Flame-retardant resin composition and molded article

Abstract

The invention relates to a flame-retardant resin composition and a molded article. Provided is a flame-retardant resin composition that achieves both a flame retardant function and mechanical strength. The flame-retardant resin composition comprises 74-93 mass% of a styrene-based resin, a crystalline resin having a melting point of 250 DEG C or higher, 4-15 mass% of a phosphorus-based flame retardant, and 0.3-3.0 mass% of a hindered amine-based light stabilizer.

Description

Technical Field

[0001] The present invention relates to a flame retardant resin composition and a molded article. Background Art

[0002] In the past, as a method for flame-retarding styrene resins, a method of adding a halogen-containing flame retardant was known. However, in recent years, since organic compounds containing halogens have adverse effects on the environment, halogen-free initiatives have become popular, centered in Europe. In addition, the demand for halogen-free type flame retardants has increased, and the development of halogen-free type flame retardants for various resins is underway. As a flame retardant for the case of using styrene resins alone, halogen-free type flame retardants are known. (For example, refer to Patent Documents 1 and 2).

[0003] Patent Document 1 describes a flame-retardant styrene resin composition containing a rubber-modified styrene resin, a halogen-free NOR-type hindered amine compound, and a phosphorus-based flame retardant.

[0004] Patent Document 2 describes a flame-retardant styrene-based resin composition comprising a styrene-based resin, a phosphate-based flame retardant, a halogen-free hindered amine-based light stabilizer, and a higher fatty acid zinc.

[0005] Prior art literature

[0006] Patent Literature

[0007] Patent Document 1: Japanese Patent Application Publication No. 2019-183084

[0008] Patent Document 2: Japanese Patent Application Publication No. 2014-95056 Summary of the invention

[0009] Technical problem solved by the invention

[0010] The flame-retardant styrene resin compositions described in Patent Documents 1 and 2 contain a phosphorus flame retardant and a halogen-free hindered amine light stabilizer. However, in a material in which other resins are mixed in the styrene resin composition in order to change the material properties, when a flame retardant that extinguishes fire by dripping is used in combination, the deviation of the burning time increases. In particular, when using recycled resins, the effect is reduced when trying to achieve V-2 in the UL flame retardancy test, and the deviation becomes larger, making it impossible to achieve V-2. On the other hand, when increasing the amount of flame retardant added to the flame-retardant styrene resin composition, there is a case where the mechanical and physical properties are reduced.

[0011] An object of the present invention is to provide a flame-retardant resin composition and a molded article that achieve both flame retardant function and mechanical strength.

[0012] Technical means of solving problems

[0013] The flame retardant resin composition according to one embodiment of the present invention comprises 74 to 93% by mass of a styrene resin, a crystalline resin having a melting point of 250° C. or higher, 4 to 15% by mass of a phosphorus flame retardant, and 0.3 to 3.0% by mass of a hindered amine light stabilizer.

[0014] A molded article according to one embodiment of the present invention is formed using the flame-retardant resin composition of the present invention. DETAILED DESCRIPTION

[0015] Hereinafter, a flame-retardant resin composition and a molded article according to an embodiment of the present invention will be described in detail.

[0016] [Constitution of flame-retardant resin composition]

[0017] The flame retardant resin composition comprises 74 to 93% by mass of a styrene resin, a crystalline resin having a melting point of 250° C. or higher, 4 to 15% by mass of a phosphorus flame retardant, and 0.3 to 3.0% by mass of a hindered amine light stabilizer.

[0018] The decomposition temperature of the flame retardant resin composition obtained by thermogravimetric analysis is preferably in the range of 390 to 410° C. When the decomposition temperature is lower than 390° C., the viscosity during combustion tends to decrease. On the other hand, when the decomposition temperature exceeds 410° C., the viscosity during combustion is difficult to decrease.

[0019] The decomposition temperature of the flame retardant resin composition obtained by thermogravimetric analysis can be measured, for example, by the following method. Using a thermogravimeter-Differential Thermal Analyzer (TGDTA), the temperature is raised from room temperature to 600°C at a heating rate of 20°C / min. The temperature at which the weight loss at this time decreases by 5% from the weight before the start of the measurement is taken as the decomposition temperature.

[0020] The content of the styrene resin as the non-crystalline resin in the flame retardant resin composition is in the range of 74 to 93% by mass, preferably in the range of 80 to 90% by mass. When the content of the styrene resin is less than 74% by mass or when the content of the styrene resin exceeds 93% by mass, the amount of the flame retardant that can be added is relatively small, and flame retardancy cannot be ensured.

