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    • 专利摘要:
    The present invention relates to a flame retardant which is obtained by mixing a flame retardant exhibiting a liquid or viscous solid state at room temperature with an inorganic fibrous substance and adhering or adsorbing the flame retardant to the fibrous substance, By weight based on the total weight of the flame retardant. The powdery flame retardant of the present invention exhibits an excellent and remarkable effect that it is easy to handle because of its powder form, can be obtained by a simple and industrially advantageous method, and does not impair the performance of the flame retardant as a raw material .
    公开号:KR20010072918A
    申请号:KR1020017002336
    申请日:1999-08-12
    公开日:2001-07-31
    发明作者:다다유지；야부하라다다오；나카노신지；가메시마다카시；니시오카요이치；다카세히로유키
    申请人:오츠카 유지로；오츠카 가가쿠 가부시키 가이샤；
    IPC主号:
    专利说明:

    POWDERY FLAME RETARDANT [0002]
    [2] A flame retardant for a synthetic resin such as a phosphazene compound or a phosphoric acid ester compound is generally in a liquid form or in a solid form even if it is a liquid form or a dot form by the by- But tend to be obtained as a mixture exhibiting an ancillary solid state. This tendency does not change even when the purity of the flame retardant is as high as, for example, 98% or more.
    [3] However, when a flame retardant is added to a synthetic resin or the like, it is needless to say that the case of a powdery material is easier to handle than the material of a liquid or a viscous solid, and the supply means is simplified. Powdery materials are also advantageous in packaging and transportation.
    [4] In general, in order to powder a liquid or viscous solid substance, a purification treatment method such as a recrystallization method using an organic solvent or a fractional distillation method is carried out. However, these methods require energy to be a special device or a heat source, and there is a drawback that recovery and reuse of the organic solvent can not be avoided.
    [1] The present invention relates to a novel powdery flame retardant.
    [5] SUMMARY OF THE INVENTION An object of the present invention is to provide a novel powdery flame retardant which overcomes the problems of the prior art.
    [6] Another object of the present invention is to provide a novel powdery flame retardant which is obtained by powdering a liquid or viscous solid flame retardant at room temperature by a convenient method without the above-mentioned conventional drawbacks.
    [7] Other objects and features of the present invention will become apparent from the following description.
    [8] The present invention relates to a flame retardant composition comprising 5 to 70% by weight of the flame retardant and 95 to 95% by weight of the fibrous material 95 To 30% by weight of the flame retardant.
    [9] As a result of diligent research to achieve the above object, the present inventors have found that the performance of the flame retardant is impaired by an extremely simple method of mixing or adsorbing a flame retardant of liquid or viscous solid at room temperature with an inorganic fibrous substance , It is possible to obtain a powdered flame retardant.
    [10] The present invention has been completed based on this new viewpoint.
    [11] The powdery flame retardant of the present invention contains a flame retardant of liquid or viscous solid at room temperature and an inorganic fibrous substance as active ingredients. Here, the " liquid at normal temperature " means that the viscosity at 25 ° C is equivalent to about 0.3 mPa · s to 10 Pa · s, and the viscosity at 25 ° C. corresponds to about 10 Pa · s or more .
    [12] As the flame retardant of liquid or viscous solid at room temperature which is a raw material of the powdered flame retardant of the present invention, any of known flame retardants may be used.
    [13] As the raw material flame retarder, a phosphazene compound, a phosphoric acid ester compound, an organic halogen compound and the like are preferable in order to obtain a powdery flame retardant in a good powder state. The "good powder state" means a state in which the particle size of the powder is not uneven, hardly solidified even when stored for a long period of time, and does not generate dust at the time of use.
    [14] As the raw material flame retardant, a phosphazene compound and a phosphate ester compound are particularly preferable in that they do not contain a halogen element that generates a harmful gas or a compound when left at a high temperature. The powdery flame retardant of the present invention containing at least one of the raw material flame retardant and the inorganic fibrous material is preferably a dripping inhibitor such as polytetrafluoroethylene ) Flame retardancy in a test based on the UL-94 Flammability Test Method (Test for Flammability of Plastic Materials for Parts and Devices UL-94, Fourth Edition) without adding . Therefore, it is very suitable as a powdered flame retardant for a completely halogen-free flame retardant resin composition.
    [15] As a phosphazene compound which is a raw material flame retardant, any of known compounds described in patent publications, literature and the like can be used. Specific examples include phosphazene compounds described in James E. Mark, Harry R. Allcock, Robert West, pages 61-140 of "Inorganic Polymers" (Prentice-Hall International, Inc., 1992) .
    [16] More specifically, for example, the following compounds (1) to (4) can be mentioned.
    [17] (1)
    [18]
    [19] Wherein m represents an integer of 3 to 25; And two R 1 s are the same or different and represent a phenyl group or an unsubstituted phenyl group substituted with at least one group selected from an alkyl group having 1 to 6 carbon atoms and an allyl group.
    [20] (2)
    [21]
    [22] Wherein n represents an integer of 3 to 1000. R 1 is as defined above. X represents -N = P (OR 1) 3 or -N = P (O) OR 1 . And Y represents -P (OR 1 ) 4 or -P (O) (OR 1 ) 2 .
    [23] (3) at least one selected from the phosphazene compounds of the above-mentioned (1) and (2) is at least one selected from the group consisting of o-phenylene, m-phenylene, p-phenylene, biphenylene, Wherein A represents -SO 2 -, -S-, -O- or -C (CH 3 ) 2 -. Wherein R < 1 > and R < 2 > The cross-linking group, and is interposed between the above-mentioned (1) and two oxygen atoms by the R 1 of the phosphazene compound of the exit (2). The content of R 1 in the crosslinked phosphazene compound is 50 to 99.9% based on the total number of R 1 in the phosphazene compound before crosslinking.
