WO2012108190A1 - Agent ignifugeant pour mélangeage à une résine thermoplastique, composition de résine ignifugée et procédé de production de la composition de résine ignifugée - Google Patents

Agent ignifugeant pour mélangeage à une résine thermoplastique, composition de résine ignifugée et procédé de production de la composition de résine ignifugée Download PDF

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Publication number
WO2012108190A1
WO2012108190A1 PCT/JP2012/000824 JP2012000824W WO2012108190A1 WO 2012108190 A1 WO2012108190 A1 WO 2012108190A1 JP 2012000824 W JP2012000824 W JP 2012000824W WO 2012108190 A1 WO2012108190 A1 WO 2012108190A1
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flame retardant
thermoplastic resin
resin
dihydrogen phosphate
flame
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PCT/JP2012/000824
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English (en)
Japanese (ja)
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岡本　忠
敬介 森川
彰 森永
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星和電機株式会社
株式会社森川商店
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Publication of WO2012108190A1 publication Critical patent/WO2012108190A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/32—Phosphorus-containing compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/16—Nitrogen-containing compounds
    • C08K5/21—Urea; Derivatives thereof, e.g. biuret
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K2201/00—Specific properties of additives
    • C08K2201/014—Additives containing two or more different additives of the same subgroup in C08K

Definitions

  • the present invention relates to a flame retardant for thermoplastic resin kneading, a flame retardant resin composition obtained by adding and kneading the flame retardant for thermoplastic resin kneading to a thermoplastic resin, and the flame retardant resin composition
  • the present invention relates to a method for manufacturing a product.
  • halogen compounds and phosphorus / nitrogen compounds are used as flame retardants for thermoplastic resins because they exhibit a remarkable flame retardant effect.
  • the flame retardant is indispensable in today's society where damages caused by fires on houses are increasing, and halogen flame retardants made of bromine compounds and chlorine compounds are widely used.
  • Patent Document 1 describes ammonium dihydrogen phosphate as one of the options. Has proposed a flame retardant for polylactic acid fiber, and Patent Document 3 proposes a flame retardant for silicon rubber.
  • the method of using a flame retardant for a thermoplastic resin includes a method of applying a solution or dispersion of the flame retardant, a method of coexisting a flame retardant during resin polymerization, and melt-kneading into a thermoplastic resin. There are methods.
  • non-halogen flame retardant such as ammonium dihydrogen phosphate can provide effective flame retardancy for, for example, polyethylene terephthalate, but the physical properties of polyethylene terephthalate are reduced when the amount added is large. There has been a problem in that, due to the deterioration of the physical properties, there is an adverse effect in processing steps for fiberizing and forming polyethylene terephthalate.
  • thermoplastic resins such as polyethylene terephthalate are poorly compatible with mixed foreign substances, and it takes time to knead ammonium dihydrogen phosphate and the resin.
  • molecular chain is cut by hydrolysis or thermal decomposition due to the decrease in molecular weight, and a decrease in physical properties accompanying this decrease in molecular weight decreases viscosity, strength, and stretchability.
  • the coating method has a high flame retardant concentration on the resin surface and excellent flame retardancy, but the durability is inferior, and it takes time for coating and drying. Therefore, there is a problem that the addition concentration and dispersion are limited.
  • the melt kneading method can obtain a resin composition having excellent durability, can be processed in a large amount by extrusion molding, and when kneading a flame retardant into a thermoplastic resin, Highly compatible and dispersible organophosphorus / nitrogen flame retardant components are used with emphasis on solubility and dispersibility, but there are limits to the flame retardant effect of organophosphorus / nitrogen flame retardant components Therefore, there is a problem that it is insufficient to obtain the high flame retardancy required in the industry.
  • the flame retardant with poor dispersibility increases the proportion of the portion where the flame retardant does not exist, and the original flame retardant effect is exhibited. Because it is difficult to burn, it is necessary to add a large amount of a flame retardant to ensure a certain level of flame retardant using a flame retardant with low dispersibility. In order to impart flame retardancy to thermoplastic resins with high flammability, the flame retardant should be made as uniform as possible. It is desirable to disperse, and the more the dispersibility is improved, the more the inherent function of the flame retardant is exerted to the maximum, and a large flame retardant effect is obtained with a small amount of addition.