[0021] Examples of styrene-based resins include polystyrene resins, syndiotactic polystyrene resins, acrylonitrile-styrene copolymers (AS resins), and acrylonitrile-butadiene-styrene resins (ABS resins). From the viewpoint of balance of mechanical properties, styrene-based resins are preferably acrylonitrile-butadiene-styrene resins.

[0022] The styrene resin is preferably a recycled resin. Here, the recycled resin means a resin component obtained by processing the recycled resin component into a form for repeated use. It should be noted that among the styrene resins, a part of the resin may be a recycled resin, and all of the resin may be a recycled resin. Among the recycled resins, preferably 90% by mass or more is a recycled styrene resin.

[0023] The styrene resin can be measured by, for example, the following method. In the method for measuring the styrene resin, first, a flame retardant resin composition is dissolved in tetrahydrofuran and then filtered. Next, the weight of the recyclate is subtracted from the weight of the flame retardant resin composition. The difference in weight can be used as the weight of the styrene resin.

[0024] The content of the crystalline resin in the flame retardant resin composition is in the range of 0.5 to 3.0% by mass, preferably in the range of 0.5 to 2.0% by mass. When the crystalline resin is less than 0.5% by mass, it becomes difficult to drip and the burning time becomes longer. When the crystalline resin exceeds 3.0% by mass, it becomes easy to drip, but the fire is not extinguished when dripping, and it becomes a state of residual fire.

[0025] The melting point of the crystalline resin is 250° C. or higher. In addition, the melting point of the crystalline resin is preferably 300° C. or lower. In addition, the melting point of the crystalline resin is preferably 250° C. or higher, and more preferably 270° C. or lower. When the melting point of the crystalline resin is lower than 250° C., it becomes easy to drip, but the dripping speed is too fast so that the fire is not completely extinguished (falls), and it is easy to remain in the sample, so the burning time becomes longer.

[0026] The melting point of a crystalline resin can be measured, for example, by the following method. DSC measurement is performed using a differential scanning calorimeter (DSC) and differential scanning calorimetry. The temperature is raised from room temperature to 300°C at a heating rate of 10°C / min, and the peak value of the peak corresponding to the melting point is taken as the melting point (°C).

[0027] Examples of crystalline resins include polyester resins, polyamide resins, PE (polyethylene), PP (polypropylene), PA (polyamide), POM (polyacetal, polyoxymethylene), PET (polyethylene terephthalate), PBT (polybutylene terephthalate), PPS (polyphenylene sulfide), PEEK (polyetheretherketone), LCP (liquid crystal polymer), and PTFE (polytetrafluoroethylene). Crystalline resins are preferably polyester resins or polyamide resins from the viewpoint of compatibility with styrene resins.

[0028] The polyester resin includes a polymer or a copolymer obtained by a condensation reaction of a dicarboxylic acid (or an ester-forming derivative thereof) and a diol (or an ester-forming derivative thereof) as main components, or a mixture thereof.

[0029] Examples of dicarboxylic acids include aromatic dicarboxylic acids such as terephthalic acid, isophthalic acid, phthalic acid, 2,6-naphthalene dicarboxylic acid, 1,5-naphthalene dicarboxylic acid, bis(p-carboxyphenyl)methane, anthracene dicarboxylic acid, 4,4′-diphenyl ether dicarboxylic acid, and sodium 5-sulfoisophthalate; aliphatic dicarboxylic acids such as adipic acid, sebacic acid, azelaic acid, and dodecanedioic acid; alicyclic dicarboxylic acids such as 1,3-cyclohexane dicarboxylic acid and 1,4-cyclohexane dicarboxylic acid; and ester-forming derivatives thereof.

[0030] Examples of the diol component include aliphatic diols having 2 to 20 carbon atoms, i.e., ethylene glycol, propylene glycol, 1,4-butanediol, neopentyl glycol, 1,5-pentanediol, 1,6-hexanediol, decamethylene glycol, cyclohexanedimethanol, cyclohexanediol, etc., or long-chain diols having a molecular weight of 400 to 6000, i.e., polyethylene glycol, poly-1,3-propylene glycol, polytetramethylene glycol, etc., and ester-forming derivatives thereof.

