Classifications

• • 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
  • C08K5/36—Sulfur-, selenium-, or tellurium-containing compounds
  • C08K5/41—Compounds containing sulfur bound to oxygen
  • C08K5/42—Sulfonic acids; Derivatives thereof
• • 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
  • C08K3/01—Use of inorganic substances as compounding ingredients characterized by their specific function
  • C08K3/016—Flame-proofing or flame-retarding additives
• • 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
  • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
  • C08K3/20—Oxides; Hydroxides
  • C08K3/22—Oxides; Hydroxides of metals
• • 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
  • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
  • C08K3/20—Oxides; Hydroxides
  • C08K3/22—Oxides; Hydroxides of metals
  • C08K3/2279—Oxides; Hydroxides of metals of antimony
• • 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
  • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
  • C08K3/24—Acids; Salts thereof
• • 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
  • C08K3/38—Boron-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
  • C08K5/04—Oxygen-containing compounds
  • C08K5/06—Ethers; Acetals; Ketals; Ortho-esters
• • 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
  • C08K5/34—Heterocyclic compounds having nitrogen in the ring
  • C08K5/3467—Heterocyclic compounds having nitrogen in the ring having more than two nitrogen atoms in the ring
  • C08K5/3477—Six-membered rings
• • 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
  • C08K5/34—Heterocyclic compounds having nitrogen in the ring
  • C08K5/3467—Heterocyclic compounds having nitrogen in the ring having more than two nitrogen atoms in the ring
  • C08K5/3477—Six-membered rings
  • C08K5/3492—Triazines
  • C08K5/34924—Triazines containing cyanurate groups; Tautomers thereof
• • 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
  • C08K5/36—Sulfur-, selenium-, or tellurium-containing compounds
  • C08K5/41—Compounds containing sulfur bound to oxygen
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
  • C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
  • C08L23/10—Homopolymers or copolymers of propene
• • 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
  • C08K3/38—Boron-containing compounds
  • C08K2003/387—Borates
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L2201/00—Properties
  • C08L2201/02—Flame or fire retardant/resistant

Definitions

• the present invention relates to a novel flame-retardant polypropylene-based resin composition.
• Polyolefins such as polypropylene are light, have high strength, have good water resistance, chemical resistance, electrical insulation, etc., and are easy to mold. Therefore, for example, building materials, materials for electric appliances, vehicle parts, automobiles, etc. It is widely used in various industrial products, household products, etc., in addition to interior materials and electric wire coating materials. However, polyolefins have the drawback of being easily burned. Therefore, many methods for making polyolefin flame-retardant have been proposed.
• a method of making flame retardant a method of blending a flame retardant with a resin has been adopted for some time.
• a flame retardant containing a bromine compound and an antimony compound and as the bromine compound, a brominated bisphenol S derivative is known to have high flame retardancy. Therefore, various resin compositions containing these flame retardants have been proposed.
• a flame-retardant polyolefin resin composition having a ratio of (A) 70 to 98% by weight of a polyolefin resin and (B) 2 to 30% by weight of a bromine-containing flame retardant, which is specified as the bromine-containing flame retardant.
• a composition containing the above compound is disclosed (Patent Document 1).
• Patent Document 1 describes that antimony trioxide may be used in combination as a flame retardant aid together with a bromine-containing flame retardant (Patent Document 1).
• a based resin composition is known (Patent Document 2).
• the flame retardant or the like is present on the resin surface when the polyolefin resin and the flame retardant are kneaded or after the kneading (including after molding). The phenomenon of exuding and whitening (blooming) is likely to occur.
• Patent Document 3 a brominated flame retardant containing a brominated bisphenol S derivative in order to develop a flame retardant capable of suppressing blooming
• the brominated flame retardant as shown in Patent Document 3 is excellent in the effect of suppressing blooming, there is room for further improvement. That is, the brominated flame retardant containing the brominated bisphenol S derivative has a problem of being thermally decomposed at the time of molding and processing of the resin composition containing the brominated bisphenol S derivative.
• thermal decomposition occurs, in addition to highly toxic acrolein, decomposition products such as halogen compounds are generated and may be released into the working environment. For this reason, it is necessary to develop a flame-retardant resin composition that also has a property (hereinafter referred to as "heat resistance") that decomposition products are unlikely to be generated even under heating during molding.
• a main object of the present invention is to provide a flame-retardant resin composition having good flame retardancy, less likely to cause blooming, and excellent heat resistance.