  • the present invention employs a non-halogen flame retardant that does not generate toxic gases or dioxins, and improves dispersibility and uniformity with a thermoplastic resin, thereby producing a non-halogen flame retardant and polyethylene terephthalate. It can be easily made into fiber while maintaining the melt viscosity, which is a feature of thermoplastic resins, by eliminating the decrease in extensibility in combination with thermoplastic resins such as It is a technical problem to provide a new technical means capable of obtaining the above.
  • Inorganic salts added as flame retardants have a relatively low polarity and a resin solubility parameter (sp value) (A. D. McNaught, A. Wilkinson, IUPAC Compendium of Chemical Terminology, 2nd ed., Blackwell Scientific Publications, Oxford (1977)), it is desirable to use a substance with a value close to that of hard / soft acid / base theory (RG Pearson, J. American Chemical Society, Vol.
  • a soft salt with reduced charge bias is suitable, and a salt of a polyvalent ion is highly hard, so if it is present in a large amount, the composition as a whole
  • a non-halogen flame retardant selective use of potassium dihydrogen phosphate and lithium dihydrogen phosphate, which are less thermally degradable and close to neutrality, is considered as a non-halogen flame retardant.
  • a flame retardant containing potassium dihydrogen phosphate and lithium dihydrogen phosphate was used.
  • thermoplastic resins It is known that the dispersion and compatibility (mutual solubility) of thermoplastic resins depends on the sp value, and substances close to the sp value are known to be compatible with each other.
  • the potassium dihydrogen phosphate and lithium dihydrogen phosphate Highly polar resins with high sp values are suitable for thermoplastic resins that exhibit good dispersion and compatibility with flame retardants that contain high and high sp values for inorganic metal salts. Because it is not suitable for hydrophobic resins with small sp value such as silicone resin, polyethylene, polypropylene, etc., it is not suitable for dispersibility, so a highly polar thermoplastic resin with a large sp value is selectively adopted.
  • the solid substance shows a lower melting point than any of the mixed substances when mixing different substances
  • the magnitude of the eutectic point depressing action is specific to the substance to be mixed.
  • the effect of the eutectic melting point lowering effect is used to control the melting point of the flame retardant within a certain range, and solid materials are crushed and micronized at temperatures near the melting point. Utilizing the phenomenon that makes it easy to generate, the melting point is near the temperature at which the thermoplastic resin softens and melts, and the flame retardant is easily crushed and refined during the thermoplastic resin kneading process.
  • thermoplastic resin kneading flame retardant according to the present invention contains at least potassium dihydrogen phosphate and lithium dihydrogen phosphate.
  • sodium dihydrogen phosphate is further blended in the flame retardant for kneading thermoplastic resin.
  • any one of the above-mentioned flame retardants for kneading a thermoplastic resin further contains aluminum dihydrogen phosphate and / or urea.
  • thermoplastic resin is a polyester resin.
  • the polyester resin is selected from polyethylene terephthalate (PET), polybutylene terephthalate (PBT), and polyethylene naphthalate (PEN).
  • thermoplastic resin is a polyamide resin.
  • the flame retardant resin composition according to the present invention is added to the thermoplastic resin so that any one of the thermoplastic resin kneading flame retardants is 1 to 25% by weight based on the total amount. It is what.
  • the present invention provides the flame retardant resin composition having a peak in the 31 P-solid NMR spectrum in a range of -18 to -20 ppm and -1 to +2 ppm based on NH 4 H 2 PO 4. is there.
  • the method for producing a flame retardant resin composition according to the present invention comprises using a polyester resin or polyamide as a flame retardant for kneading a thermoplastic resin containing at least potassium dihydrogen phosphate and lithium dihydrogen phosphate.
  • a thermoplastic resin kneading flame retardant having a melting point near the temperature at which the thermoplastic resin is softened and melted is used.
