JP2008069335A - Flame retardant composition, its manufacturing process and flame-retardant resin composition formed from the same - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a flame retardant composition which is substantially free from an atom of halogen, nitrogen and the like and organic phosphorus, contains inorganic phosphorus in an extremely small amount, is therefore environmentally friendly and gives a very high flame retardance to various kinds of resins even in a small amount, a manufacturing process of the composition and a flame retardant resin composition flame-retarded by the composition. <P>SOLUTION: The flame retardant composition is a mixture of an organosiloxane and an oxyacid constituted of vanadium, molybdenum, tungsten atoms and the like or its salt. The flame retardant resin composition is obtained by mixing the composition with a resin having an aromatic group in its main chain or a halogen-containing resin in such a way that the total content of the vanadium, molybdenum or tungsten atoms is 100 ppm-20,000 ppm. The flame retardant composition is obtained by removing the solvent from the mixed solution in which the organosiloxane and the oxyacid constituted of vanadium, molybdenum, tungsten atoms and the like or its salt is dispersed in an organic solvent. <P>COPYRIGHT: (C)2008,JPO&INPIT

Description

  The present invention relates to a flame retardant composition that does not contain an element such as halogen or phosphorus, or has an extremely low phosphorus content, a method for producing the same, and a resin composition containing the flame retardant.

  Conventionally, flame retardant technologies such as synthetic resins have been studied in various industries, and their technical contents are diverse. Among them, the technology to make the organic synthetic polymer itself flame retardant is also underway, but due to the material properties, there are limits to the flame retardant technology at the present time. Therefore, it is common to use a flame retarder (flame retardant) in combination with further flame retardancy, and studies on improving the performance of the flame retardant have been continued. As such flame retardants, most of them are halogen-based flame retardants which are compounds of bromine and chlorine, phosphorus-based flame retardants represented by phosphate esters, nitrogen-based flame retardants which are nitrogen-containing compounds such as melamine and guanidine, or metals Inorganic flame retardants such as oxides and hydrated metal compounds. In recent years, the development of non-halogen and non-phosphorous flame retardants has become active due to the increase in environmental awareness. As typical flame retardants, for example, silicone flame retardants disclosed in Patent Document 1 and Patent Document 2, The hydrated metal system disclosed in Document 3 can be mentioned.

  The flame retardant mechanism using silicone flame retardants has the effect of reducing the contact with oxygen in the atmosphere due to the formation of char during combustion resulting in a change to a structure in which combustion in the normal atmosphere is difficult to sustain. This is considered to be an effect of preventing combustion from continuing due to the effect. However, since silicone itself is not non-flammable in the first place, the materials that can be flame retardant with silicone alone are considerably limited, and the amount of phosphorus flame retardant and halogen flame retardant used alone for flame retardant is higher. It is often necessary and must be said to have low flame retardancy. In addition, flame retarding with a hydrated metal flame retardant is considered to be an effect due to an endothermic reaction during combustion and suppression of combustion duration due to dilution of combustion substances, and a large amount of addition to the resin is required. Patent Document 3 is a technique for reducing the amount of addition, but still requires a large amount of addition compared to phosphorus-based flame retardants and halogen-based flame retardants. As a result, since the physical properties of the resin molded product are inevitably lowered, a compounded resin that serves the purpose of flame retardant with such a flame retardant alone has a drawback that its use is extremely limited.

  Examples of non-halogen and non-phosphorus flame retardants other than silicone flame retardants include nitrogen flame retardants, which are nitrogen-containing compounds such as melamine and guanidine. This is considered to be a combustion suppression effect due to the dilution of the product, dehydration endotherm during combustion, and char formation, and a substantial amount of additive amount is required for the effect to be exerted. It becomes.

On the other hand, although it is not a main component of a flame retardant, there are several composite flame retardant technologies that focus on oxygen acids composed of elements such as vanadium, molybdenum, tungsten, or salts thereof. As an example, it is mentioned that a nitrogen-based flame retardant and a specific additive having a char-forming catalytic action are used in combination. For example, in Patent Document 4, about 30 to 70% by weight polyester or nylon 6,6 resin, about 15 to 40% by weight glass or inorganic reinforcing agent, about 20 to 30% by weight melamine phosphate compound, and 10% by weight. A resin composition that improves flame retardancy by using a combined char catalyst is proposed. Examples of the char catalyst include silicotungstic acid and phosphotungstic acid. Since it is essential to use a large amount of additives other than the resin including the catalyst, it cannot be denied that the characteristics of the base resin are impaired. Patent Document 5 proposes a flame retardant mixture composed of a polymer composition, a phosphorus-containing compound and a triazine flame retardant, and examples of the phosphorus compound include an oxide or hydride of phosphorus, and a reinforcing agent and / or The inclusion of a filler is also described. Furthermore, in the column of [Detailed Description of the Invention] in [Patent Document 5], there is a description of tungstic acid, silicotungstic acid, and phosphotungstic acid as catalysts for promoting the formation of charcoal. Because of the synergistic content of the triazine flame retardant, the combined use of the triazine flame retardant is essential. Further, various compounds are listed as other flame retardant components, among which organosilicon compounds are also mentioned. However, the effect is not particularly clarified, and only the additional description is given. It has not reached the composition of. A similar technique is also proposed in Patent Document 6, which relates to a salt of a melamine condensation product and a phosphorus atom-containing acid, and in the [Detailed Description of the Invention] column, a catalyst for promoting the formation of chat However, the examples do not mention any special usage. Moreover, although it is described in patent document 7 regarding a flame retardance improvement in the specification regarding the combined use with a silicate, it is a phosphate ester type flame retardant compounded composition.
JP 2001-316671 A JP 2002-114982 A JP 2001-226676 A Special Table 2000-502395 Japanese translation of PCT publication No. 2003-510392 Special table 2003-522228 gazette JP 2000-119502 A