    [24] (4)
    [25]
    [26] Wherein R 2 represents a cyano-substituted phenyl group. R 3 is an alkyl group having 1 to 18 carbon atoms or an aryl group having 6 to 10 carbon atoms, and these groups may be substituted with at least one group selected from an alkyl group having 1 to 10 carbon atoms, an allyl group and an aryl group. If R 3 is more than one, the same or different each other and they may be the R 3. p and q represent real numbers satisfying p > 0, q > 0 and p + q = 2. and r represents an integer of 3 to 25, and a cyclic phosphazene compound represented by the following formula
    [27]
    [28] Wherein R 2 , R 3 , p and q are as defined above. and s represents an integer of 3 to 1000. X 'is -P (OR 2) 4, -P (OR 2) 3 (OR 3), -P (OR 2) 2 (OR 3) 2, -P (OR 2) (OR 3) 3, -P (oR 3) 4, -P ( O) (oR 2) 2, -P (O) (oR 2) (oR 3) or -P (O) (oR 3) represents a 2, Y 'is -N = P (OR 2) 3, -N = P (OR 2) 2 (OR 3), -N = P (OR 2) (OR 3) 2, -N = P (OR 3) 3, -N = P ( O) OR < 2 > or -N = P (O) OR < 3 & gt ;.
    [29] The phosphazene compounds may be used alone or in combination of two or more. Or a mixture of a cyclic phosphazene compound and a linear phosphazene compound.
    [30] Specific examples of the cyclic phosphazene compound (1) and the linear phosphazene compound (2) include, for example, hexachlorocyclotriene, which can be obtained by reacting ammonium chloride with phosphorus pentachloride at about 120 to 130 ° C. A phosphazene compound in which a phenoxy group and / or an alkoxy group is substituted for cyclic and cyclic phosphazene mixtures such as phosphazene and octachlorocyclotetrafosphage; A single substance such as hexachlorocyclotriphosphazene, octachlorocyclotetrafosphagegene, decachlorocyclopentaphosphene and the like is extracted from the above-mentioned chlorophosphazene mixture, and hexaphenoxycyclotriphosphine substituted with a phenoxy group and / or an alkoxy group Cyclic phosphazene compounds such as phthalocyanine, phthalocyanine, phthalocyanine, phthalocyanine, phthalocyanine, phthalocyanine, phthalazine, octaphenoxycyclotetrafosphagen, decaffeoxycyclopentaphosphazene, hexaalkoxycyclotriphosphazene, octaalkoxycyclotetrafosphagen and decaalkoxycyclopentaphosphazene. Further, a straight chain phosphazene compound in which a phenoxy group and / or an alkoxy group is substituted with dichlorophosphazene which can be obtained by heating (220 to 250 ° C) ring-opening polymerization of hexachlorocyclotriphosphazene can be exemplified .
    [31] Specific examples of the crosslinked phosphazene compound of the formula (3) include phenoxyphospazene having a crosslinked structure by 4,4'-sulfonyldiphenylene (bisphenol S residue), 2,2- (4,4 ' -Diphenylene) isopropylidene group, phenoxyphosphazene having a crosslinking structure by a 4,4'-oxydiphenylene group, 4,4'-thiodiphenyl Phenoxyphosphazenes having a crosslinking structure by a phenylene group, phenoxyphosphazenes having a crosslinking structure by a 4,4'-diphenylene group, and the like.
    [32] Specific examples of the phosphazene compound of the formula (4) include, for example, monocyano phenoxypentaphenocyclo triphosphazene, dicyanophenoxy tetraphenoxycyclotriphosphazene, tricyanophenoxy triphenoxycyclotriphosphate Cyclotriphosphazene compounds such as phenanthroline, phosgene, tetracyanophenoxy diphenoxycyclotriphosphazene and pentacyano phenoxymonophenocyclotriphosphazene, monocyano phenoxy hepta phenoxycyclotetraphosphazene, dicyanophenoxy Tetracyanoquinodimethane, hexafenoxycyclotetrafluoroethane, hexafenoxycyclotetrafosphagen, tricyanophenoxypentafenoxycyclotetrafosphosgene, tetracyanophenoxytetraphenoxycyclotetrafosphagen, pentacyanophenoxy triphenoxycyclotetrafosphagen, hexacyano Cyclotetrasphosphazenes such as phenoxy diphenoxycyclotetrafosphagen, heptacyano phenoxymonophenoxycyclotetrafosphagen, and the like And the like compounds, cyano-phenoxy group and phenoxy group are mixed substituted cyclopentadienyl compounds such as phosphazene cyclic phosphazene compound, Cyano-phenoxy group and a phenoxy phosphazene compound is mixed in the substituted straight-chain.
    [33] Among them, in the cyclic phosphazene compound (1), m is an integer of 3 to 8, and in the linear phosphazene compound of the general formula (2), n is an integer of 3 to 25, (A) is -SO 2 -, -S- or -C (CH 3 ) 2 -, and the phosphazene compound of (4) is a mixture of a cyanophenoxy group and a phenoxy group .
    [34] The purity of the phosphazene compound varies depending on the raw material, the production method and the production conditions, but is usually about 98 to 99%. The purity of the phosphazene compound which can be used in the present invention is not particularly limited, but it is usually 90% or more, preferably 95% or more. When the purity is within this range, it is possible to obtain a powder which is simple and can be pulverized in a short time and further in a powder state.
    [35] Examples of phosphoric acid ester compounds which are raw flame retardants include organic phosphorus compounds such as trimethyl phosphate, triethyl phosphate, tributyl phosphate, tris (2-chloroethyl) phosphate, tris (p- tolyl) phosphate, resorcinol- ), Tris (dibromopropyl) phosphate, and the like.
    [36] Among these, trimethyl phosphate, triethyl phosphate, tributyl phosphate, tris (p-tolyl) phosphate, resorcinol-bis (diphenyl phosphate) and the like are preferable.