• the present inventors have found that the above object can be achieved by adopting a combination of specific compounds as a flame retardant, and have completed the present invention.
• the present invention relates to the following polypropylene-based resin composition.
• 1. The following components (A) to (D): (A) Polypropylene resin: 100 parts by weight (B)
• the following general formula (1) [In the formula, R 1 and R 2 indicate an alkyl group having 1 to 3 carbon atoms which may have hydrogen or a substituent which is the same as or different from each other. m and n represent integers of 0 to 2 that are the same as or different from each other.
• the bisphenol S derivative represented by the above which is a mixture of the derivative b1 having m + n of 4 and the derivative b2 having m + n of 0 to 3, which is a mixture of b1 and b2 by an area percentage method using liquid chromatography.
• Item 2 The flame-retardant polypropylene-based resin composition according to Item 1 or 2, wherein R 1 and R 2 are the same or different and have a 2,3-dibromopropyl group or a 2-hydroxy-3-bromopropyl group. 4.
• the component (B): the component (C) 40% by weight: 60% by weight to 90% by weight: 10% by weight.
• the present invention it is possible to provide a flame-retardant resin composition having good flame retardancy, less likely to cause blooming, and excellent heat resistance.
• the composition of the present invention since the first flame-retardant component and the second flame-retardant component described later are used in combination at a specific content, it is possible to obtain high heat resistance while effectively suppressing blooming. can. That is, the problems that the flame retardant seeps out to the surface of the molded body and the flame retardant volatilizes during the molding process can be solved at once.
• the flame-retardant polypropylene-based resin composition of the present invention having such characteristics can be suitably used for manufacturing (molding) polypropylene-based products that require flame retardancy.
• it can be widely used as electronic parts, home appliances, medical devices, building materials, and the like.
• the flame-retardant polypropylene-based resin composition of the present invention (the composition of the present invention) has the following components (A) to (D): (A) Polypropylene resin: 100 parts by weight (B)
• the following general formula (1) [In the formula, R 1 and R 2 indicate an alkyl group having 1 to 3 carbon atoms which may have hydrogen or a substituent which is the same as or different from each other. m and n represent integers of 0 to 2 that are the same as or different from each other.
• the polypropylene-based resin may be any homopolymer or copolymer as long as it contains [-CH (CH 3 ) CH 2- ] as a monomer. Further, it may be a polymer alloy containing a polypropylene resin. As these polypropylene-based resins, known or commercially available ones can also be used.
• the polypropylene resin When the polypropylene resin is a homopolymer, it may be either isotactic or syndiotactic.
• the other monomer is not particularly limited as long as it does not interfere with the effect of the present invention, and is an alkene having 2 to 10 carbon atoms such as ethylene, butene, hexene, and octene. At least one of the above can be mentioned.
• the content ratio of the other monomer depends on the type of the monomer used and the like, but is usually preferably 40 mol% or less (particularly 30 mol% or less).
• the polypropylene-based resin may be a polymer alloy containing a polypropylene resin.
• a polypropylene resin For example, at least one of polyamide, polylactic acid, polyester, polyacrylate, ethylene propylene rubber, polystyrene and the like can be mentioned.
• the polypropylene content in the case of the polymer alloy can be set to, for example, 60 to 90% by weight, but is not limited thereto.
• the weight average molecular weight of the polypropylene-based resin may be, for example, in the range of about 100,000 to 1,500,000, but is not limited to this.
• the MFR (Japanese Industrial Standard JIS K7210, measurement temperature 230 ° C.) of the polypropylene resin may be, for example, in the range of about 0.5 to 50, but is not limited to this.
• the content of the polypropylene-based resin in the composition of the present invention is not particularly limited, but can be appropriately set within the range of usually 80 to 100% by weight. Therefore, for example, it can be in the range of 90 to 95% by weight. That is, resin components other than the polypropylene-based resin (for example, polyamide, polylactic acid, polyester, polyacrylate, ethylene propylene rubber, polystyrene, etc.) may be contained within a range that does not interfere with the effects of the present invention. In this case, the content of the resin component may be set so that the content of the polypropylene-based resin is within the above range.
• resin components other than the polypropylene-based resin for example, polyamide, polylactic acid, polyester, polyacrylate, ethylene propylene rubber, polystyrene, etc.
• the content of the resin component may be set so that the content of the polypropylene-based resin is within the above range.