  In view of the current situation as described above, the present invention substantially does not contain atoms such as halogen and nitrogen and organic phosphorus, and the inorganic phosphorus content is kept as small as possible in consideration of the environment. , A flame retardant composition capable of imparting extremely high flame retardancy with a small amount of addition to a resin intended to be flame retardant, a method for producing the same, and flame retardancy made flame retardant using the composition The object is to provide a resin composition.

  As a result of investigating the flame retardant effect by paying attention to the compound that does not substantially contain atoms such as halogen, phosphorus, nitrogen and the like, the present inventors further investigated the dispersibility of the compound in the resin. It came.

  More specifically, since the combustion reaction occurs in a short time in the same system in the combustion reaction, the solution to this problem is the oxidation reaction time for substances that do not substantially contain atoms such as halogen, phosphorus, and nitrogen. The material properties that are related to In particular, when a molded product obtained by mixing with a resin is in contact with flame, in the oxidation reaction of a vaporized product accompanied by a flame, the behavior of the flame and fuming, a solid without flame such as charcoal and incense burning In the oxidation reaction, the burning rate and smoke generation were observed. Furthermore, the combination of the substance which can give flame retardance fundamentally was examined by judging the combustion behavior comprehensively. As a result, it was found that it is effective to make the dispersion of the specific substance into the resin as fine as possible in order to further enhance the flame retardant effect. Therefore, a method capable of further fine dispersion was examined. As a result, it has been possible to provide a flame retardant capable of imparting extremely high flame retardancy in a small amount by improving the dispersion characteristics of the flame retardant having a specific substance in the resin. Further details of the technology will be apparent from the following description.

  That is, the present invention provides a flame retardant composition comprising an organopolysiloxane mixed with an oxygen acid or a salt thereof composed of at least one element selected from vanadium, molybdenum, and tungsten, and a composition thereof. The present invention relates to a production method and a flame retardant resin composition flame-retarded with the flame retardant composition.

  By using the flame retardant composition of the present invention, the content of halogen, nitrogen, and organic phosphorus due to the flame retardant can be substantially eliminated, and the content of inorganic phosphorus can be minimized as much as possible. Because it is a flame retardant formulation that takes into account, it is possible to obtain a flame retardant resin molded product with a reduced amount of mixed use of flame retardant compared to conventional products, and an environmentally friendly resin composition for making the resin flame retardant Things can be provided. Furthermore, the fluororesin that is usually added to enhance the drip prevention effect does not generate drip even if it is not used together. Resin can be provided. Further, since the increase in melt viscosity due to the addition of the fluororesin can be suppressed, it is expected that the processability is improved by improving the fluidity and that the heat resistance can be maintained as it is.

As the organopolysiloxane referred to in the present invention, an organopolysiloxane that can be produced by a known technique can be used, and SiO _4/2 (Q unit), RSiO _3/2 (T unit), R ₂ SiO _2/2 (D unit). ), An organopolysiloxane comprising at least one unit selected from the group consisting of hydrogen, a hydrocarbon comprising C _{1 to} C ₂₀ or a hydrocarbon group containing a hetero atom, which may be the same or different. ) Is applicable. By polymerizing a bifunctional D unit, a trifunctional T unit, and a tetrafunctional Q unit alone or in combination of two or three kinds, the properties can be changed to oil, resin, or rubber.

The end of the molecular structure in the organopolysiloxane may be blocked with R ₃ SiO _1/2 (M units). R bonded to the M unit is hydrogen or an alkyl group having 1 to 4 carbon atoms, an aromatic group represented by a phenyl group or a naphthyl group, an alkyl group or a part thereof, or a part of an aromatic ring. It has been substituted with lower alkyl groups such as methyl and ethyl groups, vinyl groups, carboxyl groups, amino groups, epoxy groups, hydroxyl groups, mercapto groups, sulfonic acid groups and functional groups containing heteroatoms such as halogen atoms. They may be the same or different, and preferably a methyl group or a phenyl group is frequently used. The terminal of the molecular structure in the organopolysiloxane here means Si-OX (X is composed of hydrogen, methyl group or ethyl group), and does not necessarily indicate the longest end of the molecular chain, but in the middle of the main chain. And Si-OX contained in the branched chain.

