001 to 5% by mass, more preferably from 0.05 to 3% by mass, in the synthetic resin composition.
    [0073] Examples of the thioether-based antioxidant include dialkyl thiodipropionates, such as dilauryl thiodipropionate, dimyristii thiodipropionate, and distearyl thiodipropionate, and pentaerythritol tetra (β-alkyl mercaptopropionates). The amount of the thioether-based antioxidant(s) used when mixed with a synthetic resin is preferably from 0.001 to 5% by mass, more preferably from 0.05 to 3% by mass, in the synthetic resin composition.
    [0074] Examples of the UV absorber include: 2-hydroxybenzophenones such as 2,4-dihydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone, 2-hydroxy-4-octoxybenzophenone, and 5,5'-methylene-bis(2-hydroxy-benzophenone). 4-methoxybenzophenone); 2-(2'-hydroxyphenyl)benzotriazoles such as 2-(2'-hydroxy-5'-methylphenyl)benzotriazole, 2-(2'-hydroxy-3',5'-di-tert-butylphenyl)-5-chlorobenzotriazole, 2-(2'-hydroxy-3'-tert-butyl-5'-methylphenyl)-5-chlorobenzotriazole, 2-(2'-hydroxy-5'-tert-octylphenyl)benzotriazole, 2-(2'-hydroxy- 3',5'-dicumylphenyl)benzotriazole, 2,2'-methylene-bis(4-tert-octyl-6-(benzotriazolyl)phenol), and 2-(2'-hydroxy-3'-tert-butyl-5 '-carboxyphenyl)benzotriazole; benzoates such as phenyl salicylate, resorcinol monobenzoate, 2,4-di-tert-butylphenyl-3,5-di-tert-butyl-4-hydroxybenzoate, 2,4-di-tert-amylphenyl-3,5-di-tert -butyl-4-hydroxybenzoate, and hexadecyl-3,5-di-tert-butyl-4-hydroxybenzoate; substituted oxanilides 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 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. The amount of the UV absorber(s) used when mixed with a synthetic resin is preferably from 0.001 to 5% by mass, more preferably from 0.05 to 3% by mass, in the synthetic resin composition.
    [0075] Examples of the hindered amine based light stabilizer include hindered amine such as 2,2,6,6-tetramethyl-4-piperidyl stearate, 1,2,2,6,6-pentamethyl-4-piperidyl, 2,2,6,6-Tetramethyl-4-bis(2,2,6,6-tetramethyl-4-piperidylamino)hexane/2,4-dichloro-6-tert-octylamino-s-triazine benzoate, 1, 5,8,12-tetrakis[2,4-bis(N-butyl-N-(2,2,6,6-tetramethyl-4-piperidyl)amino)-s-triazin-6-yl]-1,5 ,8,12-tetraaza pentamethyl-4-piperidyl) tris[2,4-bis(N-butyl-N-aminoundecane, piperidyl)amino)-s-triazin-6-yl]aminoundecane. The amount of the hindered amine based light stabilizer(s) used when mixed with a synthetic resin is preferably from 0.001 to 5% by mass, more preferably from 0.05 to 3% by mass. mass, in the synthetic resin composition.
    [0076] Examples of the anti-aging agent include naphthylamine-based agents, diphenylamine-based agents, p-phenyldiamine-based agents, quinoline-based agents, hydroquinone derivatives, monophenol-based agents, thiobisphenol, hindered phenol-based agents, and phosphite ester-based agents. The amount of anti-aging agent(s) used when mixed with a synthetic resin is preferably from 0.001 to 5% by mass, more preferably from 0.05 to 3% by mass, in the synthetic resin composition. .