• (B) First Flame Retardant Component In the composition of the present invention, the following general formula (1) is used as one of the flame retardant components.
• R 1 and R 2 indicate an alkyl group having 1 to 3 carbon atoms which may have hydrogen or a substituent which is the same as or different from each other.
• m and n represent integers of 0 to 2 that are the same as or different from each other.
• the bisphenol S derivative represented by the above which is a mixture of the derivative b1 having m + n of 4 and the derivative b2 having m + n of 0 to 3, which is a mixture of b1 and b2 by an area percentage method using liquid chromatography.
• a mixture having a ratio [b1: b2] of 92%: 8% to 70%: 30% (hereinafter, also referred to as "first flame-retardant component”) is used.
• the first flame-retardant component is a derivative having m + n of 4 (that is, a derivative having a total number of bromine substituted with a phenyl group of 4; hereinafter referred to as "tetra body”) and m + n. It consists of a mixture with a derivative having a value of 0 to 3 (that is, a derivative having a total number of bromine substituted on a phenyl group of 0 to 3; hereinafter referred to as "non-tetra form").
• the mixing ratio of the tetra-form and the non-tetra-form in the mixture is 92%: 8% to 70%: 30%. When it is within the range of this mixing ratio, a better blooming suppressing effect and heat resistance can be obtained.
• the above mixing ratio is a value obtained by the area percentage method using liquid chromatography. That is, the total area of the detected peaks in the chromatogram may be set to 100%, and the ratio of the total peak area of the tetra body to the total peak area of the non-tetra body may be obtained and quantified.
• the liquid chromatography apparatus and operating conditions used in the present invention are as shown below.
• Equipment used ACQUITY UPLC H-Class, Column: ACQUITY UPLC BEH C 18 1.7 ⁇ m, inner diameter 2.1 mm ⁇ length 100 mm (manufactured by Waters)
• Flow velocity 0.35 mL / min
• Column temperature 40 ° C.
• R 1 and R 2 represent an alkyl group having 1 to 3 carbon atoms which may have hydrogen or a substituent, which may be the same or different.
• Examples of the above-mentioned substituent include a halogen group and a hydroxyl group.
• the alkyl group having 1 to 3 carbon atoms which may have a substituent is not limited, but a bromine-substituted propyl group is preferable.
• the bromine-substituted propyl group may be any as long as at least one of the substituents is bromine, and the bromine-substituted propyl group is not limited to those in which all the substituents are bromine.
• a bromine-substituted propyl group a 2,3-dibromopropyl group or a 2-hydroxy-3-bromopropyl group is particularly preferable.
• m and n represent integers of 0 to 2 which are the same as or different from each other.
• m + n is 4 (tetra form)
• two bromine atoms are substituted for each phenyl group.
• Suitable specific examples of the tetra body are shown below.
• the non-tetra body is classified into a "tri body” in which m + n is 3, a "di body” in which m + n is 2, a “mono body” in which m + n is 1, and a “zero body” in which m + n is 0.
• a "tri body” in which m + n is 3
• a "di body” in which m + n is 2
• a zero body in which m + n is 0.
• Examples of the bird body include the following.
• Examples of the mono body include the following.
• the first flame retardant component is substantially a mixture of 70 to 92% tetra and 8 to 30% non-tetra.
• first flame-retardant component itself, known or commercially available ones can be used. Further, those manufactured according to a known manufacturing method can also be used. For example, it can be suitably produced by the method described in Japanese Patent No. 4817726.
• the content of the first flame-retardant component is usually 2 to 50 parts by weight, particularly preferably 3 to 20 parts by weight, particularly 4 to 15 parts by weight, based on 100 parts by weight of the polypropylene resin. Is more preferable. By setting it within the above range, excellent flame retardancy, blooming suppressing effect and heat resistance can be obtained.
• (C) Second Flame Retardant Ingredient in the composition of the present invention, at least one of (c1) tetrabromobisphenol A bis (2,3-dibromopropyl) ether and (c2) tris (2,3-dibromopropyl) isocyanurate. (Hereinafter also referred to as "second flame-retardant component”) is used.
• second flame-retardant component By coexisting the first flame-retardant component together with the second flame-retardant component in the composition of the present invention, it is possible to obtain excellent heat resistance as well as a high bleeding suppressing effect.