  The molecular weight of the organopolysiloxane is preferably 500 to 200,000 in terms of weight average molecular weight. The terminal blocking rate is not particularly limited, but 50 mol% or more is preferably blocked by M units, and more preferably 70 mol% or more. If the terminal blocking rate is less than 50 mol%, the contribution to flame retardancy may be small. As the organic group bonded to the polysiloxane, a methyl group or a phenyl group is frequently used, but the molar ratio of the phenyl group is 20 mol% or more in consideration of dispersibility in the resin of the flame retardant composition. More preferably, it is 40 mol% or more, but it is not particularly limited.

  The oxygen acid or salt thereof composed of elements such as vanadium, molybdenum and tungsten in the present invention is a simple acid such as vanadic acid, molybdic acid or tungstic acid, or a mononuclear metal oxygenate ion which is an acid ion thereof. Is an isopolyacid, a heteropolyacid or a salt thereof obtained by polynuclearization by dehydration condensation. Among them, a heteropolyacid and a salt thereof are preferred. Preferable representative compounds include phosphotungstic acid, silicotungstic acid, phosphomolybdic acid, silicomolybdic acid, phosphovanadomolybdic acid, phosphotungstomolybdic acid, etc., and salts thereof include 1 such as ammonium, sodium, potassium, etc. The compound which consists of a combination with a valent cation is mentioned, Preferably it is an acid and a sodium salt.

Further, as the heteropolyacid, in addition to the above basic type acid as a molecular formula, as a mixed coordination type, H ₃ (PW _x Mo _(12-x) O ₄₀ ) .nH ₂ O [where 1 ≦ x ≦ 11 (X is an integer)] phosphotungstomolybdic acid represented by H ₄ (SiW _y Mo _(12-y) O ₄₀ ) · nH ₂ O [where 1 ≦ y ≦ 11 (y is an integer)] Caitungsto molybdic acid, represented by H _i (PV _j W _(12-j) O ₄₀ ) .nH ₂ O (where 4 ≦ i ≦ 7, 1 ≦ j ≦ 4, i and j are integers)] Phosphovanadotungstic acid, phosphovanadomolybdic acid represented by H _15-k [PV _12-k Mo _k O ₄₀ ] .nH ₂ O (6 <k <12), but is not limited thereto. These may be used in combination.

  The content of the oxygen acid or the salt thereof in the flame retardant composition is 1% to 99% by weight, preferably 2% to 95% by weight, more preferably 5% as a metal element compound contained therein. % By weight to 90% by weight. When it is less than 1% by weight, the effect of improving the flame retardancy of the matrix resin that imparts flame retardancy when used alone is small, and when it exceeds 99% by weight, the effect of the metal element compound on the matrix resin is small. The dispersibility is lowered, and the effect of improving flame retardancy is small for the amount of addition, which is uneconomical in terms of cost.

  In the method for producing a flame retardant composition according to the present invention, the above components may be simply physically mixed, but after adding the oxygen acid to a solution in which organopolysiloxane is dissolved, the solvent is added. Manufacturing method for recovering as a mixture from which oxygen is removed, organopolysiloxane being dispersed or dissolved in the oxygen acid solution and then recovered as a mixture from which the solvent has been removed, or mixing and stirring the organopolysiloxane solution and the oxygen acid solution In the dispersion or emulsion obtained in this way, there is a method of recovering the mixture as a mixture from which the respective solvents have been removed. The solvent is removed after mixing and dissolving both in a common solvent of organopolysiloxane and oxygen acid. Thus, it is preferable to recover the mixed spots and the crystal particles of oxygen acid as finely dispersed so that they cannot be recognized with the naked eye. When oxygen acid is mixed with the organopolysiloxane solution, if the oxygen acid is insoluble in the solution, it is necessary to reduce the particle diameter of the oxygen acid in advance, and the average particle diameter is 10 μm or less, preferably 5 μm. Hereinafter, it is more preferably 2 μm or less. The particle size of the oxygen acid is preferably as small as possible to increase the flame retardancy, and if the size exceeds 10 μm, the effect of imparting flame retardancy is reduced. On the other hand, when the organopolysiloxane is insoluble in the oxygen acid solution, the applicable organopolysiloxane is preferably finely divided, and the particle size is preferably 100 μm or less. If it exceeds 100 μm, the presence distribution of oxygen acid is uneven, and the flame-retardant effect is reduced.