    [0077] The flame retardant composition of the present invention may include, as optional components, reinforcing materials, in amounts that do not affect the effects of the present invention. These components can be mixed with a synthetic resin at the time of mixing the flame retardant composition of the invention with the synthetic resin. Fibrous, tabular, granular, or powdered reinforcing materials that are commonly used for reinforcing synthetic resins can be used as reinforcing materials. Specific examples include: inorganic fibrous reinforcing materials such as fiberglass, asbestos fiber, carbon fiber, graphite fiber, metal fiber, potassium titanate whisker, aluminum borate whisker, magnesium-based whisker, whisker based on silicon, wollastonite, sepiolite, asbestos, slag fiber, zonolite, ellestadite, gypsum fiber, silica fiber, alumina silica fiber, zirconia fiber, boron nitride fiber, silicon nitride fiber and fiber boron; organic fibrous reinforcing materials such as polyester fibers, nylon fiber, acrylic fiber, regenerated cellulose fiber, acetate fibers, kenaf, ramie, cotton, jute, hemp, sisal, linen, silk, Manila hemp, sugar cane , wood pulp, waste paper, waste paper and wool; and tabular/granular reinforcing materials such as glass flakes, non-swellable mica, graphite, thin sheet metal, ceramic beads, clay, mica, sericite, zeolite, bentonite, dolomite, kaolin, micronized silicate, feldspar powder, titanate of potassium, shirasu flask, calcium carbonate, magnesium carbonate, barium sulfate, calcium oxide, aluminum oxide, titanium oxide, aluminum silicate, silicon oxide, gypsum, novaculite, dawsonite, and white clay. These reinforcing materials may be coated or bundled with a thermoplastic resin, such as an ethylene/vinyl acetate copolymer, or a thermoset resin, such as an epoxy resin, or they may be treated with, for example, a coupling agent such as amino silane or epoxy silane.
    [0078] The flame retardant composition of the present invention may further include, as an optional component, a crystal nucleator, in an amount that does not affect the effects of the present invention. Any nucleator commonly used as a polymeric crystal nucleator can be properly used as the crystal nucleator. In the present invention, both inorganic and organic crystal nucleators can be used. These components can be mixed with a synthetic resin at the time of mixing the flame retardant composition of the invention with the synthetic resin.
    [0079] Specific examples of inorganic crystal nucleators include kaolinite, synthetic mica, clay, zeolite, silica, graphite, carbon black, magnesium oxide, titanium oxide, calcium sulfide, boron nitride, calcium carbonate, barium sulfate , aluminum oxide, neodymium oxide, and metal salts of phenylphosphonate and others. These inorganic based crystal nucleators can be modified by organic substances in order to improve their dispersibility in the composition.
    [0080] Specific examples of organic crystal nucleators include: organic metal carboxylate salts such as sodium benzoate, potassium benzoate, lithium benzoate, calcium benzoate, magnesium benzoate, barium benzoate, lithium terephthalate, sodium terephthalate , potassium terephthalate, calcium oxalate, sodium laurate, potassium laurate, sodium myristate, potassium myristate, calcium myristate, sodium octacosanoate, calcium octacosanoate, sodium stearate, potassium stearate, lithium stearate, stearate calcium, magnesium stearate, barium stearate, sodium montanate, calcium montanate, toluic acid, sodium salt, sodium salicylate, potassium salicylate, zinc salicylate, aluminum dibenzoate, potassium dibenzoate, lithium dibenzoate, β- sodium naphthalate, and sodium cyclohexane carboxylate; organic sulfonate salts such as sodium p-toluene sulfonate and sodium sulfoisophthalate; carboxylic acid amides, such as stearamide, ethylene-bis-lauric acid amide, palmitic acid amide, hydroxystearamide, erucamide, and tris(tert-butyramide) trimesic acid; benzylidenesorbitol and its derivatives, metal salts of phosphorus compounds, such as sodium 2,2'-methylenebis(4,6-di-tert-butylphenyl)phosphate; and sodium 2,2-methylbis(4,6-di-tert-butylphenyl).
    [0081] The flame retardant composition of the present invention may include, as an optional component, a plasticizer, in an amount that does not affect the effects of the present invention. Any plasticizer commonly used as a polymer plasticizer can be used as appropriate as the plasticizer, and examples include polyester-based plasticizers, glycerol-based plasticizers, polycarboxylic acid ester-based plasticizers, polyalkylene glycol-based plasticizers, and plasticizers. epoxy based.
    [0082] These components can be mixed with a synthetic resin at the time of mixing the flame retardant composition of the invention with the synthetic resin.
    [0083] Specific examples of polyester-based plasticizers include: polyesters of an acid component, such as adipic acid, sebacic acid, terephthalic acid, isophthalic acid, naphthalene dicarboxylic acid, diphenyldicarboxylic acid, and pitch resin, and a diol component, such as propylene glycol, 1,3-butane-diol, 1,4-butane diol, 1,6-hexane diol, ethylene glycol, and diethylene glycol; and polyesters consisting of hydroxycarboxylic acids, such as polycaprolactone. The ends of these polyesters can be blocked by a monofunctional carboxylic acid or a monofunctional alcohol, or they can be blocked by an epoxy compound, etc.