[0031] Examples of these polymers or copolymers include polybutylene terephthalate, polybutylene terephthalate / isophthalate, polybutylene terephthalate / adipate, polybutylene terephthalate / sebacate, polybutylene terephthalate / decanedicarboxylate, polybutylene naphthalate, polyethylene terephthalate, poly(ethylene terephthalate / isophthalate), poly(ethylene terephthalate / adipate), poly(ethylene terephthalate / 5-sodiosulfoisophthalate), poly(butylene terephthalate / 5-sodiosulfoisophthalate), polyethylene naphthalate, and polycyclohexanedimethanol terephthalate. From the viewpoint of the moldability of the polyester composition, the polymer or copolymer is preferably polybutylene terephthalate, polybutylene (terephthalate / adipate), polybutylene (terephthalate / sebacate), polybutylene naphthalate, polyethylene terephthalate, poly(terephthalate / adipate), polyethylene naphthalate, polycyclohexanedimethanol terephthalate, etc., and particularly preferably polyethylene terephthalate and polybutylene terephthalate.

[0032] Polyamide resin is a resin containing a polymer having an amide bond, and uses amino acids, lactams or diamines and dicarboxylic acids as main raw materials. Examples of raw materials include amino acids such as 6-aminocaproic acid, 11-aminoundecanoic acid, 12-aminododecanoic acid, and p-aminomethylbenzoic acid, lactams such as ε-caprolactam and ω-laurolactam, tetramethylenediamine, pentamethylenediamine, hexamethylenediamine, 2-methylpentamethylenediamine, undecamethylenediamine, dodecamethylenediamine, 2,2,4- / 2,4,4-trimethylhexamethylenediamine, 5-methylnonamethylenediamine, m-xylylenediamine, p-xylylenediamine, 1,3-bis(aminomethyl)cyclohexane, 1,4-bis(aminomethyl)cyclohexane, 1-amino-3-aminomethyl-3 , 5,5-trimethylcyclohexane, bis(4-aminocyclohexyl)methane, bis(3-methyl-4-aminocyclohexyl)methane, 2,2-bis(4-aminocyclohexyl)propane, bis(aminopropyl)piperazine, aminoethylpiperazine and other aliphatic, alicyclic, aromatic diamines, and adipic acid, suberic acid, azelaic acid, sebacic acid, dodecanedioic acid, terephthalic acid, isophthalic acid, 2-chloroterephthalic acid, 2-methylterephthalic acid, 5-methylisophthalic acid, 5-sodium sulfoisophthalate, hexahydroterephthalic acid, hexahydroisophthalic acid and other aliphatic, alicyclic, aromatic dicarboxylic acids. In addition, polyamide homopolymers or copolymers derived from these raw materials can be used alone or in the form of a mixture.

[0033] Examples of the polyamide resin include polycaproamide (polyamide 6), polyhexamethylene adipamide (polyamide 66), polypentamethylene adipamide (polyamide 56), polytetramethylene adipamide (polyamide 46), polyhexamethylene sebacamide (polyamide 610), polypentamethylene sebacamide (polyamide 510), polyhexamethyl ene ... dodecanamide, polyamide 612), polyundecanamide (polyamide 11), polydecanamide (polyamide 12), polycaproamide / polyhexamethylene terephthalamide copolymer (polyamide 6 / 6T), polyhexamethylene adipamide / polyhexamethylene terephthalamide copolymer (polyamide 66 / 6T), polyhexamethylene adipamide / polyhexamethylene isophthalamide copolymer (polyamide 66 / 6I), polyhexamethylene adipamide / polyhexamethylene isophthalamide / polycaproamide copolymer (polyamide 66 / 6I / 6), polyhexamethylene terephthalamide / polyhexamethylene isophthalamide copolymer (polyamide 6T / 6I), polyhexamethylene terephthalamide / polydodecanamide copolymer (polyamide 6T / 12), polyhexamethylene adipamide / polyhexamethylene terephthalamide / polyhexamethylene isophthalamide copolymer (polyamide 66 / 6T / 6I), polyxylene adipamide (polyamide MXD6), polyhexamethylene terephthalamide / poly-2-methylpentamethylene terephthalamide copolymer (polyamide 6T / M5T), polyhexamethylene terephthalamide / polypentamethylene terephthalamide copolymer (polyamide 6T / 5T) and mixtures or copolymers thereof.

[0034] The polyamide resin is preferably polyamide 6 resin, polyamide 66 resin, polyamide 610 resin, polyamide 11 resin, polyamide 12 resin, polyamide 6 / 66 copolymer, polyamide 6 / 12 copolymer, and more preferably polyamide 6 resin or polyamide 610 resin.

[0035] The content of crystalline resin can be measured, for example, by the following method. As for the method for measuring the content of crystalline resin, the flame retardant resin composition (molded product) can be first measured by Fourier transform infrared spectrometer (FT-IR), and the content of crystalline resin can be calculated based on the ratio of the peak intensity caused by styrene to the peak intensity caused by the crystalline resin.