  Representative examples of such solvents include water, lower alcohols such as methyl alcohol, ethyl alcohol, propyl alcohol, and butyl alcohol, and ethers such as diethyl ether, diisopropyl ether, tetrahydrofuran, dioxane, methyl cellosolve, ethyl cellosolve, and butyl cellosolve. , Lower ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone and cyclohexanone, carboxylic acid esters such as ethyl acetate, butyl acetate and glycol acetate, and normal silicic acids such as normal methyl silicate, normal ethyl silicate and normal isopropyl silicate Lower alkyl esters, chloroform, carbon tetrachloride, 1,2-dichloroethane, perchloroethylene, methylene chloride and other halogenated hydrocarbons, dimethylformamide and dimethyla Polar solvents such as toamide, dimethyl sulfone, dimethyl sulfoxide, tetramethylene sulfone, butyrolactone, ethylene carbonate, propylene carbonate, and aromatics such as benzene, toluene, xylene, m-cresol, chlorinated diphenyl, nitrophenol, chloronaphthalene It may be a solvent or a mixed solvent of two or more of them. Preferred are organic solvents having a boiling point of 250 ° C. or lower, more preferably 200 ° C. or lower, including lower alcohols and lower ketones.

  As a method for removing the solvent, a normal pressure or vacuum distillation method can be generally applied.

  Although the flame retardant composition obtained by removing the solvent depends on the properties of the organopolysiloxane used, it will remain as it is if it is fluid, and it will be cooled if it is extremely viscous and difficult to measure. If it is pulverized or solid, it can be used as a flame retardant composition by pulverization.

  The resin having aromaticity in the main chain constituting the flame-retardant resin composition means a resin in which the matrix resin has aromaticity in the main chain, and as the resin, for example, a polyester resin that is a polycondensation type , Polysulfone resin, aromatic polyamide resin, polycarbonate resin, poly addition type polyurethane resin, epoxy resin, phenoxy resin polyether resin that is oxidation polymerization resin, polyimide resin, polyamideimide resin, polyarylate resin , Polyether ether ketone resins and the like, and further, polymer alloys composed of at least two of these, or other than these, for example, polyamide resins, polystyrene resins and styrene copolymer ABS resins, AS resins, AAS Various other trees that do not contain aromatic groups such as resin and SMA resin It may be used as alloys with.

  Halogen-containing resins include halogenated vinyl resins, vinylidene halide resins obtained by polymerizing halogen-containing vinyl monomers, and other vinyl monomers such as vinyl acetate, acrylonitrile, ethylene, propylene, and vinyl ether. And a halogen-containing copolymer and a penton resin.

  Among these, aromatic polyether resins, polysulfone resins, epoxy resins, polyimide resins, polyamide imide resins, polyarylate resins, polyether ether ketone resins, and the like are suitable. Of course, an aromatic thermosetting resin having a three-dimensional structure is also suitable. Aromatic polyether (PPE) resin is a typical resin of poly (2,6-dimethyl-1,4-phenylene) ether resin, but is a polymer alloy compounded with polystyrene resin to improve its processability. It may be a modified PPE resin or a modified PPE / PA alloy resin alloyed with a polyamide (PA) resin to improve mechanical properties.

  The form of the flame retardant resin composition to which the flame retardant composition of the present invention is applied may be appropriately selected from powder, granule, pellet, lump, viscous liquid, and the like. The product can be used as a molded product, a film, a sheet, a fiber or the like.

  The proportion of the flame retardant composition in the flame retardant resin composition of the present invention depends on the mixing ratio of organopolysiloxane and oxygen acid or a salt thereof composed of elements such as vanadium, molybdenum and tungsten, It is preferable that the total amount of each element is 100 ppm to 20,000 ppm with respect to the flame retardant resin composition, more preferably 500 ppm to 15,000 ppm, still more preferably 1,000 ppm to 10,000 ppm. More preferably, it is 1,000 ppm to 7,000 ppm. If it is less than 100 ppm, the effect of flame retardancy is hardly exhibited, and if it exceeds 20,000 ppm, the flame retardancy tends to deteriorate rather.

  The amount of elements such as vanadium, molybdenum, tungsten in the flame retardant resin composition may be calculated from the content of each metal compound in the flame retardant composition, or the flame retardant resin composition It may be a value measured in the above analysis.

  The flame retardant resin composition referred to in the present invention is at least one selected from a resin having an aromatic main chain and / or a matrix resin which is a halogen-containing resin, the organopolysiloxane, vanadium, molybdenum and tungsten. It means a mixture containing an oxyacid or a salt thereof composed of seed elements. The organopolysiloxane, oxygen acid or salt thereof and the matrix resin may be mixed and processed at the same time, or the organopolysiloxane and oxygen acid or salt thereof may be mixed in advance. After preparing as a flame retardant composition, it may be mixed with the matrix resin and molded. Further, the flame retardant composition and an appropriate amount of organopolysiloxane and / or the oxygen acid may be mixed to form. The organopolysiloxane, oxygen acid or salt thereof, and the matrix resin are preferably mixed at the same time from the viewpoint that the process can be simplified, and from the point that dispersibility is improved. It is preferable to prepare a flame retardant composition by mixing polysiloxane and oxygen acid or a salt thereof in advance and then mix with the matrix resin.

  The organopolysiloxane contained in the flame retardant resin composition is preferably 0.1 to 20 parts by weight, more preferably 0.3 to 15 parts by weight, even more preferably 100 parts by weight of the matrix resin. Is 0.5 to 10 parts by weight. When the content of the organopolysiloxane is less than 0.1 parts by weight, the synergistic effect on flame retardancy with the oxygen acid used in combination is weakened, but when it exceeds 20 parts by weight, flame retardancy is not particularly affected. The benefits are less than the economics of manufacturing.