    [37] Among them, tris (p-tolyl) phosphate, resorcinol-bis (diphenylphosphate) and the like are more preferable.
    [38] In addition, methods for producing these organic phosphorus compounds are described in "New Experimental Chemistry Lecture (Maruzen), Vol. 12, p421 to p470, John R. Van Wazer," Phosphorus and its Compounds ", Interscience Publishers, York, Harry R. Allcock, et. al., " Inorganic Polymers " Prentice-Hall International, Inc. p61 to p140, JP-A-6-19003, Macromolecules 1985, 18, p139 to p144 and the like can be used.
    [39] Examples of the organic halogen compounds which are raw flame retardants include dibromocresylglycidyl ether and chlorinated paraffin.
    [40] Examples of the inorganic fibrous substance that is a raw material of the powdered flame retardant of the present invention include talc, silica, clay, barium carbonate, calcium carbonate, calcium sulfate, calcium silicate, titanium oxide, glass beads, glass balloons, Glass flakes, glass fibers, fibrous titanate alkali metal salts, fibrous boric acid transition metal salts, fibrous boric acid alkaline earth metal salts, fibrous zinc oxide, fibrous titanium oxide, fibrous magnesium oxide, fibrous gypsum, fibrous aluminum silicate (mineral mullite) Fibrous titanium carbide, fibrous silicon nitride, fibrous titanium nitride, carbon fiber, alumina fiber, alumina-silica fiber, zirconia fiber, quartz fiber, and the like can be given as examples of the fibrous silicon carbide (mineral wollastonite). Representative fibers of fibrous titanic acid alkali metal salt, fibrous boric acid transition metal salt and fibrous boric acid alkaline earth metal salt include potassium titanate fiber, aluminum borate fiber and magnesium borate fiber. Among these, preferred are fibrous titanic acid alkali metal salts, wollastonite and magnesium borate fibers, and particularly preferred are fibrous titanic acid alkali metal salts and wollastonite. These may be one kind or a mixture of two or more kinds. In addition, it may be used in combination with a commonly used inorganic additive.
    [41] The inorganic fibrous substance is prepared based on a method described in known patent publications, literature and the like. For example, in the case of fibrous zinc oxide, Japanese Examined Patent Publication No. 60-5529, Japanese Examined Patent Publication No. 3-51657, etc., and fibrous magnesium oxide, Japanese Examined Patent Publication No. 60-11223, Japanese Examined Patent Publication No. 61-210000 For fibrous gypsum, Japanese Patent Publication No. 58-12235, Japanese Patent Publication No. 58-34410, etc. For fibrous aluminum silicate (mineral mullite), Japanese Patent Publication No. 4-76956, Japanese Patent Publication No. 7 Japanese Patent Application Laid-Open No. 8-319199 and Japanese Patent Laid-Open No. 9-40840 for fibrous calcium silicate (mineral name wollastonite), such as fibrous silicon carbide, Japanese Patent Application Laid-Open No. 56-109811, Japanese Patent Publication No. 59-45638 and Japanese Patent Laid-Open No. 62-250225 for fibrous titanium carbide, etc., and fibrous silicon nitride for fibrous titanium carbide, Japanese Patent Application Laid-Open No. 57-17499, Japanese Patent Laid- -17500, etc., and for fibrous titanium nitride, Japanese Patent Application Laid-Open No. 2-221198, And the like can be mentioned Laid-Open Patent Publication No. 7-173000.
    [42] The potassium titanate fiber is preferably a potassium hexatitanate fiber having an aspect ratio of 10 or more. When the aspect ratio is 10 or more, there is no particular limitation, and known ones can be used. The aspect ratio means the fiber length / fiber diameter. When the ratio is less than 10, sufficient flame retarding effect can not be obtained. The potassium titanate fiber can be produced by a known method using a potassium compound and a titanium compound as starting materials. Usually, those having an average fiber diameter of about 0.05 to 2.0 mu m and an average fiber length of about 1 to 500 mu m can be suitably used.
    [43] Of the potassium titanate fibers, those having a pH of 6.0 to 8.5 are preferably used. Here, the pH of potassium titanate fiber refers to a value obtained by stirring a 1.0 wt% aqueous slurry of potassium titanate fibers (using deionized water) for 10 minutes and then continuing to stir again and measuring the pH of the aqueous slurry at 20 ° C. If the pH of the potassium titanate fiber exceeds 8.5, the physical properties and heat discoloration resistance of the powder may deteriorate when the powdery flame retardant containing the powder is blended with the resin to be subjected to the flame retardation, which is not preferable. On the other hand, when the pH is extremely lower than 6.0, not only the effect of improving the strength of the molded article of the resin composition blended with the resin to be flame retarded is deteriorated, but also the processing machine and the mold are corroded And it is not preferable.
    [44] The powdery flame retardant of the present invention is obtained by mixing a flame retardant exhibiting a liquid or viscous solid state at room temperature with an inorganic fibrous material and attaching or adsorbing the flame retardant to the fibrous material. 5 to 70% by weight of a flame retardant representing a solid state and 95 to 30% by weight of an inorganic fibrous material. It is preferably 80 to 40% by weight, in particular 70 to 50% by weight, of the inorganic fibrous material, relative to 20 to 60% by weight, in particular 30 to 50% by weight, of the flame retardant exhibiting a liquid or viscous solid state at room temperature. When the content of the inorganic fibrous substance is more than 95% by weight, the flame retardancy is lowered. When the content is less than 30% by weight, the whole is tacky, the powder tends to harden, becomes uneven, . When the amount of the flame retardant exhibiting the state of liquid or viscous solid at room temperature is more than 70% by weight, the tackiness as a whole appears and the cost is disadvantageous. When the amount is less than 5% by weight, the flame retardancy is deteriorated.