  • the flame retardant is added to the thermoplastic resin and kneaded at a temperature equal to or higher than the temperature at which the thermoplastic resin softens in the kneading process, and then the flame retardant is crushed and subdivided. By continuing the above, the flame retardant is uniformly dispersed and compatible in the thermoplastic resin.
  • At least potassium dihydrogen phosphate and lithium dihydrogen phosphate are blended in a desired amount, or further, sodium dihydrogen phosphate and / or dihydrogen phosphate metal salt or urea of aluminum dihydrogen phosphate.
  • the melting point was adjusted so that the thermoplastic resin of the polyester resin and polyamide resin that knead the melting point of the flame retardant by blending with the thermoplastic resin is softened and melted, making it flame retardant in the kneading process Since the agent is crushed and refined and can be dispersed and compatible in the resin at the nano level or lower molecular level, it satisfies the IV value that can be formed on fibers and films, and also has a flame retardant effect. Thus, a flame retardant resin composition that can be easily processed as a fiber or a film can be obtained.
  • composition of the flame retardant comprising three salts of potassium dihydrogen phosphate (A), lithium dihydrogen phosphate (B) and sodium dihydrogen phosphate (C) and the melting temperature of the initial reaction product It is a schematic phase diagram shown. 31 is a graph showing a 31 P-solid NMR spectrum.
  • Embodiment 1 FIG.
  • the flame retardant for thermoplastic resin kneading according to the present embodiment is formed by blending at least potassium dihydrogen phosphate and lithium dihydrogen phosphate.
  • the temperature is an actually measured temperature
  • values of each side of the triangle are potassium dihydrogen phosphate (KH 2 PO 4 ), lithium dihydrogen phosphate (LiH 2 PO 4 ), and phosphoric acid shown at the right end of the side.
  • the compounding ratio (% by weight) of the component of sodium dihydrogen (NaH 2 PO 4 ) is shown.
  • the shaded area in the figure indicates the flame retardant composition range suitable for PET (melting point around 255 ° C), and the suitable area for 6-nylon (melting point 225 ° C) is the flame retardant composition range indicated by the wavy line in the figure. Show.
  • polyamide resins have extremely high melt viscosity
  • flame retardants that melt at higher temperatures than polyester resins, and the appropriate melting temperature correlation of resin-flame retardants found in polyester resins. Different from the higher temperature region becomes the suitable region.
  • the compounding ratio of potassium dihydrogen phosphate and lithium dihydrogen phosphate is 25% as the proportion of potassium dihydrogen phosphate according to the phase diagram of FIG. 1 as a composition having a eutectic point corresponding to the melting temperature of the thermoplastic resin. Since the range of ⁇ 90% by weight is applied, it is preferable to use 10 to 300 parts by weight of lithium dihydrogen phosphate with respect to 100 parts by weight of potassium dihydrogen phosphate, and less than 10 parts by weight is preferable because the melting temperature becomes too high. If the amount exceeds 300 parts by weight, the melting temperature is similarly high, which is not preferable. More preferred is 35 to 300 parts by weight.
  • the mixture of potassium dihydrogen phosphate and lithium dihydrogen phosphate is heated in a 200 ° C. to 300 ° C. environment with stirring and completely melted, and then mixed well for 15 to 30 minutes, and then cooled. To obtain a crystalline solid.
  • the crystalline solid is pulverized into a flame retardant.
  • the flame retardant for kneading thermoplastic resin may contain sodium dihydrogen phosphate.
  • the compounding ratio of potassium dihydrogen phosphate, lithium dihydrogen phosphate and sodium dihydrogen phosphate is a composition having a melting point corresponding to the melting temperature of the thermoplastic resin. Since the ranges of 20 to 85% by weight potassium hydrogen, 5 to 75% by weight lithium dihydrogen phosphate, and 50% by weight or less sodium dihydrogen phosphate apply, lithium dihydrogen phosphate with respect to 100 parts by weight potassium dihydrogen phosphate 10 to 300 parts by weight and 10 to 100 parts by weight of sodium dihydrogen phosphate are preferably used. If the amount of sodium dihydrogen phosphate is less than 10 parts by weight, the effect of adding sodium dihydrogen phosphate is not significantly recognized. Also, if it exceeds 100 parts by weight, the melting temperature becomes too low, which is not preferable. More preferred is 25 to 250 parts by weight of lithium dihydrogen phosphate and 15 to 80 parts by weight of sodium dihydrogen phosphate.