[0036] The phosphorus flame retardant in the flame retardant resin composition is in the range of 4 to 15% by mass, preferably in the range of 7 to 12% by mass. When the phosphorus flame retardant is less than 4% by mass, the flame retardant performance is reduced. When the phosphorus flame retardant exceeds 15% by mass, the mechanical physical properties, especially the impact strength, are reduced. When the phosphorus flame retardant is within the above range, a composition that can provide a molded body excellent in flame retardancy, heat resistance, and mechanical strength such as flexural strength and impact resistance can be obtained.

[0037] The phosphorus flame retardant may be a phosphorus compound having an aromatic ring in its structure or a phosphorus compound without an aromatic ring. Examples of phosphorus compounds having an aromatic ring include phosphazene compounds having a skeleton represented by the general formula (1).

[0038] [Chemical formula 1]

[0039]

[0040] Here, in the formula, X represents an alkyl group, an aryl group, an alkoxy group, an aryloxy group or an amino group.

[0041] Specifically, the phosphazene compound is a compound represented by the general formula (2) or (3), and at least one of the Xs has an aromatic ring.

[0042] [Chemical formula 2]

[0043]

[0044] Here, in the formula, n is preferably 3 to 20. X represents an alkyl group, an aryl group, an alkoxy group, an aryloxy group or an amino group.

[0045] The -P=N- structure in the general formula (1) may be cyclic as in the general formula (2) or chain as in the general formula (3).

[0046] In the general formula (1), X's may be the same as or different from each other.

[0047] The number of carbon atoms in the alkyl group is preferably 1 to 10, more preferably 1 to 6. Examples of the alkyl group include methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, tert-butyl, n-pentyl, and isopentyl.

[0048] The number of carbon atoms of the aryl group is preferably 6 to 11. The aryl group may be substituted with an alkyl group having 1 to 6 carbon atoms. Examples of the aryl group include phenyl, 2-methylphenyl, 3-methylphenyl, 4-methylphenyl, 2,6-dimethylphenyl, 3,5-dimethylphenyl, 2,5-dimethylphenyl, 2,4-dimethylphenyl, and 3,4-dimethylphenyl.

[0049] The number of carbon atoms of the alkoxy group is preferably 1 to 10, more preferably 1 to 6. Examples of the alkoxy group include methoxy, ethoxy, propoxy, isopropoxy, butoxy, sec-butoxy, isobutoxy, and tert-butoxy.

[0050] The number of carbon atoms of the aryloxy group is preferably 1 to 10. Examples of the aryloxy group include phenoxy, naphthyloxy, and anthracenyloxy. In addition, the aryloxy group may have a substituent in the aryl moiety. As the substituent, an alkyl group having 1 to 6 carbon atoms is preferred.

[0051] In the cyclic compound of the general formula (2), n is preferably 3 or more and 20 or less. In addition, it may be a mixture of cyclic compounds in which n is 3 or more and 20 or less. In the case of a mixture, a cyclic compound in which n is 3 is less than 50% by mass and can also be applied to the present invention. When it is less than 50% by mass, the melting point becomes low and it is easier to agglomerate in the feed section during the process of kneading into a resin. Preferably, it is a mixture containing 90% or more of cyclic compounds in which n is 3 and 4, and particularly preferably a mixture in which n=3 is 100%. That is, it is preferably a cyclophosphazene oligomer represented by the general formula (4).

[0052] [Chemical formula 3]

[0053]

[0054] In the general formula (4), X1 to X6 are preferably an alkoxy group, a fluorine atom, an aryloxy group, or an alkoxy group, and more preferably a fluorine atom, a phenoxy group, an ethoxy group, or a methoxy group.

[0055] Other examples of phosphorus compounds having an aromatic ring include phosphate compounds and condensed phosphate compounds. Other examples of phosphorus compounds having an aromatic ring include phosphate esters such as triphenyl phosphate, tricresyl phosphate, tricresyl phosphate, dimethylphenyl phosphate, methyl diphenyl phosphate, ethyl diphenyl phosphate, and hydroxyphenyl diphenyl phosphate, and compounds modified with various substituents. Condensed phosphate compounds may include, for example, compounds represented by general formula (5).

[0056] [Chemical formula 4]

[0057]

[0058] Here, in the formula, Ra, Rb, Rc and Rd are each independently an aromatic group, one or more hydrogen atoms may be substituted or unsubstituted, n is a natural number, Xa is an aromatic group derived from a divalent phenol, and j, k, l and m are each independently 0 or 1.