• the content of the second flame-retardant component is usually 0.2 to 20 parts by weight, particularly 0.5 to 15 parts by weight, based on 100 parts by weight of the polypropylene-based resin from the viewpoint of the above-mentioned action and effect. Is preferable.
• the ratio is preferably 60% by weight to 90% by weight: 10% by weight.
• the composition of the present invention is at least one selected from the group consisting of antimony trioxide, antimony pentoxide, zinc molybdate, boron trioxide and zinc borate (hereinafter also referred to as "flame retardant aid"). ) Includes. When these flame-retardant aids are contained, better flame-retardant performance can be exhibited. Among the above, at least one of antimony trioxide and antimony pentoxide is preferable, and antimony trioxide is more preferable in that it can impart a high degree of flame retardancy. Further, the properties of the flame retardant aid are not particularly limited, and for example, those in the form of powder can be used. As these flame retardant aids, known or commercially available ones can be used.
• the content of the flame retardant aid in the composition of the present invention is usually 1 to 20 parts by weight, particularly preferably 2 to 15 parts by weight, based on 100 parts by weight of the polypropylene-based resin.
• additives contained in a known or commercially available resin composition or a molded product thereof are added as necessary within a range that does not interfere with the effects of the present invention. be able to.
• resin components other than polypropylene-based resins dispersants, surfactants, weather-resistant stabilizers, antioxidants, ultraviolet absorbers, anti-fog agents, antistatic agents, antibacterial agents, impact-resistant agents, foaming agents, and fillers.
• examples thereof include materials (fillers), conductive powders, nucleating agents, cross-linking agents, coloring agents, lubricants and the like.
• composition of the present invention are not particularly limited, and may be a solid (powder) under normal temperature and pressure, or may be in a molten state under heating. good. Further, the melt may be in the form of a solidified solid. Further, it may be a liquid in which the solid is dissolved or dispersed in a solvent, if necessary.
• the method for preparing the composition of the present invention is not particularly limited as long as each component can be uniformly mixed. Further, a method of obtaining an unmolded / unmelted mixture (powder) by mixing each component may be used, or a method of obtaining a solid substance by melting and solidifying may be used. For example, by premixing each component constituting the composition of the present invention with a mixer such as a Henshell mixer, a tumbler type mixer, or a rotor type mixer, and then supplying the mixture to a kneader heated to the melting temperature of the polypropylene resin. A method for obtaining resin composition pellets can be adopted.
• each component may be separately supplied to the kneader by a quantitative feeder without premixing (premixing).
• Each component for example, a first flame-retardant component, a second flame-retardant component, a flame-retardant aid, etc.
• a polypropylene-based resin may be separately supplied to the kneader by a quantitative feeder.
• the present invention also includes a molded body obtained by molding the composition of the present invention.
• the size, shape, and the like of the molded product can be appropriately set according to the intended use, usage pattern, and the like of the molded product.
• the molding method of the molded body is not limited as long as it can be molded from the melt of the composition of the present invention, the sheet-like product of the composition of the present invention, etc., for example, press molding, injection molding, extrusion molding, blow molding, vacuum molding.
• Various molding methods such as molding can be adopted. Therefore, for example, a known or commercially available molding device such as a heat compression molding machine or an injection molding machine can be used.
• the use of the molded body of the present invention is not particularly limited as long as it is an article that requires flame retardancy, for example, a washing machine, a refrigerator, a dish dryer, a rice cooker, a fan, a television, a personal computer, a stereo, and a microwave oven. , Parts and covers for heating toilets, irons, etc .; Electronic equipment circuit boards for mobile phones, personal computers, printers, facsimiles, etc .; Parts and covers for air conditioners, stoves, stoves, fan heaters, water heaters, etc .; Building materials, automobiles, ships, etc. Examples include parts for aircraft and interior materials.
• polypropylene resin As the polypropylene resin, a commercially available polypropylene resin (product name "Prime Polypro J707G” (MFR: 30 g / 10 min, block-PP), made of prime polymer (PP)) was used.
• the first flame-retardant component was produced by the following method.
• Production Example 1 (Product of the present invention) A glass reaction vessel equipped with a stirrer, a condenser, a thermometer, a dropping funnel and a heating / cooling device was prepared. The reaction vessel contained 1000 g of water and 250 g (1 mol) of bisphenol S. The phenyl group was replaced with bromine by dropping 591 g (3.7 mol) of bromine over 2 hours while stirring the inclusions. Due to the dripping, the temperature of the contained material increased from 5 ° C to 40 ° C. After the completion of the dropping, the reaction was continued for another 1 hour.