  • the mixture of the potassium dihydrogen phosphate, lithium dihydrogen phosphate, and sodium dihydrogen phosphate is heated in a 250 ° C. to 350 ° C. environment with stirring and completely melted for 15 to 30 minutes. Mix and then cool to obtain a crystalline solid. The crystalline solid is pulverized into a flame retardant.
  • the flame retardant for kneading thermoplastic resin may contain aluminum dihydrogen phosphate (Al (H 2 PO 4 ) 3 ) and / or urea (CO (NH 2 ) 2 ).
  • Al (H 2 PO 4 ) 3 aluminum dihydrogen phosphate
  • CO (NH 2 ) 2 urea
  • Each compounding ratio is 10 to 300 parts by weight of lithium dihydrogen phosphate, 10 to 100 parts by weight of sodium dihydrogen phosphate, and 0 to 5 parts by weight of aluminum dihydrogen phosphate with respect to 100 parts by weight of potassium dihydrogen phosphate.
  • urea forms a nitrogen-containing condensate through a complex reaction at high temperatures, and this is estimated to contribute to flame retardancy and solubility, so that flame retardancy is improved.
  • lithium dihydrogen phosphate is 20 to 250 parts by weight
  • sodium dihydrogen phosphate is 10 to 80 parts by weight
  • aluminum dihydrogen phosphate is 0 to 3 parts by weight
  • urea is 0 to 7 parts by weight
  • urea 0 to 2 parts by weight.
  • the compounded potassium dihydrogen phosphate and lithium dihydrogen phosphate and / or sodium dihydrogen phosphate undergo a dehydration condensation reaction with each other by heating, and the dihydrogen phosphate metal salt and the reaction thereof.
  • r K m Li n Na o H p PO q
  • r K m Li n Na o H p PO q
  • the mixture is prepared as a powdery solid that is easy to knead and is thermoplastic.
  • a flame retardant effect can be obtained because it has a melting point near the melting temperature of the resin and disperses and liquefies during the kneading process with the thermoplastic resin, and disperses and dissolves with high uniformity.
  • the preparation of the flame retardant used for flame retarding of the thermoplastic resin is preferably controlled by the reaction time after the blended metal dihydrogen phosphate is completely melted and mixed.
  • the reaction time after the blended metal dihydrogen phosphate is completely melted and mixed.
  • the flame retardant according to the present embodiment utilizes the phenomenon that the melting point changes depending on the composition, potassium dihydrogen phosphate and lithium dihydrogen phosphate, and, if necessary, sodium dihydrogen phosphate as an accessory component, Prepared to melt at the temperature most suitable for dispersion and dissolution near the softening and melting temperature of each thermoplastic resin using aluminum dihydrogen phosphate and urea.
  • An optimized flame retardant can be used, and an environment-friendly flame retardant that contributes to a reduction in time and temperature required for kneading can be obtained.
  • the flame retardant according to the present embodiment has high transparency when melted and dispersed completely by blending, and is excellent in dispersibility in the resin. Therefore, the flame retardant resin composition ( Film and fiber) and can be used in a wide range. Moreover, when the dispersibility is improved, the amount added can be reduced, the economic efficiency is increased, the physical properties of the flame retardant resin composition are improved, and processing such as production of a thinner film becomes possible.
  • additives include phosphoric acid of other typical metals and transition metals.
  • Functional compounds such as dihydrogen salts, urea, borates, heteropolyacid salts and various pigments can be mentioned.
  • the flame retardant resin composition according to the present embodiment is obtained by adding the flame retardant for thermoplastic resin kneading to the thermoplastic resin to a temperature equal to or higher than the softening temperature of the thermoplastic resin (for example, 200 ° C. for general-purpose PET resin). The mixture is heated and kneaded and molded into pellets to obtain a flame retardant resin composition. In order to suppress deterioration of the physical properties of the resin due to heat, it is preferable that the kneading temperature is not excessively raised.