    [45] The powdery flame retardant of the present invention can be prepared by mixing a flame retardant exhibiting a liquid or viscous solid state at room temperature with an inorganic fibrous substance and attaching or adsorbing the flame retardant to the surface of the fibrous substance. As a mixing means at this time, generally known devices can be used. For example, a mixer equipped with a stirrer such as a spade mixer, a ribbon mixer, a screw mixer, or the like can be used. As a specific method of pulverization, a necessary amount of the fibrous material is mixed with a mixer equipped with a stirrer in advance, and a flame retardant exhibiting a liquid or viscous solid state at room temperature is mixed with the fibrous material under agitation and mixing, The mixture is heated to form a liquid phase, which is added little by little dropwise to the mixture to form a powder. The agitation rotation speed of the mixer varies depending on the type or type of the mixer, but is generally about 100 to 5,000 rpm, more preferably 500 to 1,000 rpm. In the pulverization, when the flame retardant to be added is a relatively low-viscosity liquid phase material, a known liquid injection device can be used and the mixture can be supplied directly to the above-mentioned mixer. When the flame retardant to be added has a high viscosity or is in the form of a viscous liquid such as a wax phase, the viscosity of the flame retardant is preferably from 0.01 to 1 Pa · s, preferably from 0.05 to 0.5 Pa · s s. After completion of the addition of the flame retardant, stirring and mixing are continued for 0.5 to 10 minutes, preferably 1 to 2 minutes, to complete the pulverization.
    [46] Thus, the powdered flame retardant of the present invention can be obtained. The powdered flame retardant of the present invention can be suitably used for the purpose of flame retardation of various synthetic resins. When the flame retardant of the present invention is kneaded with a resin, a sieve of 4 to 16 meshes, preferably 6 to 10 meshes, is passed in order to obtain a more uniform dispersibility of the flame retardant , It is preferable to adjust the particle diameter to an average particle diameter of about 500 mu m to about 4 mm, preferably 1 to 3 mm. The term " kneading " means that when a powdered flame retardant is mixed with a resin, a shearing force is simultaneously applied to the resin and the powdered flame retardant to uniformly disperse the powdered flame retardant in the resin.
    [47] Examples of the resin to which the powdered flame retardant of the present invention can be applied include resins such as polyethylene, polypropylene, polyisoprene, polybutadiene, polystyrene, impact resistant polystyrene (HIPS), acrylonitrile-styrene resin (AS resin), acrylonitrile · Butadiene · Styrene resin (ABS resin) · Methyl methacrylate · Butadiene · Styrene resin (MBS resin) · Methyl methacrylate · Acrylonitrile · Butadiene · Styrene resin (MABS resin) · Acrylonitrile · Acrylic rubber · (AES resin), polyalkyl (meth) acrylate, aromatic polycarbonate (PC), polyphenylene ether (PPE), polyphenylene sulfide (PPS), polyether sulfone (PES) , Polybutylene terephthalate (PBT), polyethylene terephthalate (PET), polyethylene naphthalate (PEN), polyamide (PA), polyether ketone (PEK), polyetheretherketone (PEEK), polyamideimide I), polyetherimide (PEI) and polyimide (PI), thermosetting resins such as epoxy resin, and the like.
    [48] In the case of obtaining a flame retardant resin composition by kneading the powdered flame retardant of the present invention with a synthetic resin, 20 to 60 parts by weight, preferably 25 to 50 parts by weight, of the powdered flame retardant is added to 100 parts by weight of the resin Suitable. If the amount of the powdery flame retardant exceeds 60 parts by weight, the mechanical properties of the flame retardant resin composition are lowered and the cost is disadvantageously lowered. On the other hand, if the amount is less than 20 parts by weight, the flame retardancy becomes insufficient.
    [49] When the flame-retardant resin composition of the present invention is kneaded with various synthetic resins, additives of various kinds and amounts that do not impair the properties of the flame retardant may be appropriately combined and added. Examples of the additives for various kinds of resins (hereinafter, referred to as various additives) include other flame retardants, ultraviolet absorbers, light stabilizers, antioxidants, light shielding agents, metal deactivators, quenchers, heat stabilizers, lubricants, release agents, An antistatic agent, an antioxidant, a plasticizer, an impact strength improver, a filler, and a compatibilizer.
    [50] Specific examples of these various additives include aluminum hydroxide, magnesium hydroxide, antimony trioxide, antimony pentoxide, boric acid, barium borate, calcium borate, magnesium carbonate, zinc oxide, barium sulfate, aluminum sulfate, magnesium sulfate, ammonium polyphosphate, Soda, sodium naphthalenesulfonate, guanidine, melamine cyanurate, melamine, chitin, chitosan, liquid crystal polymer, mica, and kaolin. Of these, preferred are aluminum hydroxide, magnesium hydroxide, barium sulfate, aluminum sulfate, ammonium polyphosphate and liquid crystal polymers, and particularly preferred are aluminum hydroxide and barium sulfate. These various additives may be used alone or in combination of two or more. These additives can also be added during the production of the flame retardant of the present invention.
    [51] When the above-mentioned various additives are used, it is usually preferable to use 0.01 to 30 parts by weight, preferably 0.5 to 20 parts by weight, of the various additives in combination with 100 parts by weight of the synthetic resin in combination with the powdery flame retardant of the present invention . When various additives are used in combination, for example, flame retardancy and the like may be further improved depending on the properties of the additive. When the amount of the additive is less than 0.01 part by weight, the effect of improving the flame retardancy is not exhibited. When the amount is more than 30 parts by weight, the mechanical properties of the resin after kneading are lowered.
    [52] The flame retardant resin composition containing the powdered flame retardant of the present invention is excellent in mechanical properties after molding and flame retardancy. The composition can be molded into various molded articles by, for example, injection molding, sheet extrusion, vacuum molding, profile extrusion molding, blow molding, foam molding, injection press molding, gas injection molding, .
    [53] Hereinafter, the present invention will be described more specifically with reference to Synthesis Examples, Examples, Comparative Examples and Test Examples. In each example, parts and percentages are by weight unless otherwise specified.