  By using a combination of the flame retardant composition of the present invention and other known various flame retardants, a higher level of flame retardancy can be obtained. It is possible to obtain a flame retardant resin composition even with an added amount of. As such flame retardants, halogen flame retardants obtained by known techniques, phosphorus flame retardants, nitrogen flame retardants, hydrated metal flame retardants and other flame retardants can be used as long as desired characteristics can be maintained. It can be applied as a flame retardant technology that reduces the amount used and considers the environment.

  Furthermore, it is of course effective to use a fluororesin in combination with the flame retardant resin composition of the present invention in order to further improve the flame retardancy, particularly the drip prevention. The fluororesin here means a resin having a fluorine atom in the resin. Specific examples include polymonofluoroethylene, polydifluoroethylene, polytrifluoroethylene, polytetrafluoroethylene, and tetrafluoroethylene / hexafluoropropylene copolymer. The addition amount of the fluororesin is not limited as long as the properties of the present invention (chemical resistance, heat resistance, physical properties, etc.) are not impaired, but with respect to 100 parts by weight of the matrix resin constituting the flame retardant resin composition, The amount is preferably 10 parts by weight or less of the fluororesin, and the lower limit is not particularly limited. Exceeding 10 parts by weight is not preferable because moldability and physical properties may be deteriorated.

  Further, in order to make the flame retardant resin composition of the present invention higher performance, one or more thermal stabilizers such as a phenol stabilizer, a thioether stabilizer and a phosphorus stabilizer are used in combination. May be. If necessary, lubricants, mold release agents, plasticizers, flame retardants, flame retardant aids, ultraviolet absorbers, light stabilizers, colorants such as pigments and dyes, antistatic agents, conductivity-imparting agents, dispersants, phases You may use together 1 type (s) or 2 or more types, such as a solubilizer, an antibacterial agent, and another performance improvement agent, in the range from which the target performance is acquired.

  Furthermore, in the flame-retardant resin composition of the present invention, it is possible to use a reinforcing filler (material) as long as the characteristics (for example, flame retardancy) of the present invention are not impaired. By using the reinforcing filler (material) in combination, it is possible to further improve heat resistance, mechanical strength, and the like. Such reinforcing fillers (materials) are not particularly limited. For example, fibrous fillers such as glass fibers, carbon fibers, potassium titanate fibers and various inorganic whiskers; glass beads, glass flakes; talc, mica And composite silicates including kaolin, calcium carbonate, calcium sulfate, and barium sulfate. Among the reinforcing fillers (materials), the composite silicate is particularly preferable because the use of organopolysiloxane and the oxygen acid or a salt thereof further improves flame retardancy. These reinforcing fillers (materials) may be added directly to the matrix resin or, of course, may be a component of the flame retardant composition. When mixed and used as a flame retardant composition, if the mixture of polysiloxane and the oxygen acid shows stickiness, an improvement in handling properties can be expected. The composition ratio of the reinforcing filler (material) to the flame retardant resin composition is 0.1 to 50 parts by weight, more preferably 0.5 to 20 parts by weight, more preferably 100 parts by weight of the matrix resin. 1 to 10 parts by weight. If the amount exceeds 50 parts by weight, the flame retardancy and physical properties of the resulting molded product are lowered, and kneading with a resin during melt kneading tends to be difficult. On the other hand, if it is less than 0.1 part by weight, it is difficult to obtain the purpose of mixing as a reinforcing filler (material).

  The method for producing the flame retardant resin composition of the present invention is not particularly limited. For example, it can be produced by a method of drying the components as described above, if necessary, followed by melt kneading in a melt kneader such as a single screw or twin screw extruder. Moreover, when a compounding agent is a liquid, it can also add and manufacture in the middle of a twin-screw extruder using a liquid supply pump etc.

  The molding method of the flame retardant resin composition of the present invention is not particularly limited, and generally used molding methods such as injection molding, blow molding, extrusion molding, vacuum molding, press molding, calendar molding, foam molding, etc. Can be used.

  Moreover, the flame-retardant resin composition of this invention can be used conveniently for various uses. Preferred applications include injection molded products such as home appliances, OA equipment parts, automobile parts, blow molded products, extrusion molded products, foam molded products, and the like.

  Hereinafter, the present invention will be described in more detail with reference to examples. In addition, the preparation of the resin composition in an Example, preparation of a test piece, and the evaluation method followed the following method.