    [0084] Specific examples of glycerol-based plasticizers include glycerol monoacetomonolaurate, glycerol diacetomonolaurate, glycerol monoacetomonostearate, glycerol diacetomonooleate and glycerol monoacetomonomontanate. Specific examples of polycarboxylic acid ester-based plasticizers include: phthalate esters, such as dimethyl phthalate, diethyl phthalate, dibutyl phthalate, dioctyl phthalate, diheptyl phthalate, dibenzyl phthalate, and benzyl butyl phthalate ; trimellitate esters such as tributyl trimellitate, trioctyl trimellitate, trihexyl trimellitate; adipate esters such as diisodecyl adipate, n-octyl-n-decyl adipate, methyl diglycol butyldiglycol adipate, benzyl methyl diglycol adipate, and benzyl butyl diglycol adipate; citrate esters such as triethyl acetyl citrate and tributyl acetyl citrate; azelate esters such as di-2-ethylhexyl azelate; and sebacate esters such as dibutyl sebacate and di-2-ethylhexyl sebacate.
    [0085] Specific examples of plasticizers based on polyalkylene glycol include: polyalkylene glycols such as polyethylene glycol, polypropylene glycol, block and/or random copolymers of poly(ethylene oxide-propylene oxide), polytetramethylene glycol, addition polymers ethylene oxide bisphenols, propylene oxide addition polymers of bisphenols, tetrahydrofuran addition polymers of bisphenols; and compounds blocked at the termini thereof, such as epoxy terminal modified compounds, ester terminal modified compounds, and ether terminal modified compounds.
    [0086] An epoxy-based plasticizer generally refers, for example, to an epoxy triglyceride consisting of alkyl epoxy stearate and soybean oil, so-called epoxy resins - which primarily employ bisphenol A and epichlorohydrin as materials - may be used.
    [0087] Specific examples of other plasticizers include benzoic acid esters of aliphatic polyols such as neopentyl glycol dibenzoate, diethylene glycol dibenzoate, and triethylene glycol di-2-ethylbutyrate, fatty acid amides such as stearamide, acid esters aliphatic carboxylic acids such as butyl oleate, oxyacid esters such as methyl acetylricinoleate and butyl acetyl ricinoleate, pentaerythritol, various sorbitols, polyacrylic esters and paraffins.
    [0088] Only one type of plasticizer may be used, or two or more types of plasticizer may be used in combination, in cases of using plasticizer(s) in the present invention.
    [0089] In addition, if necessary, the flame retardant composition of the present invention may include additives - such as cross-linking agents, anti-static agents, metal soaps, fillers, anti-fog agents, anti-plaque agents, surface treatment agents, fluorescents, fungicides, bactericides, foaming agents, metal deactivators, mold release agents, pigments, processing aids, flow improvers, thickening agents, thixotropics and fumigated silica - which are commonly used for synthetic resins in amounts that do not affect the effects of the present invention.
    [0090] These components can be mixed with a synthetic resin at the time of mixing the flame retardant composition of the invention with the synthetic resin.
    [0091] When the flame retardant composition of the present invention is dispersed in water in an amount that is 9 times the mass of the composition and is thus made into a liquid in a slurry state, it is preferable that the liquid has a pH at 25°C within a range of 3.0 to 5.0, more preferably in the range of 3.5 to 5.0, most preferably within a range of 4.0 to 5.0.
    [0092] It is not preferable for the pH to be below 3.0, because the heat resistance may be impaired and the composition may corrode the processing machines, and the weather resistance may be impaired when the composition is used with a resin synthetic.
    [0093] The pH range can be adjusted by raising the pH by adding the hydrotalcite compound of component (C).
    [0094] The flame retardant composition of the present invention is effective in flameproof synthetic resins and is preferably used as a flame retardant synthetic resin composition when mixed with a synthetic resin.