    [54] Synthesis Example 1: Synthesis of Phenoxyphosphazene (Compound 1) as a raw material flame retardant
    [55] To a 1 liter four-necked flask equipped with a stirrer, a thermometer and a reflux condenser, 1.30 moles (123.0 g) of phenol was added, 500 ml of tetrahydrofuran (THF) was added and dissolved homogeneously. Subsequently, 7.6 g of sodium metal was added at 25 DEG C or lower, the temperature was raised to 61 DEG C over 1 hour, and stirring was continued at 61 to 68 DEG C for 6 hours to prepare a sodium phenolate solution.
    [56] In parallel with the above reaction, 0.5 unit moles (58 g) of dichlorophosphazene oligomer (mixture of 59% of trimer, 12% of tetramer, 11% of 5 and 6mers, 3% of 7mers and 15% 290 g of a 20% chlorobenzene solution was prepared in a 2-liter four-necked flask, and the sodium phenolate mixed solution prepared earlier was added dropwise into the flask while stirring at 25 占 폚 or lower. After dropwise addition, the mixture was stirred and reacted at 71 to 73 ° C for 15 hours.
    [57] After completion of the reaction, the reaction mixture was concentrated, redissolved in 500 ml of chlorobenzene, washed with water, washed with 5% aqueous sodium hydroxide solution three times, washed with 5% sulfuric acid, washed with 5% sodium bicarbonate, And concentrated to dryness to obtain 108 g of a pale yellow waxy substance. (Yield: 98.5%)
    [58] The weight average molecular weight (Mw) determined by GPC analysis of the product is 810 in terms of polystyrene, the melting temperature (Tm) by the TG / DTA analysis is 103 ℃, 5% weight loss temperature (T 5) and the decomposition starting temperature (Td ) Were 330 ° C and 347 ° C, respectively. Further, it was confirmed that the residual chlorine amount (Hy-Cl) was 0.09% and that the compound had a constitutional unit represented by the following chemical structural formula from analysis values of phosphorus and CHN elements.
    [59] Compound 1: [N = P (-O-Ph) 2.00 ]
    [60] In the above formula, -Ph represents a phenyl group. Hereinafter, the same applies.
    [61] Synthesis Example 2: Synthesis of phenoxyphospazene (Compound 2) having a crosslinking structure by 4,4'-sulfonyldiphenylene (bisphenol S residue) as a raw material flame retardant
    [62] 1.85 mol (118.0 g) of phenol and 0.033 mol (8.3 g) of bisphenol S were reacted in the same manner as in Synthesis Example 1 to obtain a pale yellow waxy substance. (Yield: 91.5%)
    [63] The product had a weight average molecular weight (Mw) of 820 in terms of polystyrene and a 5% weight reduction temperature (T 5 ) and a decomposition start temperature (Td) of 342 ° C and 357 ° C, respectively. Further, it was confirmed that the residual chlorine amount (Hy-Cl) was 0.01% and that the compound had the constitutional unit represented by the following chemical structural formula from analysis values of phosphorus and CHN elements.
    [64] Compound 2: [N = P (-O -Ph-SO 2 -Ph-O-) 0.05 (-O-Ph) 1.90]
    [65] In the above formula, -Ph- represents a p-phenylene group.
    [66] Synthesis Example 3: Synthesis of resorcinol-bis (diphenylphosphate) (Compound 3) as a raw flame retardant agent [
    [67] 1.92 mol (234.4 g) of 2,6-xylenol, 19.2 g of xylene, and 0.02 mol (1.4 g) of magnesium chloride were placed in a two-liter four-necked flask, followed by heating and mixing. When the temperature of the reaction solution reached 120 캜, 1.0 mol (147.2 g) of phosphorus oxychloride was added over about 2 hours. The hydrochloric acid gas generated at this time was led by a water screw scrubber. After the addition of phosphorus oxychloride was completed, the temperature of the reaction solution was gradually raised to 180 DEG C over 2 hours to complete the reaction.
    [68] Subsequently, 0.53 mol (52.8 g) of resorcin and 0.01 mol (1.4 g) of aluminum chloride were added to the reaction mixture, followed by heating and mixing. The reaction temperature was gradually raised to 180 캜 over 2 hours. After stirring at the same temperature for 2 hours, stirring was further carried out at 200 mmHg under reduced pressure for 2 hours to complete the reaction. After completion of the reaction, 330 g of xylene and 33 g of a 10% hydrochloric acid solution were added to the reaction solution, and the remaining catalyst and the like were removed by stirring, followed by washing with 99 g of 4% saline.
    [69] 1.0 g of 2,6-di-tert-butyl-p-cresol (0.3% based on the compound 3) and 3% aqueous solution of sodium hydroxide were added to the mixture of the obtained compound 3 and the solvent , And the mixture was heated to 70 占 폚 and stirred with heating for 1 hour. Subsequently, 132 g of the oil phase of the reaction liquid was washed with 6% saline at 70 占 폚 and then washed again with 132 g of 4% oxalic acid solution at 90 占 폚 to obtain 653 g of an oil phase (concentration of Compound 3 was about 50% . From the obtained oil phase, xylene was removed under reduced pressure to obtain compound 3 as an oily substance. (Yield: 99.2%)
    [70] The chemical structure of Compound 3:
    [71] [(2,6-Me 2 C 6 H 3 O) 2 P (= O) OC 6 H 4 OP (= O) (2,6-Me 2 C 6 H 3 O) 2]
    [72] Example 1
    [73] First, 1,350 g of the viscous compound obtained in Synthesis Example 1 was placed in an oven at 130 캜 and heated for 1 hour to obtain a liquid product. Then, potassium titanate fiber (trade name: TISMO N-102, manufactured by Otsuka Chemical Co., Ltd., hereinafter abbreviated as "TISMO") was added to a super mixer (made by Kawada Manufacturing Co., 1,350 g of the oily substance of Synthesis Example 1, which had been preheated, was dropped little by little over 5 minutes from the inlet of the upper portion while stirring at 700 rpm while rotating at room temperature. After the injection, stirring was continued again for 2 minutes at 700 rpm at room temperature, and the pulverization was completed. The white powder mixture was extracted from the bottom of the super mixer to obtain the powdered flame retardant of the present invention.