(Preparation of resin composition)
Modified PPE resin (Noryl EFN4230-111 (polyphenylene ether / polystyrene ratio 70/30): 50 parts by weight of GE Plastics Japan), polyphenylene ether resin (PPE: PX100F manufactured by Mitsubishi Engineering Plastics Co., Ltd.) and polystyrene Adeka Stub HP-10 (manufactured by Asahi Denka Co., Ltd.) as a stabilizer is added to 100 parts by weight of a matrix resin consisting of 50 parts by weight of a resin mixture in which a resin (PSJ-polystyrene HF-77: PS Japan) is adjusted to a predetermined mixing ratio. 0.2 parts by weight, and ADK STAB AO-60 (Asahi Denka Co., Ltd.) 0.2 parts by weight. Further, Polyflon MPA FA-500 (Daikin Industries, Ltd.) 0.5 Parts by weight and a predetermined amount of flame retardant composition (or a predetermined amount of acid) After dry blending (acidic acid and / or organopolysiloxane), it is melt-extruded using a twin-screw extruder JSW TEX30HSS (manufactured by Nippon Steel Works Co., Ltd.) and processed into a plastic processing machine (pelletizer: Isuzu Processing Machinery Co., Ltd.) , Model SCF-100) to prepare pellets.

(Creation of specimen)
Test pieces were prepared using an injection molding machine FAS 100B (manufactured by FANUC CORPORATION).

(Flammability evaluation method)
In accordance with the UL94V vertical flammability test method, a flammability test was performed with a test piece thickness of 1/16 ", and the total burn time of five samples was evaluated.

(Element amount measurement)
The elemental amounts of molybdenum and tungsten in the flame retardant composition are measured with an energy dispersive X-ray fluorescence spectrometer SEA2200A (SII Nanotechnology Co., Ltd.) and converted to the molecular weight of each polyoxyacid. The amount of polyoxygen acid was estimated. Next, the amount of element in the resin composition was calculated from the number of added parts of the flame retardant composition based on the measured amount of element in the flame retardant composition.

(Production Example 1): Production of organopolysiloxane 48-kg of 4-methyl-2-pentanone was charged with 18.7 kg of dichlorodiphenylsilane, 3.2 kg of dichlorodimethylsilane and 11.6 kg of M silicate 51 (manufactured by Tama Chemical Co., Ltd.). After stirring and mixing to a liquid temperature of 10 ° C., 6.74 kg of water was added dropwise with stirring while mixing at a liquid temperature of 15 ° C. or lower. Thereafter, the liquid temperature was raised to 76 ° C. while stirring, and after reaching a predetermined temperature, the polymerization reaction was carried out by further stirring for 3 hours at the same temperature. The polymerization solution was once cooled to 15 ° C. or lower, and further dropped and mixed with 10.7 kg of trimethylchlorosilane maintained at 15 ° C. or lower, and further dropped and mixed with 1.76 kg of water similarly maintained at 15 ° C. or lower. The mixture was heated again to a liquid temperature of 56 ° C. while stirring, and after reaching a predetermined temperature, the mixture was further stirred for 3 hours to be reacted. The obtained reaction liquid was cooled to room temperature, and then 100 L of water was added and stirred, followed by washing with water to extract a water-soluble substance in the reaction liquid and remove the aqueous layer portion. This water washing operation was repeated until the pH reached 6 or more. The polymer solution obtained by removing and separating the aqueous layer was 65.6 kg. A part of the polymer solution was sampled, heated to 150 ° C. under reduced pressure with a rotary pump using a rotary evaporator, and concentrated under reduced pressure at a predetermined temperature for 1.5 hours to recover the non-volatile content. The concentration was 37.6%. The obtained non-volatile silicone polymer was pulverized in a mortar to obtain a powder. The characteristics of this organopolysiloxane were 3,700 in terms of polystyrene-reduced weight average polymerization degree by GPC, and the ratio of phenyl group / methyl group by NMR measurement was 44.4 / 55.6.

(Example 1): Production method of flame retardant composition (A) 667 g of a polymer solution obtained by removing and separating the aqueous layer part in (Production Example 1) and 12 Tungsto (VI) n-phosphate aqueous solution as a commercially available reagent 25 g of Japanese product is weighed and mixed, put in a rotary evaporator, heated to 150 ° C. under reduced pressure with a vacuum pump, concentrated under reduced pressure at a predetermined temperature for 1.5 hours to recover the non-volatile content and pulverized in a mortar. Thus, a flame retardant composition (A) composed of a tungsten compound and an organopolysiloxane containing 9.1% by weight in terms of 12 tungsto (VI) phosphoric acid n-hydrate was obtained.

Example 2 Production Method of Flame Retardant Composition (B) 12 molybdo (VI) phosphate n-hydrate was used instead of 12 tungsto (VI) phosphate n-hydrate used in Production Example 2. Except for the above, the same procedure as in Example 1 was carried out to obtain a flame retardant composition (B) composed of a molybdenum compound and an organopolysiloxane containing 9.1% by weight in terms of 12 molybdo (VI) phosphate n-hydrate.

(Example 3): Production method of flame retardant composition (C) Instead of 12 tungsto (VI) phosphoric acid n hydrate used in Production Example 2, 12 tungsto (VI) silicic acid n hydrate was used. Except for the above, the same procedure as in Example 1 was performed to obtain a flame retardant composition (C) composed of a tungsten compound and an organopolysiloxane containing 9.1% by weight in terms of 12 tungsto (VI) n-silicate hydrate.