    [0095] Specific examples of synthetic resins that are flameproof by the flame retardant composition of the present invention include thermoplastic resins and mixtures thereof, including polyolefins and copolymers thereof, for example α-olefin polymers such as polypropylene, high density, low density polyethylene, linear low density polyethylene, crosslinked polyethylene, ultra high molecular weight polyethylene, polybutene-1, and poly-3-methylpentene, ethylene-vinyl acetate copolymer, ethylene-ethyl acrylate copolymer , and ethylene-propylene copolymer; halogen-containing resins such as polyvinyl chloride, chlorinated polyethylene polyvinylidene chloride, chlorinated polypropylene, polyvinylidene fluoride, chlorinated rubber, vinyl chloride-vinyl acetate copolymer, vinyl chloride-ethylene copolymer, vinyl chloride-chloride copolymer vinylidene, vinyl chloride-vinylidene chloride-vinyl acetate terpolymer, vinyl chloride-acrylic ester copolymer, vinyl chloride-maleic ester copolymer, and vinyl chloride-cyclohexyl maleimide copolymer; petroleum resins, coumarone resins, polystyrene, polyvinyl acetate, acrylic resins, copolymers of styrene and/or a-methyl styrene with other monomers, (e.g. maleic anhydride, phenyl maleimide, methyl butadiene methacrylate, acrylonitrile, etc.) , (eg AS resin, ABS resin, ACS resin, MBS resin, SBS resin, heat resistant ABS resin, etc.); polymethyl methacrylate, polyvinyl alcohol, polyvinyl formal, polyvinyl butyral; linear polyesters, for example, polyalkylene terephthalates, such as polyethylene terephthalate, polybutylene terephthalate, and polycyclohexane dimethylene terephthalate; aromatic polyesters, for example, polyalkylene naphthalates, such as polyethylene naphthalate and polybutylene naphthalate, and polytetramethylene terephthalate; degradable aliphatic polyesters such as polyhydroxybutyrate, polycaprolactone, polybutylene succinate, polyethylene succinate, polylactic resin, polymalic acid, polyglycolic acid, polydioxane, and poly(2-oxetanone); polyphenylene oxide; polyamides such as polycaprolactam, and polyhexamethylene adipamide; polycarbonate; branched polycarbonate; polyacetal; polyphenylene sulfide; polyurethane; and cellulose-based resins. Other examples include: thermosetting resins such as phenolic resin, urea resin, melamine resin, epoxy resin, unsaturated polyester resin; fluorine-based resin; silicone resin, polyether sulfone silicone rubber; polysulfone; polyphenylene ether; polyether ketone; polyether ether ketone; and liquid crystal polymers. Also, other examples include elastomers such as isoprene rubber, butadiene rubber, acrylonitrile-butadiene copolymer rubber, styrene-butadiene copolymer rubber, fluorine rubber, silicone rubber, olefin-based elastomers, styrene-based elastomers , polyester-based elastomers, nitrile-based elastomers, nylon-based elastomers, vinyl chloride-based elastomers, polyamide-based elastomers, and polyurethane-based elastomers.
    [0096] Two or more types of these synthetic resins can be used, or the synthetic resins can be bonded.
    [0097] Any type of synthetic resin can be used in the present invention, whatever the factors such as molecular weight, degree of polymerization, density, softening point, proportion of solvent-insoluble moieties, degree of three-dimensional regularity, presence/absence of catalyst residue, types and content ratio of starting materials such as monomers etc, and types of polymerization catalysts (eg Ziegler catalyst or metallocene catalyst etc).
    [0098] Among the synthetic resins mentioned above, polyolefin-based resins are particularly preferred. Examples of polyolefin-based resins include: o-olefin polymers such as low density polyethylene, linear low density polyethylene, high density polyethylene, isotactic polypropylene, syndiotactic polypropylene, hemiisotactic polypropylene, polybutene, cycloolefin polymer, stereo-polypropylene block, poly-3-methyl-1-butene, poly-3-methyl-1-pentene, and poly-4-methyl-1-pentene, and α-olefin copolymers, such as ethylene/propylene block or random copolymer, ethylene-methyl methacrylate copolymer, and ethylene-vinyl acetate copolymer.
    [0099] The flame retardant synthetic resin composition of the present invention preferably from 3 to 100 parts by mass—more preferably from 10 to 90 parts by mass, even more preferably from 20 to 80 parts by mass—of the flame retardant composition of the present invention. present invention with respect to 100 parts by mass of the aforementioned synthetic resin(s).
    [00100] A molded product having excellent flame retardancy can be produced by forming the flame retardant synthetic resin composition of the present invention. There is no particular limitation on forming methods, and examples thereof include extrusion, calendering, injection molding, rolling, compression molding and blow molding. Various molded products having a variety of shapes can be manufactured, such as resin boards, sheets, films, as well as irregularly shaped components.