• reaction product was transferred to a porcelain filter, and then 1000 ml of water was poured to completely dissolve and remove unnecessary alkali salts, IPA, allyl chloride and the like.
• the reaction product after washing was transferred to a glass eggplant flask having a capacity of 2 liters, and then the eggplant flask was connected to an evaporator at a hot water temperature (60 ° C.) and dried under reduced pressure at a reduced pressure of 20 Torr.
• a glass reaction vessel equipped with a stirrer, a condenser, a thermometer, a dropping funnel and a heating / cooling device was prepared.
• the reaction product after drying was placed in a reaction vessel, and 600 g of methylene chloride (solvent) was further added to completely dissolve the reaction product. 2 mol of bromine was added dropwise to this solution using a dropping funnel. By this dropping, bromine is added to the unsaturated bond of the allyl group of the bromine-substituted bisphenol S derivative. Since this reaction was accompanied by rapid heat generation, stirring and cooling were sufficiently performed. The liquid temperature during the reaction was controlled so as not to exceed 40 ° C. The end point of the bromine addition reaction was when a predetermined amount of bromine was added dropwise and the reaction solution was in a state of retaining redness. In Production Example 1, it took 2 hours from the start of dropping bromine.
• reaction was continued for another 1 hour for aging. Then, 1000 ml of water was added to the reaction solution, and the mixture was vigorously stirred to dissolve unnecessary unreacted bromine in the aqueous phase, and then decantation was repeated to remove the aqueous phase. Next, the reaction product was poured into 2000 ml of methanol in a strong stirring state for 5 minutes and reprecipitated. The precipitate was once pulverized and further allowed to stand in methanol for 10 hours to crystallize. Subsequently, after removing most of the methanol by filtration, the mixture was transferred to a glass 2000 ml eggplant flask.
• the eggplant flask was connected to an evaporator of hot water (70 ° C.), and an unnecessary solvent (methanol, water, etc.) was distilled off at a reduced pressure of 10 Torr.
• the yield of the reaction product (bromine flame retardant) was 745 g.
• the area percentage of the tetra-form: non-tetra-form of the reaction product was identified by liquid chromatography and found to be 89:11. Further, as a result of measuring the melting endothermic peak temperature of the reaction product with a differential scanning calorimeter, a melting point peak was confirmed at 122 ° C.
• the chemical formula of the obtained reaction product is shown below.
• Production Example 2 (Product of the present invention) Except that 559.3 g (3.5 mol) of bromine was added to bisphenol S to make the amount of 50% sodium hydroxide aqueous solution added for the allyl etherification reaction 448 g (5.6 mol of sodium hydroxide). A brominated flame retardant was obtained in the same manner as in Production Example 1. The yield of the reaction product (bromine flame retardant) was 711 g. The area percentage of the tetra-form: non-tetra-form of the reaction product was identified by liquid chromatography and found to be 73:27. Further, as a result of measuring the melting endothermic peak temperature of the reaction product with a differential scanning calorimeter, a melting point peak was confirmed at 105 ° C. The chemical formula of the obtained reaction product is shown below.
• the area percentage of the tetra-form: non-tetra-form of the reaction product was identified by liquid chromatography and found to be 99: 1. Further, as a result of measuring the melting endothermic peak temperature of the reaction product with a differential scanning calorimeter, a melting point peak was confirmed at 120 ° C. The chemical formula of the obtained reaction product is shown below.
• Production Example 4 (Comparative product) Except that 527.3 g (3.3 mol) of bromine was added to bisphenol S to make the amount of 50% sodium hydroxide aqueous solution added for the allyl etherification reaction 432 g (5.4 mol of sodium hydroxide). A brominated flame retardant was obtained in the same manner as in Production Example 1. The yield of the reaction product (bromine flame retardant) was 670 g. The area percentage of the tetra-form: non-tetra-form of the reaction product was identified by liquid chromatography and found to be 65:35. Further, as a result of measuring the melting endothermic peak temperature of the reaction product with a differential scanning calorimeter, a melting point peak was confirmed at 98 ° C. The chemical formula of the obtained reaction product is shown below.
• (C) Second flame-retardant component The following commercially available product was used as the second flame-retardant component.