(Example 4): Production method of flame retardant composition (D) XC99 B5664 (silicon flame retardant manufactured by GE Toshiba Silicone) 200 g, 12 tungsto (VI) phosphoric acid n hydrate 50 g and methyl isobutyl ketone (MIBK) 350 g Were mixed and dissolved. After that, it is put in a rotary evaporator, heated to 150 ° C. under reduced pressure with a vacuum pump, concentrated under reduced pressure at a predetermined temperature for 1.5 hours to recover the non-volatile content, pulverized with a mortar to form a powder, ) A flame retardant composition (D) composed of a tungsten compound and an organopolysiloxane having 20% by weight in terms of phosphoric acid n-hydrate was obtained.

(Examples 5 to 8)
In advance, 50 parts by weight of the modified PPE resin was added to 50 parts by weight of the resin mixed at a mixing ratio of polyphenylene ether resin / polystyrene resin = 90/10 described in (Preparation of resin composition), and the composition of the matrix resin was changed to polyphenylene. 100 parts by weight of a mixed resin adjusted to a composition ratio of ether / polystyrene = 80/20 was prepared, and a predetermined amount of a stabilizer and an anti-drip reinforcing agent were mixed into this matrix resin, and further prepared in Examples 1 to 3. For the flame retardant compositions (A) to (C), 6 parts by weight (for Examples 5 to 7) were blended, and for the flame retardant composition (D) prepared in Example 4, 3 parts by weight (Examples). 8) and blended dry. Thereafter, pellets were prepared from each blend using a twin-screw extruder to obtain a flame retardant resin composition, and further test pieces (Examples 5 to 8) were prepared using an injection molding machine.

(Comparative Example 1)
In place of the flame retardant composition (A) mixed in Example 1, 12 tungsto (VI) phosphoric acid n-hydrate was not added, and the polymer solution was used as it was under reduced pressure with a vacuum pump using a rotary evaporator. The organopolysiloxane obtained by heating to 150 ° C. and concentrating under reduced pressure at a predetermined temperature for 1.5 hours is pulverized into a powder by a mortar, and 5.45 parts of the powder is dry blended in the same manner. A test piece was prepared.

(Comparative Example 2)
Instead of the flame retardant composition (A) prepared in Example 1, 0.55 parts of 12 tungsto (VI) phosphoric acid n-hydrate was dry blended to prepare a test piece by the same method.

  Flame retardancy evaluation was performed on the test pieces of Examples 5 to 8 and Comparative Examples 1 and 2, and the results are shown in Table 1.

表１から、本発明の難燃剤組成物は、その難燃剤組成物を構成する単独成分の難燃効果より優れているのが分かる。

From Table 1, it can be seen that the flame retardant composition of the present invention is superior to the flame retardant effect of a single component constituting the flame retardant composition.

(Example 9, Comparative Example 3)
It is a non-volatile content obtained by concentrating under reduced pressure from the polymer solution of organopolysiloxane obtained by polymerization in Production Example 1 (12-tungsto (VI) phosphate non-added solution) under the same conditions. Organopolysiloxane was prepared. This organopolysiloxane is mixed with 12 tungsto (VI) phosphoric acid n-hydrate so as to have a predetermined content, and then acetone is added to dissolve, mix and concentrate under reduced pressure to recover the non-volatile content. 12 tungsto (VI) Organos containing 5% by weight (E), 9.1% by weight (F), 15% by weight (G), 20% by weight (H) and 33% by weight (I) in terms of phosphoric acid n-hydrate. A flame retardant composition to be a polysiloxane mixture was prepared. In addition, a flame retardant composition containing only 12 polytungsto (VI) phosphate n-hydrate and containing only organopolysiloxane was also prepared (Comparative Example 3). Next, according to (Preparation of resin composition), 3 parts by weight of the obtained various flame retardant compositions were dry blended with 100 parts by weight of the matrix resin having a polyphenylene ether / polystyrene ratio of 80/20 to prepare pellets. And finished into a test piece. The result of flame retardance evaluation of each test piece is shown in FIG.

(Example 10, comparative example 4)
To 100 parts by weight of a matrix resin having a polyphenylene ether / polystyrene ratio of 80/20, 0.3 parts by weight of 12 tungsto (VI) phosphate n-hydrate finely pulverized in a mortar (the amount of tungsten element is 0% with respect to the matrix resin). .19 parts by weight) and a predetermined amount of organopolysiloxane which is a non-volatile component used in Example 9 was prepared. A test piece was prepared according to (Preparation of resin composition) and (Preparation of test piece) (12 Tungsto (VI) phosphoric acid n-hydrate and organopolysiloxane were mixed as they were without a flame retardant composition) .) Also, a test piece was prepared in which a predetermined amount of 12-tungsto (VI) phosphate n-hydrate was not added and only organopolysiloxane was added as a flame retardant (Comparative Example 4). The results of those flammability evaluations are shown in FIG.