    [00101] The resin composition can be used for, for example: housing (e.g. frames, cases, covers and exterior materials) and components of electric vehicles, machinery, electrical/electronic equipment, and office automation equipment, and materials for automotive exteriors/interiors.
    [00102] The flame retardant synthetic resin composition and molded product according to the present invention can be used in a wide variety of industries, such as electricity, electronics, telecommunications, agriculture, forestry, fishing, mining, construction, food, textiles , clothing, medical products/services, coal, petroleum, rubber, leather, automobiles, precision equipment, wood, construction materials, civil engineering, furniture, printing, musical instruments. More specifically, the present invention can be used for: office supplies and office automation equipment such as printers, personal computers, word processors, keyboards, PDAs (or compact information terminals, telephones, copiers, fax machines, ECRs (electronic cash registers), calculators, electronic organizers, cards, holders, and stationery; home appliances, such as washing machines, refrigerators, vacuum cleaners, microwave ovens, lighting equipment, game machines, irons, and foot warmers ; audio-visual equipment, such as TV sets, VCRs, camcorders, cassette recorders, tape recorders, mini-discs, CD players, loudspeakers and liquid crystal displays; electrical/electronic components and telecommunications equipment , such as connectors, relays, capacitors, switches, printed circuit boards, coils, sealing materials for semiconductors, mat sealing materials for LEDs, electrical wires, cables, transformers, deflection coils, distribution boards and clocks; housing (frames, cases, covers and exterior materials) and components of office automation equipment, etc.; and materials for automotive interiors and exteriors.
    [00103] In addition, the flame retardant synthetic resin composition and molded product according to the present invention can be used in various applications, such as: materials for automobiles, hybrid cars, electric cars, vehicles, ships, aircraft, architecture , houses and constructions such as seats (fillers, outer cloth, etc.), belts, roof coverings, convertible benches, armrests, door moldings, rear packing trays, rugs, doormats, sun shields, wheel covers , mattress covers, air bags, insulating materials, strips, strip straps, wire covers, electrical insulators, paints, coating materials, wrapping materials, flooring materials, corner walls, carpets, wallpaper, flooring wall, exterior cladding, interior cladding, roofing materials, flooring materials, wall materials, pillar materials, flooring, fencing materials, frames, frames, windows, s in the form of doors, roof tiles, wainscoting, terraces, balconies, soundproof boards, thermal insulation boards, and window materials; civil engineering materials; and everyday household items and sporting equipment such as clothing, curtains, sheets, chipboards, synthetic fiber boards, small mats, mats, sheets, buckets, hoses, containers, eyeglasses, bags, cases, goggles, skis, rackets , tents and musical instruments. EXAMPLES
    [00104] The present invention is described in more detail below, in accordance with the Examples. The present invention, however, is not limited by any of the following Examples. {Examples 1 to 6 and Comparative Examples 1 to 4}
    [00105] Component (A) and component (B) were produced according to the following methods.{Production Example 1} Component (A): Melamine salt
    [00106] Melamine orthophosphate was subjected to a heating and condensation reaction at 220°C for 6 hours, in a solid phase state, to produce a melamine salt including melamine pyrophosphate as a main component. Melamine salt was used as is, without refining. The purity of melamine pyrophosphate in the melamine salt was 98.5%.
    [00107] Purity was measured using an HPLC device (pump: SSC-3150; RI detector: ERC-7515A) from Senshu Scientific Co., Ltd., a column oven (CO-965) from JASCO Corporation, and a OHpak column (SB-802.5 HQ) from Shodex.{Production Example 2}Component (B): Piperazine Salt
    [00108] Piperazine orthophosphate was subjected to a heating and condensation reaction at 250°C for 1 hour in a solid phase state, to produce a piperazine salt, including piperazine pyrophosphate as the main component. The piperazine salt was used as is, without refining. The purity of piperazine pyrophosphate in the piperazine salt was 99.0%.
    [00109] Purity was measured using an HPLC device (pump: SSC-3150; RI detector: ERC-7515A) from Senshu Scientific Co., Ltd., a column oven (CO-965) from JASCO Corporation, and a OHpak column (SB -802.5 HQ) from Shodex.
    [00110] Next, according to each formulation shown in Table 1, flame retardant compositions were prepared according to the respective examples. Likewise, according to each formulation shown in Table 1, flame retardant compositions were prepared according to the respective comparative examples.