  • thermoplastic resin polyester resin or polyamide resin of PET, PBT and PEN can be used.
  • the IV value that can be used for fiber and film formation is generally 0.5 to 0.6 or more (Togi Suzuki, Fiber and Industry 59, 7, p223 (2003)), and the quality of PET resin
  • the amount of the flame retardant added to the thermoplastic resin is preferably adjusted so that the IV value is 0.63 to 0.88. If the amount added is excessively increased, a decrease in physical properties is induced. Therefore, it is necessary to suppress the amount to an appropriate amount. That is, the flame retardant is added to the thermoplastic resin so that the IV value satisfies 0.63 to 0.88, the addition amount is small, and the total amount is 1 to 25% by weight, more preferably 1 to 20% by weight.
  • flame retardants for kneading thermoplastic resins are selected on the basis of ease of melting point adjustment and excellent flame retardant effect of the kneaded resin when kneaded into polyester resin or polyamide resin.
  • sodium hydride as an accessory component, as shown in FIG. 1, the range of the melting point adjustment can be further expanded, and the compatibility with the melting point of the resin can be increased, and the viscosity of the polyester resin rapidly decreases after melting. Therefore, when the flame retardant is kneaded, it is desirable that the polyester resin and the flame retardant have close melting points so that good dispersion can be easily obtained.
  • a flame retardant having a melting point slightly higher than the melting temperature of the polyamide resin is suitable.
  • the flame retarding effect of the resin when the flame retardant is kneaded with a thermoplastic resin varies depending on the resin.
  • a thermoplastic resin such as a polyester resin or a polyamide resin
  • the melting point of the mixture changes as shown in FIG. 1 depending on the type of salt used and the mixing ratio thereof, so that an appropriate dispersion temperature in the vicinity of the melting point of the thermoplastic resin to be added.
  • thermoplastic resin containing at least potassium dihydrogen phosphate and lithium dihydrogen phosphate when adding a flame retardant for kneading thermoplastic resin containing at least potassium dihydrogen phosphate and lithium dihydrogen phosphate to a polyester resin or polyamide resin, Since the flame retardant having a melting point near the melting temperature is added to the resin and kneaded at a temperature equal to or higher than the temperature at which the resin softens. Since the flame retardant is crushed and refined and dispersed in the smelting process, the flame retardant can be uniformly dispersed and compatible in the resin.
  • Examples 1 to 6 potassium dihydrogen phosphate (KH 2 PO 4 ), lithium dihydrogen phosphate (LiH 2 PO 4 ), sodium dihydrogen phosphate (NaH 2 PO 4 ), aluminum dihydrogen phosphate (Al ( H 2 PO 4 ) 3 ) and / or urea (CO (NH 2 ) 2 ) are blended in the proportions shown in Table 1, and this mixture is stirred while being heated and completely stirred at a temperature of 200 ° C to 350 ° C. After melting, the mixture was thoroughly mixed for 15 to 30 minutes and cooled, and the obtained crystalline solid was pulverized to prepare flame retardants a (Example 1) to f (Example 6).
  • the melting temperature indicates an actually measured temperature at which the flame retardant is completely dissolved by heating on a hot plate, and it was judged whether the melted state was uniform or transparent by visual observation.
  • Examples 7 to 20 Flaked PET resin obtained by pulverizing and washing used PET bottles (R-PET: melting temperature Tm254 ° C.), commercially available PET resin (Recron, Mitsubishi V-PET; melting temperature Tm 244 ° C.), PEN (Teijin Chemicals Co., Ltd .; Tm265 ° C.) Pellets and commercially available polyamide resin (6-nylon manufactured by Toray Industries, Inc .; Tm 225 ° C.) were crushed to prepare polyamide resin crushed materials. After adding f so that the addition weight becomes the blending ratio shown in Table 2, Table 3, and Table 4 with respect to the total amount (total amount) of the flame retardant and the thermoplastic resin, the mixture is stirred and mixed in a mixer.
  • the yarn was molded and cut with a twin-screw extruder at a high temperature above the softening point of the thermoplastic resin to obtain each flame-retardant resin composition in the form of pellets.