    [74] Examples 2 to 3
    [75] The potassium titanate fiber was obtained in the same manner as in Example 1 except that the potassium titanate fiber was replaced with wollastonite (trade name "Bystal", hereinafter sometimes abbreviated as "WN") or magnesium borate fiber (trade name: PGM (Hereinafter sometimes abbreviated as " PGM ", hereinafter abbreviated as "PGM").
    [76] Examples 4 to 5
    [77] A powder flame retardant of the present invention was obtained in the same manner as in Example 1 except that Compound 1 was changed to Compound 2 or Compound 3 in Example 1.
    [78] Comparative Examples 1 to 5
    [79] A comparative powdery flame retardant was obtained in the same manner as in Examples 1 to 5 except that the amount of the fibrous material added was changed to 450 g.
    [80] Then, the powdery state of each powdery flame retardant obtained in Examples 1 to 5 and Comparative Examples 1 to 5 was evaluated based on the following criteria.
    [81] A shows complete powdering (uniform and completely powdered state), B shows partial powdering (state where the powdered part remains), and C shows incomplete powdering.
    [82] The average particle diameter (mm) of each powdery flame retardant was measured using a particle size distribution analyzer (trade name "Luzex", manufactured by Nicole).
    [83] Table 1 below shows the raw material composition, average particle diameter and powdered state of each powdered flame retardant.
    [84] Raw material flame retardant (part)Fibrous material (part)Average particle diameter (mm)Powdered state ExampleOneSynthesis Example 1 (50)TISMO (50)1.5A 2Synthesis Example 1 (50)WN 50,1.5A 3Synthesis Example 1 (50)PGM (50)2.0A 4Synthesis Example 2 (50)TISMO (50)1.2A 5Synthesis Example 3 (50)TISMO (50)2.3A Comparative ExampleOneSynthesis Example 1 (71)TISMO (29)5.5B 2Synthesis Example 2 (71)WN (29)7.1C 3Synthesis Example 3 (71)PGM (29)6.0C 4Synthesis Example 1 (80)TISMO (20)4.9B 5Synthesis Example 2 (80)WN (20)5.7C
    [85] It can be seen from Table 1 that the powdery flame retardants according to the present invention of Examples 1 to 5 are smaller in average particle diameter than the comparative powdery flame retardants of Comparative Examples 1 to 5 and superior in powdered state.
    [86] Test Examples 1 to 13
    [87] Each of the powdered flame retardants obtained in Examples 1 to 5 and Comparative Examples 1 to 5 was blended in a thermoplastic resin at a blending ratio shown in the following Table 2 and extruded in a twin-screw extruder (trade name: S1-KRC, 25 mm Kneader, (Manufactured by Sumitomo Heavy Industries, Ltd.) to obtain a test piece, which was then melt-kneaded using pelletizing machine (made by Kilimo Iron Works Co., Ltd.) .
    [88] The following thermoplastic resins were used.
    [89] PC / ABS: a mixture of "IUPILON S-2000" manufactured by Mitsubishi Engineering Plastics Co., Ltd. and "SANTAC UT-61" = 3/1 (weight ratio) manufactured by Mitsui Chemicals,
    [90] PBT-1200 S = 7/3 (weight ratio) mixture, manufactured by Mitsubishi Engineering-Plastics Co., Ltd., trade name "YuPiron S-2000" / TORAY Co.,
    [91] PPE / HIPS: trade name "XYRON X-9108" manufactured by Asahi Chemical Industry Co., Ltd.
    [92] The test pieces thus obtained were evaluated by the following evaluation method.
    [93] 1. Flexural modulus: JIS-K7203.
    [94] 2. Heat deflection temperature: ASTM D-648. Measured with a load of 18.6 kgf / cm 2 .
    [95] 3. Izod impact strength (IZ): JIS-K7110. Measured at 23 ° C.
    [96] 4. Melt flow rate (MFR): JIS-K7210. Measure at 240 ° C with a load of 10 kgf.
    [97] 5. Flame Retardancy: Based on UL-94 test method (Test for Flammability of Plastic Materials for Parts and Equipment UL-94, Fourth Edition), use a specimen of 1/16 inch thickness, 5 inch length and 0.5 inch width And evaluation tests were carried out. The evaluation criteria are as follows.
    [98] V-0: All of the following conditions A to E are satisfied.
    [99] A; One set of five specimens were flaming after the flame was applied, and the flaming was continued for less than 10 seconds,
    [100] B; Two sets of five specimens per set, total of 10 flames after touching the flaming sum is less than 50 seconds,
    [101] C; One set of five specimens does not flame to the clamp,
    [102] D; One set of five specimens did not drop flaming particles that fired cotton below 305 mm,
    [103] E; One set of five specimens, after the second flame contact, is glowing within 30 seconds, which does not burn but burns red.
    [104] V-1: All of the following conditions A to E are satisfied.
    [105] A; Flaming of any set of 5 specimens in a set is within 30 seconds after flame contact,
    [106] B; Two sets of five specimens per set, with a total of 10 flaming contacts, will total less than 250 seconds,
    [107] C and D; V-0,
    [108] E; Glowing is within 60 seconds after the second flame contact of any set of five specimens.
    [109] V-2: All of the following requirements are fulfilled.
    [110] A, B, C, and E; V-1,
    [111] D; One set of five test specimens drop flaming particles which ignite cotton below 305 mm.
    [112] HB: In the horizontal test, one set of three specimens does not burn up to the 101.6mm standard line after flame contact.