    [00111] The pH of each flame retardant composition obtained was measured according to the following measurement method. The results are shown in Table 1.
    [00112] A corrosion test of each flame retardant composition obtained was conducted according to the following corrosion test method. The results are shown in Table 1.
    [00113] A heat resistance test of each flame retardant composition obtained was conducted according to the following heat resistance test method. The results are shown in Table 1.{pH measurement method}
    [00114] To 36 g of water in a 100 ml beaker, 4 g of the flame retardant composition was added. The beaker was subjected to ultrasonic vibration at room temperature for 30 minutes to obtain a slurry liquid including 10% by mass of the flame retardant composition. The pH of the slurry liquid obtained at 25°C was measured with a pH meter (F-72 LaQua from Horiba, Ltd). This operation was performed three times, and the average value was taken as the pH of the flame retardant composition.{Corrosion Test Method}
    [00115] 10 g of the flame retardant composition was placed in a 100 ml glass test tube. A 10 mm diameter brass test rod was placed in the test tube such that the lower half of the test rod was immersed in the flame retardant composition. The test tube was placed in a block bath at 200°C in air and heated. After 400 hours, the surface condition of the portion of the brass test rod that was immersed in the flame retardant composition was visually checked, and it was evaluated as follows. Poor: Blackening of the test rod surface due to corrosion. Satisfactory: Slight color change on test rod surface. Good: Almost no change on test rod surface. {Heat resistance test method}
    [00116] The temperature was raised from 30°C to 310°C at a temperature rise rate of 10°C/minute under an air flow of 200 ml/minute using a Thermo plus EVO differential thermogravimetric thermal analysis device ( product of Rigaku Co., Ltd), to measure the temperature of 1% weight loss.{Examples 7 to 12 and Comparative Examples 5 to 8}
    [00117] A polypropylene resin composition was obtained by mixing, at 70 parts by mass of polypropylene (melt flow rate: 8 g/10 min), 0.1 part by mass of calcium stearate (slip additive) , 0.1 part by mass of tetrakis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)methylpropionate]methane (phenol-based antioxidant), 0.1 part by mass of tris (2.4 -di-tert-butylphenyl) phosphite (phosphorus-based antioxidant), and 0.3 part by mass of glycerol monostearate (slip additive). To the obtained polypropylene resin composition, the respective flame retardant compositions obtained according to Examples 1 to 6 were added according to the proportion (% by mass) shown in Table 2, to obtain flame retardant synthetic resin compositions. resulting from Examples 7 to 12. Note that with respect to used flame retardant compositions, the flame retardant composition obtained according to Example 1 is indicated as flame retardant composition 1, the flame retardant composition obtained according to Example 2 is indicated as flame retardant composition 2, and the same applies to flame retardant composition 6.
    [00118] Likewise, the flame retardant composition obtained according to Comparative Example 1 is indicated as comparative flame retardant composition 1, the flame retardant composition obtained according to Comparative Example 2 is indicated as flame retardant composition comparative 2, and the same applies for comparative flame retardant composition 4. The respective comparative flame retardant compositions were used according to the formulation indicated in Table 2, to obtain the resulting flame retardant synthetic resin composition according to Comparative Examples 5 to 8.
    [00119] Each of the flame retardant synthetic resin compositions obtained according to respective Examples 7 to 12 was extruded at a temperature of 200 to 230°C and made into granules, and the granules were used for injection molding at 200° C, in test bodies 127 mm long and 12.7 mm wide and 1.6 mm thick. A flame retardancy test was performed using each test piece, whereby a UL-94V test was performed according to the following test method. The results are shown *• in Table 2. Likewise, the respective flame retardant synthetic resin compositions of comparative examples 5 to 8 were each subjected to the UL-94V test. The results are shown in Table 2.
    [00120] In addition, the resulting flame retardant synthetic resin compositions obtained by Examples 7 to 12 were each subjected to a weather resistance test according to the following test method. The results are shown in Table 2.
    [00121] Likewise, the respective flame retardant synthetic resin compositions obtained by Comparative Examples 5 to 8 were each subjected to the weather resistance test. Results are shown in Table 2. {UL-94V Flame Retardance Test)
    [00122] The test body 127 mm long, 12.7 mm wide and 1.6 mm thick was held vertically, a flame from the burner was placed in contact with the lower end of the test body for 10 seconds and then the flame was removed, and the time it took for the fire that caught the test body to cease was measured. Then, at the same time as the burning ceased, a flame from the burner was brought into contact with the test piece for 10 seconds for the second time, and the time it took for the fire that caught the test piece to cease was measured, as at the first time. At the same time, evaluation was made with respect to whether or not ignited particles that fell from the specimen ignited a piece of cotton located below the specimen.