  • Tables 2, 3, and 4 show the results of flame retardant evaluation tests performed on the respective flame retardant resin compositions.
  • “Flame retardance (resin)” in the table is the temperature at which the resin melts by adding the flame retardant to the weight percentage indicated by the “addition amount of flame retardant” with respect to the total amount.
  • “ ⁇ ” indicates that the specimen did not ignite even when the paper burned out, “ ⁇ ” indicated that the specimen had ignited but was extinguished within a few seconds, and “ ⁇ ” once indicated the specimen. Ignited and burned for a while, but self-extinguishing.
  • “Flame retardance (fiber)” indicates the flame retardancy evaluation of the filamentous flame retardant resin composition, “ ⁇ ” indicates that the fiber did not ignite or self-extinguished within 1 second after ignition, “ ⁇ ” indicates that the flame ignited but extinguishes within a few seconds, and “ ⁇ ” indicates that the fiber self-extinguishes but the ignited drop ignites a cotton placed 30 cm below. .
  • Fiber uniformity indicates the visual uniformity of the thread-like flame retardant resin composition, “ ⁇ ” is uniform, “ ⁇ ” indicates that dispersion unevenness of 1 or less in 100 mm length is recognized, “ ⁇ ” indicates that two or more dispersion irregularities are observed in a length of 100 mm.
  • Example 7 flame retardant a (melting temperature: 240 ° C.) prepared by adding half the amount of lithium dihydrogen phosphate to potassium dihydrogen phosphate and melt-kneading was adjusted to 5% by weight based on the total amount. Added to R-PET. As shown in Table 2, the flame retardant resin composition obtained by kneading at or above the softening point of the resin showed good flame retardancy and good dispersibility. Next, in Example 8, the blending ratio of the flame retardant raw material is different between the flame retardant a and the flame retardant b, and the melting temperature of the flame retardant generated for this change also changes. Different results were obtained. For R-PET, flame retardant b was superior to flame retardant a.
  • Example 14 5% by weight of flame retardant c in 90% by weight of V-PET and organophosphorous flame retardant as a dissolution aid (manufactured by Daihachi Chemical Industry Co., Ltd .: product name: PX200) After adding 5% by weight and stirring and mixing with a mixer, a yarn is molded and cut with a twin-screw extruder at a temperature higher than the softening point of the resin to obtain a flame-retardant resin composition in the form of pellets. is there.
  • the flame retardant evaluation of this composition was “ ⁇ ”.
  • Example 13 and Example 14 when the IV value of the composition and the flame retardance by the UL flammability test were evaluated, the IV values were 0.639 and 0.643, respectively. Moreover, the flame retardance index based on the method shown in UL94 was both V-0. In Example 19, good flame retardancy and excellent moldability were exhibited.
  • the phosphorus-31 solid state NMR (MAS 31 PNMR) in each flame retardant resin composition was measured, and was found to be ⁇ 18 to 20 ppm and ⁇ 1 to +2 ppm (NH 4 H 2 PO 4 standard). ) was confirmed to have absorption (peak).
  • the peaks in the 31 P-solid state NMR spectrum are in the range of ⁇ 18 to ⁇ 20 ppm and ⁇ 1 to +2 ppm on the basis of NH 4 H 2 PO 4. I had to.
  • Comparative Example 1 100 parts by weight of water was added to 100 parts by weight of ammonium dihydrogen phosphate to form an aqueous solution. Thereafter, the aqueous solution was stirred while heating at 100 to 120 ° C. to evaporate the water, and the ammonia was scattered to obtain a powder of particulate crystals.
  • the pH value of the 5% aqueous solution of the powder was 4.7, and the pH value after firing of the 5% aqueous solution after burning at 200 ° C. was 2.5.
  • the IV value of the PET resin composition to which 5% by weight of the powder was added relative to the total amount showed 0.629, and it was not possible to obtain an IV value capable of forming PET fibers and films with the added amount.
  • the result of the iron nail corrosion test showed a weight loss of 7.36%, indicating high corrosivity.