    [113] 6. Dripping property: When flame-retardant test was performed, the presence or absence of flaming particles (dripping) to ignite the surface was observed.
    [114] 7. Viscosity: Using a "Type B Viscometer" manufactured by Tokyo Instruments Co., Ltd., a new experimental chemistry lecture (March 20, 1978, 3rd edition, Maruzen Co., Ltd.) 1- (1) 172 pages.
    [115] Table 2 shows the blending ratios of the thermoplastic resin and the powdered flame retardant.
    [116] Test ExampleThermoplastic resin (part)Powdered flame retardant (part) OneThe PC / ABS (100)Example 1 (30) 2The PC / ABS (100)Example 2 (30) 3The PC / ABS (100)Example 3 (30) 4The PC / ABS (100)Example 4 (30) 5The PC / ABS (100)Example 5 (30) 6PC / PBT 100,Example 2 (30) 7PPE / HIPS (100)Example 3 (30) 8PPE / HIPS (100)Example 1 (30) 9The PC / ABS (100)Comparative Example 1 (20) 10The PC / ABS (100)Comparative Example 2 (20) 11The PC / ABS (100)Comparative Example 3 (20) 12PC / PBT 100,Comparative Example 4 (25) 13PPE / HIPS (100)Comparative Example 5 (25)
    [117] Table 3 below shows the test results of the test pieces of each test example.
    [118] Test ExampleFlammability UL-94Presence or absence of drippingBending modulus of elasticity kgf / ㎠Heat deformation temperature ℃IZkgf · cm / cmMFRg / 10 min OneV-0none2.4 × 10⁴1016735 2V-0none2.4 × 10⁴997333 3V-0none2.4 × 10⁴1207860 4V-0none2.4 × 10⁴1105454 5V-0none2.4 × 10⁴1036540 6V-0none2.4 × 10⁴1207860 7V-0none2.3 × 10⁴986141 8V-0none2.3 × 10⁴985538 9V-2has exist2.4 × 10⁴1287860 10V-2has exist2.4 × 10⁴1105454 11V-2has exist2.4 × 10⁴1036540 12V-2has exist2.3 × 10⁴986141 13V-2has exist2.3 × 10⁴985538
    [119] From the results shown in Table 3, the molded articles obtained from the flame retardant resin compositions containing the inventive powder flame retardants of Examples 1 to 10, compared with the molded articles obtained from the flame retardant resin compositions containing the comparative powder flame retardants of Comparative Examples 1 to 5, It can be seen that the flame retardancy is remarkably excellent.
    [120] According to the powdery flame retardant of the present invention, since the flame retardant of a liquid or viscous liquid at room temperature is mixed with or adsorbed on an inorganic fibrous material, it is easy to handle because of its powdery form and can be pulverized in a short period of time , A simple and industrially advantageous method can be obtained, and an excellent and remarkable effect is obtained in that the performance of the flame retardant as a raw material is not deteriorated.
    [121] Further, according to the powdery flame retardant of the present invention using the raw material flame retardant containing no halogen element, when the flame retardant resin composition is blended with a synthetic resin, it is possible to obtain UL- Flame retardancy at the V-0 level can be achieved by a test based on the flame retardancy test method of 94. Therefore, it is very suitable as a powdered flame retardant for a completely halogen-free flame retardant resin composition.
    [122] The various molded articles formed by molding the flame retardant resin composition containing the powdered flame retardant of the present invention can be used in various fields such as electric, electronic, communication, agriculture, forestry and fisheries, mining, construction, food, textile, clothing, medical, coal, , Automobiles, precision instruments, wood, furniture, printing, and musical instruments. More specifically, for example, a printer, a personal computer, a word processor, a keyboard, a PDA (small information terminal), a telephone, a facsimile, a copier, an ECR (electronic money register), an electronic calculator, TV sets, VCRs, video cameras, radio cassettes, tapes, etc., such as stationery, OA equipment such as office stationery, washing machines, refrigerators, vacuum cleaners, microwave ovens, lighting equipment, game machines, irons, and kotatsu Relays, capacitors, switches, printer substrates, coil bobbins, semiconductor encapsulating materials, wires, cables, transformers, deflection yokes, distribution boards (such as electronic devices, recorders, compact discs, CD players, speakers and liquid crystal displays) Electric distribution boards), watches and other electric and electronic parts, and communication devices. In addition, it is also possible to provide a seat for a seat, such as a seat (padding, a cover), a belt, a ceiling cover, a convertible tops, an armrest, a door trim, a rear package trays, a carpet, Coverings, airbags, insulators, handles, hand straps, wire cladding, electrical insulation, paints, coatings, overlaying materials, flooring, corner walls, deck panels, covers, plywood, Automobiles, vehicles, ships, aircraft and building materials such as partition boards, side walls, carpets, wallpaper, wall materials, exterior materials, interior materials, roofing materials, sound insulation boards, insulation panels, window materials, Suitable for daily life and sports goods such as sheet, plywood, synthetic plate, carpet, door mat, sheet, buckets, hose, container, glasses, bag, case, goggles, ski plate, racket, tent, musical instruments Do.
    权利要求:
    Claims (11)
    [1" claim-type="Currently amended] Mixing a flame retardant exhibiting a liquid or viscous solid state at room temperature with an inorganic fibrous substance and adhering or adsorbing the flame retardant to the fibrous substance,
    5 to 70% by weight of the flame retardant and 95 to 30% by weight of the fibrous material.
    [2" claim-type="Currently amended] The method according to claim 1,
    A flame retardant which is at least one selected from a phosphazene compound and a phosphoric ester compound, wherein the flame retardant exhibiting a liquid or viscous solid at room temperature is a flame retardant.