(Example 11): Method for producing flame retardant composition (J) 12 Tungsto (VI) sodium phosphate n hydrate used in Example 1 instead of 12 Tungsto (VI) sodium phosphate n hydrate Except that it was used, the same procedure as in Example 1 was carried out to obtain a flame retardant composition (J) comprising a tungten compound and an organopolysiloxane containing 9.1% by weight in terms of 12 tungsto (VI) sodium phosphate n hydrate. It was.
(Examples 12 to 17 and Comparative Examples 5 and 6)
In advance, 50 parts by weight of modified PPE resin was added to 50 parts by weight of the resin mixed in the mixing ratio of polyphenylene ether / polystyrene = 90/10 described in the above (Preparation of resin composition), and the composition of the matrix resin was changed to polyphenylene ether / 100 parts by weight of a mixed resin adjusted to a composition ratio of polystyrene = 80/20 was prepared, and talc (Nippon Talc (Nippon Talc) as a composite silicate was added to this matrix resin with a predetermined amount of stabilizer and addition amount changed. SG-200) or mica (A-21S manufactured by Yamaguchi Mica Industry Co., Ltd.) was mixed, and the flame retardant composition (A) prepared in Example 6, Example 9 and Example 10, About (G) and (J), 3 parts by weight of each was blended and dry blended. Thereafter, pellets were prepared from each blend using a twin-screw extruder to obtain a flame retardant resin composition, and further test pieces (Examples 12 to 17) were prepared using an injection molding machine.

  On the other hand, it was obtained from a composition containing an organopolysiloxane not containing a heteropoly acid in addition to a stabilizer, an anti-drip strengthening agent, and a composition containing a composite silicate (talc) and an anti-drip reinforcing agent. Resin compositions (Comparative Example 5 and Comparative Example 6) as test pieces were prepared, and the results of their flammability evaluation are shown in Table 2.

表２からは、難燃性樹脂組成物において同一量の１２タングスト（VI）りん酸ｎ水和物の混合であっても、複合ケイ酸塩が混合されている方が難燃性は優れているのがわかる。しかも複合ケイ酸塩とヘテロポリ酸またはその塩を混合してなる難燃性樹脂組成物は実施例１３〜１７を観察すると、一様にその難燃効果が顕著に優れているのが分る。

From Table 2, it can be seen that even if the same amount of 12 tungsto (VI) phosphate n-hydrate is mixed in the flame-retardant resin composition, the flame retardant is better when the composite silicate is mixed. I can see that Moreover, when Examples 13 to 17 are observed in the flame retardant resin composition obtained by mixing the composite silicate and the heteropolyacid or a salt thereof, it is found that the flame retardant effect is remarkably excellent uniformly.

It is a graph which shows the relationship between 12 tungsto (VI) phosphoric acid n hydrate content and the flame retardance of a resin composition in Example 9 and Comparative Example 3. It is a graph which shows the relationship between the organopolysiloxane addition amount and the flame retardance of a resin composition in Example 10 and Comparative Example 4.

Claims (10)

Organopolysiloxane,
An oxygen acid or a salt thereof composed of at least one element selected from vanadium, molybdenum and tungsten;
A flame retardant composition comprising:   The flame retardant composition according to claim 1, wherein the oxygen acid is at least one of an isopolyacid and a heteropolyacid.   The flame retardant composition according to claim 2, wherein the oxygen acid is a heteropolyoxyacid composed of at least one of molybdenum and tungsten containing at least one element selected from phosphorus, silicon, and vanadium. The organopolysiloxane is a silicone comprising one or more units selected from SiO _4/2 (Q unit), RSiO _3/2 (T unit), and R ₂ SiO _2/2 (D unit). And a hydrocarbon group comprising C _{1 to} C ₂₀ or a hydrocarbon group containing a heteroatom, which may be the same or different).   An organopolysiloxane and oxygen acid or a salt thereof composed of at least one element selected from the group consisting of vanadium, molybdenum and tungsten are dispersed or dissolved in an organic solvent to form a mixed solution, and the solvent is removed from the mixed solution. It removes, The method to manufacture the flame retardant composition in any one of Claims 1-4 characterized by the above-mentioned.   The method for producing a flame retardant composition according to claim 5, wherein the organic solvent is at least one of an organopolysiloxane solvent and a swelling agent. At least one resin selected from a resin having an aromatic main chain and a halogen-containing resin;
Organopolysiloxane,
An oxygen acid or a salt thereof composed of at least one element selected from vanadium, molybdenum and tungsten;
A flame retardant resin composition comprising:
A flame retardant resin composition containing the elements of vanadium, molybdenum and tungsten in a total amount of 100 ppm to 20,000 ppm.   The flame-retardant resin composition according to claim 7, wherein the resin having an aromatic group in the main chain uses an aromatic polyether resin as a matrix resin.   The flame retardant composition according to any one of claims 1 to 4, comprising a composite silicate compound.   The flame-retardant resin composition according to claim 7 or 8, comprising a composite silicate compound.

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