  • Comparative Example 2 12.8% by weight of potassium hydroxide and 8.2% by weight of glycerin were mixed with 72.8% by weight of ammonium dihydrogen phosphate, and 100 parts by weight of water was added to make an aqueous solution. Thereafter, the aqueous solution was stirred while heating at 100 to 120 ° C. to evaporate the water, and the ammonia was scattered to obtain a powder of particulate crystals, which was used as a flame retardant.
  • Comparative Example 3 Flame retardant for particulate crystals (melting temperature 275 ° C) obtained by heating and melting reaction of 53.1% by weight potassium dihydrogen phosphate and 46.9% by weight sodium dihydrogen phosphate in R-PET as a whole After adding 5% by weight to the amount and stirring and mixing with a mixer, the yarn was molded and cut with a twin screw extruder at a high temperature of 250 ° C. or higher to obtain a flame retardant resin composition in the form of pellets. .
  • Comparative Example 4 A composition obtained by adding 5% by weight of sodium dihydrogen phosphate (melting temperature of 300 ° C. or higher) to V-PET and heating and kneading the mixture is sodium dihydrogen phosphate and PET resin. Therefore, the dispersibility was poor and a uniformly dispersed composition could not be obtained. Moreover, the flame retardance of a test piece molded from the composition into a plate shape was low, and evaluations ⁇ to ⁇ lacking practicality.
  • sodium dihydrogen phosphate melting temperature of 300 ° C. or higher
  • Comparative Example 5 5% by weight of flame retardant c (melting temperature: 240 ° C.) is added using polylactic acid (manufactured by Toyota; PLA, melting point: 167 ° C.), which is a biological resin, and kneaded in the same manner to make it flame retardant When the characteristic which evaluated the characteristic which obtained the resin composition was evaluated, all showed that it was not mutually compatible in both flame retardance and moldability.
  • flame retardant c melting temperature: 240 ° C.
  • polylactic acid manufactured by Toyota; PLA, melting point: 167 ° C.
  • Comparative Example 6 Flame retardant c was added to V-PET so as to be 30% by weight, and melt kneading was attempted. However, uniform kneading was difficult and a uniform resin composition could not be obtained. .
  • a flame-retardant resin composition for a thermoplastic resin that can be easily fiberized while maintaining the viscosity, which is a physical property of a thermoplastic resin, and at the same time, can be provided.
  • the problem of generating toxic gases and dioxins inherent in the flame retardants can be solved, contributing to environmental conservation.

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Abstract

La présente invention concerne un agent ignifugeant pour mélangeage à une résine thermoplastique, l'agent ignifugeant ne générant ni gaz toxiques ni dioxines, ce qui permet à la résine de conserver sa viscosité à l'état fondu et de pouvoir être aisément façonnée en fibres ou en pellicules, tout en présentant un effet ignifugeant. La présente invention concerne également une composition de résine ignifugée et un procédé de production de la composition de résine ignifugée. L'agent ignifugeant pour mélangeage à une résine thermoplastique est constitué de dihydrogénophosphate de potassium, de dihydrogénophosphate de lithium, de dihydrogénophosphate de sodium et de dihydrogénophosphate d'aluminium et/ou d'urée et est employé dans une résine polyester choisie parmi le polyéthylène téréphtalate, le polybutylène téréphtalate et le polyéthylène naphtalate, ou dans une résine polyamide. La composition de résine ignifugée comprend une résine thermoplastique et l'agent ignifugeant pour mélangeage à une résine thermoplastique, l'agent ignifugeant ayant été ajouté à la résine thermoplastique à une teneur comprise entre 1 et 25 % en masse par rapport à la quantité totale.
PCT/JP2012/000824 2011-02-09 2012-02-08 Agent ignifugeant pour mélangeage à une résine thermoplastique, composition de résine ignifugée et procédé de production de la composition de résine ignifugée WO2012108190A1 (fr)

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Cited By (2)

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CN112172077A (zh) * 2020-07-31 2021-01-05 任丘市华凯通信设备有限公司 一种梅花管材及其制备方法
WO2022089468A1 (fr) * 2020-10-29 2022-05-05 广东广山新材料股份有限公司 Ignifugeant polymère, son procédé de préparation et son utilisation

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