• -Product name "Pyroguard SR720” Tetrabromobisphenol A-bis (2,3-dibromopropyl ether), manufactured by Dai-ichi Kogyo Seiyaku Co., Ltd. (hereinafter referred to as "TBA-DBP”).
• TAIC-6B Tris (2,3-dibromopropyl) isocyanurate
• Nihon Kasei hereinafter referred to as "TBIC"
• (D) Flame-retardant aid As the flame-retardant aid, powdered antimony trioxide (average particle size 3 ⁇ m) was used.
• the obtained pellets were molded by an injection molding machine (FE80S 18ASE manufactured by Nissei Jushi Kogyo Co., Ltd., cylinder temperature 200 ° C., mold temperature 40 ° C.), and a vertical combustion test piece (127 mm ⁇ 12. 7 mm, thickness; 1/32 inch) was produced.
• a plate for evaluating blooming property 35 mm ⁇ 48 mm ⁇ thickness 1.5 mm was produced by molding with an injection molding machine (FE80S 18ASE manufactured by Nissei Jushi Kogyo Co., Ltd., cylinder temperature 200 ° C., mold temperature 40 ° C.). ..
• Test Example 1 Using the samples prepared in each Example and Comparative Example, the following physical properties were investigated respectively. The results are also shown in Table 1.
• the combustibility of the resin composition was evaluated by performing a vertical combustion test using the above vertical combustion test piece in accordance with the safety standard "UL-94 combustion test" of Underwriter Laboratories in the United States.
• the UL94 combustion test is roughly divided into two types, a horizontal test (HB method) and a vertical test (V method).
• HB method horizontal test
• V method vertical test
• the flame retardancy increases in the order of FAIL ⁇ HB ⁇ V-2 ⁇ V-1 ⁇ V-0. It shows that V-0 has the highest flame retardancy.
• the molded product according to the present invention exhibits excellent flame retardancy and maintains an excellent appearance without causing blooming.
• the TVOC value is less than 1 ppm (particularly 0.70 ppm or less), it is possible to effectively suppress the gas (odorous harmful gas) that may be generated during the molding process (that is, it is excellent in heat resistance). ) Is understood.
• the molded product of the comparative example has a problem in at least one of blooming property and heat resistance.
• Comparative Example 1 the mixing ratio of the tetra body and the non-tetra body is within the range of the present invention, but the second flame-retardant component is not contained. It can be seen that the value of TVOC is higher than that in Example 4 in which the 1st flame-retardant component and the 2nd flame-retardant component are used in combination. Similarly, in Comparative Example 2, the mixing ratio of the tetra body and the non-tetra body is within the range of the present invention, but the second flame-retardant component is not contained, so that the first flame-retardant component and the second flame-retardant component are not contained. It can be seen that the value of TVOC is higher than that of Example 5 or Example 6 in which the above is used in combination.
• Comparative Example 3 gas generation is suppressed by blending 10 parts by weight of the first flame-retardant component having a mixing ratio of tetra-form and non-tetra-form of 99: 1, and high flame retardancy of V-0 level is achieved. Although it can be imparted, blooming occurs and the appearance of the molded product is significantly deteriorated. Therefore, it can be seen that the tetra body has no effect of suppressing blooming.
• Comparative Example 4 was excellent in that high flame retardancy was imparted by blending 10 parts by weight of the first flame-retardant component having a mixing ratio of tetra-form and non-tetra-form at 65:35 and a high non-tetra-form content. Although it retains its appearance, it has poor heat resistance because it contains a large amount of non-tetra body, and it can be seen that gas can be generated during processing.
• Comparative Examples 5 to 6 by blending 10 parts by weight of each of the second flame-retardant components TBA-DBP and TBIC, high flame retardancy is imparted and gas generation is suppressed, but the first flame retardant is suppressed. It can be seen that since no component is contained, blooming occurs and the appearance of the molded product is significantly deteriorated.
• Comparative Example 8 imparts high flame retardancy by blending 10 parts by weight of a mixture of a first flame-retardant component containing 35% of a non-tetra compound and a TBA-DBP second flame-retardant component of 9: 1. It can be seen that it retains an excellent appearance, but has poor heat resistance and can generate gas during processing.
• the first flame-retardant component and the second flame-retardant component are used in combination, but blooming occurs because the mixing ratio of the tetra-form and the non-tetra-form in the first flame-retardant component is 99: 1. It can be seen that the appearance of the molded product is significantly deteriorated.

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• 2020
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