    [3" claim-type="Currently amended] 3. The method of claim 2,
    Wherein the phosphazene compound is represented by Formula 1
    (Formula 1)

    Wherein m represents an integer of 3 to 25; And two R 1 s are the same or different and each represents a phenyl group or an unsubstituted phenyl group substituted with at least one group selected from an alkyl group having 1 to 6 carbon atoms and an allyl group, .
    [4" claim-type="Currently amended] 3. The method of claim 2,
    Wherein the phosphazene compound is represented by Formula 2
    (2)

    Wherein n represents an integer of 3 to 1000. Two R < 1 > are the same or different and each represents a phenyl group or an unsubstituted phenyl group substituted with at least one group selected from an alkyl group having 1 to 6 carbon atoms and an allyl group; X represents -N = P (OR 1) 3 or -N = P (O) OR 1 . And Y represents -P (OR 1 ) 4 or -P (O) (OR 1 ) 2 .
    [5" claim-type="Currently amended] 3. The method of claim 2,
    Wherein the phosphazene compound is at least one phosphazene compound selected from a cyclic phosphazene compound represented by the formula (1) and a linear phosphazene compound represented by the formula (2) in the presence of an o-phenylene group, a m- p-phenylene group, biphenylene group and Wherein A represents a group -SO 2 -, a group -S-, a group -O- or a group -C (CH 3 ) 2 -. Wherein the crosslinking agent is a crosslinked phosphazene compound crosslinked with at least one kind of crosslinking group selected from the group represented by the following formula:
    [6" claim-type="Currently amended] 3. The method of claim 2,
    Wherein said phosphazene compound is represented by the following formula
    (Formula 3)

    Wherein R 2 represents a cyano-substituted phenyl group. R 3 is an alkyl group having 1 to 18 carbon atoms or an aryl group having 6 to 10 carbon atoms, and these groups may be substituted with at least one group selected from an alkyl group having 1 to 10 carbon atoms, an allyl group and an aryl group. When the R 3, which has two or more, they each other R 3, may be the same or different. p and q represent real numbers satisfying p > 0, q > 0 and p + q = 2. and r represents an integer of 3 to 25, and a cyclic phosphazene compound represented by the following formula
    (Formula 4)

    Wherein R 2 , R 3 , p and q are as defined above. and s represents an integer of 3 to 1000. X 'is -P (OR 2) 4, -P (OR 2) 3 (OR 3), -P (OR 2) 2 (OR 3) 2, -P (OR 2) (OR 3) 3, -P (oR 3) 4, -P ( O) (oR 2) 2, -P (O) (oR 2) (oR 3) or -P (O) (oR 3) represents a 2, Y 'is -N = P (OR 2) 3, -N = P (OR 2) 2 (OR 3), -N = P (OR 2) (OR 3) 2, -N = P (OR 3) 3, -N = P ( O) OR < 2 > or -N = P (O) OR < 3 & gt ;, wherein at least one of R < 1 >
    [7" claim-type="Currently amended] 3. The method of claim 2,
    Wherein the phosphoric acid ester compound is at least one selected from the group consisting of trimethyl phosphate, triethyl phosphate, tributyl phosphate, tris (2-chloroethyl) phosphate, tris (p-tolyl) phosphate and resorcinol- Wherein the flame retardant is at least one selected from the group consisting of resorcinol-bis (diphenyl phosphate) and tris (dibromopropyl) phosphate.
    [8" claim-type="Currently amended] 8. The method of claim 7,
    Wherein the phosphoric acid ester compound is at least one member selected from the group consisting of trimethyl phosphate, triethyl phosphate, tributyl phosphate, tris (p-tolyl) phosphate and resorcinol-bis (diphenyl phosphate).
    [9" claim-type="Currently amended] The method according to claim 1,
    Wherein the inorganic fibrous material is selected from the group consisting of fibrous titanic acid alkali metal salts, fibrous boric acid transition metal salts, fibrous boric acid alkaline earth metal salts, fibrous zinc oxide, fibrous titanium oxide, fibrous magnesium oxide, fibrous gypsum, fibrous calcium silicate, fibrous silicon carbide, Wherein the powdery flame retardant is at least one selected from the group consisting of titanium carbide, fibrous silicon nitride, fibrous titanium nitride, carbon fiber, alumina fiber, alumina-silica fiber, zirconia fiber, glass fiber and quartz fiber.
    [10" claim-type="Currently amended] The method according to claim 1,
    Wherein said inorganic fibrous substance is at least one selected from the group consisting of fibrous titanic acid alkali metal salts, wollastonite, and magnesium borate fibers.
    [11" claim-type="Currently amended] The method according to claim 1,
    A powdery flame retardant having an average particle diameter of about 500 탆 to about 4 mm.
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    同族专利:
    公开号 | 公开日
    JP3364679B2|2003-01-08|
    DE69918721D1|2004-08-19|
    KR100441920B1|2004-07-27|
    CN1120197C|2003-09-03|
    AT271092T|2004-07-15|
    TWI225875B|2005-01-01|
    EP1153971A1|2001-11-14|
    EP1153971B1|2004-07-14|
    US6627122B1|2003-09-30|
    DE69918721T2|2005-07-21|
    WO2000012603A1|2000-03-09|
    EP1153971A4|2002-05-22|
    JP2000063564A|2000-02-29|
    CN1313877A|2001-09-19|
    引用文献:
    公开号 | 申请日 | 公开日 | 申请人 | 专利标题
    法律状态:
    1998-08-26|Priority to JP24010498A
    1998-08-26|Priority to JP240104/1998
    1999-08-12|Application filed by 오츠카 유지로, 오츠카 가가쿠 가부시키 가이샤
    2001-07-31|Publication of KR20010072918A
    2004-07-27|Application granted
    2004-07-27|Publication of KR100441920B1
    优先权:
    申请号 | 申请日 | 专利标题
    JP24010498A|JP3364679B2|1998-08-26|1998-08-26|Powdered flame retardant|
    JP240104/1998|1998-08-26|
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