    [00123] From the first and second combustion times and whether or not the piece of cotton caught fire, each test piece was classified according to UL-94V. The V-0 combustion rating is the highest rating, and flame retardancy decreases on the order of V-1 to V-2. Note that test specimens that do not fall into any of the V-0 to V-2 classifications are indicated as NR.{Weather Resistance Test Method} *•
    [00124] The yellowness index (Yl) of each of the above mentioned test bodies was measured at 240 hours and 360 hours using a Sunshine weather gauge (product of Suga Test Instruments Co., Ltd.) under the following conditions: 63°C, with rain. A TC-8600A color difference meter (product of Tokyo Denshoku Co., Ltd.) was used to measure the yellowing index.

    权利要求:
    Claims (5)
    [0001]
    1. Flame retardant composition, characterized in that it comprises from 20 to 50 parts by mass of component (A) described below, 50 to 80 parts by mass of component (B) described below (the total of component (A) and the component (B) is 100 parts by mass) and 0.01 to 5 parts by mass of component (C) described below: component (A): at least one type of melamine salt selected from melamine orthophosphate, melamine pyrophosphate, melamine polyphosphate, or a mixture including two or more types of melamine salts; component (B): at least one type of piperazine salt selected from piperazine orthophosphate, piperazine pyrophosphate, piperazine polyphosphate or a mixture including two or more types of piperazine salts; ecomponent (C): a hydrotalcite compound, wherein a liquid obtained by dispersing the flame retardant composition in water in an amount that is 9 times the mass of the composition has a pH within a range of 4.0 to 5.0 at 25°C.
    [0002]
    2. Flame retardant composition according to claim 1, characterized in that: at least one type of melamine salt selected as component (A) is a melamine salt obtained by subjecting melamine orthophosphate to heating and condensation; and at least one type of the piperazine salt selected as component (B) is a piperazine salt obtained by subjecting piperazine orthophosphate to heating and condensation.
    [0003]
    3. Composition of flame retardant synthetic resin, characterized in that it is made by mixing the flame retardant composition as defined in any one of claims 1 or 2, with a synthetic resin.
    [0004]
    4. Flame retardant synthetic resin composition according to claim 3, characterized in that the synthetic resin is a polyolefin-based resin.
    [0005]
    5. Molded product, characterized in that it is obtained from the flame retardant synthetic resin composition as defined in any one of claims 3 or 4.
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    同族专利:
    公开号 | 公开日
    TW201510032A|2015-03-16|
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    BR112015029500A2|2017-07-25|
    US20160152798A1|2016-06-02|
    KR102230010B1|2021-03-19|
    JP6387007B2|2018-09-05|
    JPWO2015025658A1|2017-03-02|
    EP3037502A4|2017-04-26|
    EP3037502A1|2016-06-29|
    WO2015025658A1|2015-02-26|
    TWI672333B|2019-09-21|
    EP3037502B1|2019-10-16|
    KR20160045627A|2016-04-27|
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    法律状态:
    2018-02-27| B06F| Objections, documents and/or translations needed after an examination request according [chapter 6.6 patent gazette]|
    2019-10-29| B06U| Preliminary requirement: requests with searches performed by other patent offices: procedure suspended [chapter 6.21 patent gazette]|
    2021-07-20| B350| Update of information on the portal [chapter 15.35 patent gazette]|
    2021-08-24| B06A| Patent application procedure suspended [chapter 6.1 patent gazette]|
    2021-12-07| B09A| Decision: intention to grant [chapter 9.1 patent gazette]|
    2022-02-01| B16A| Patent or certificate of addition of invention granted [chapter 16.1 patent gazette]|Free format text: PRAZO DE VALIDADE: 20 (VINTE) ANOS CONTADOS A PARTIR DE 18/07/2014, OBSERVADAS AS CONDICOES LEGAIS. |
    优先权:
    申请号 | 申请日 | 专利标题
    JP2013171458|2013-08-21|
    JP2013-171458|2013-08-21|
    PCT/JP2014/069172|WO2015025658A1|2013-08-21|2014-07-18|Flame-retardant composition and flame-retardant synthetic resin composition|
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