[0059] The phosphorus compound is most preferably a condensed phosphoric acid ester compound. Examples of the phosphoric acid ester compound include esters of phosphorous acid, phosphoric acid, phosphonous acid, and phosphonic acid.

[0060] Examples of the phosphite include triphenyl phosphite, tris(nonylphenyl) phosphite, tris(2,4-di-tert-butylphenyl) phosphite, distearyl pentaerythritol diphosphite, bis(2,6-di-tert-butyl-4-methylphenyl) pentaerythritol diphosphite, and bis(2,4-di-tert-butylphenyl) pentaerythritol diphosphite.

[0061] Examples of the phosphoric acid ester include triphenyl phosphate (TPP), tris(nonylphenyl) phosphate, tris(2,4-di-tert-butylphenyl) phosphate, distearyl pentaerythritol diphosphate, bis(2,6-di-tert-butyl-4-methylphenyl)pentaerythritol diphosphate, bis(2,4-di-tert-butylphenyl)pentaerythritol diphosphate, tributyl phosphate, and bisphenol A bis-diphenyl phosphate.

[0062] Examples of the phosphonite include tetrakis(2,4-di-tert-butylphenyl)-4,4′-biphenylene diphosphonite.

[0063] Examples of the phosphonic acid ester include dimethyl phenylphosphonate and phenylphosphonate.

[0064] The phosphoric acid ester compound is preferably an ester of phosphorous acid, phosphoric acid and phosphonic acid, and particularly preferably a phosphoric acid ester.

[0065] Examples of the phosphazene compound having an aromatic ring represented by the general formula (2) or (3) include cyclic and chain alkylaryloxyphosphazenes such as (poly)tolyloxyphosphazenes (e.g., o-tolyloxyphosphazene, m-tolyloxyphosphazene, p-tolyloxyphosphazene), (poly)xylyloxyphosphazenes, (poly)methylnaphthyloxyphosphazenes, (poly)phenoxytolyloxyphosphazenes (e.g., phenoxy-o-tolyloxyphosphazene, phenoxy-m-tolyloxyphosphazene, phenoxy-p-tolyloxyphosphazene), (poly)phenoxyxylyloxyphosphazenes, (poly)phenoxytolyloxyxylyloxyphosphazenes, and (poly)phenoxymethylnaphthyloxyphosphazenes.

[0066] Examples of commercially available phosphorus flame retardants include PX200, PX202, TPP, TCP, TEX P, CDP, NDPP, PX-110, CR-733S, and CR-741 (all from Daihachi Chemical Industry Co., Ltd.), and SPS100 (from Otsuka Chemical Co., Ltd.).

[0067] The hindered amine light stabilizer in the flame retardant resin composition is in the range of 0.3 to 3.0 mass %, preferably in the range of 0.5 to 1.0 mass %. When the hindered amine light stabilizer is less than 0.3 mass %, the time until dripping starts becomes longer, and it is difficult to extinguish the fire, so the burning time becomes longer. When the hindered amine light stabilizer exceeds 3.0 mass %, dripping is easier, but the fire is not extinguished during dripping, and the fire remains, so the burning time becomes longer.

[0068] The hindered amine light stabilizer may be a NOR-type hindered amine compound in which the H of the imino group of the piperidine ring is substituted by an alkoxy group (-OR (R represents a cycloalkyl group, an aralkyl group or an aryl group)), or an NH-type hindered amine compound in which the part of the imino group (>NH) of the piperidine ring is NH itself, or an NM-type hindered amine compound in which the H of the imino group of the piperidine ring is substituted by a methyl group.

[0069] Examples of commercially available products of the NOR-type hindered amine compound include Flamestab (registered trademark) NOR116FF, TINUVIN (registered trademark) NOR371, TINUVIN XT850FF, TINUVIN XT855FF, TINUVIN PA123 (all from BASF), LA-77Y, LA-81, and FP-T80 (all from ADEKA Corporation).

[0070] Examples of commercially available products of NH-type hindered amine compounds include TINUVIN 770DF (BASF), KEMISTAB 29, KEMISTAB 77, and KEMISTAB 94 (all from CHEMIPRO Co., Ltd.), and ADK STAB LA-52, ADK STAB LA-57, ADK STAB LA-68, and ADK STAB LA-72 (all from ADEKA).

[0071] Examples of commercially available products of the NM-type hindered amine compound include TINUVIN 765 (from BASF) and ADK STABLA-63P (from ADEKA).

[0072] The hindered amine light stabilizers may be used alone or in combination of two or more.

[0073] The flame retardant resin composition may contain other ingredients as long as it does not hinder the function. Examples of other ingredients include inorganic fillers, antioxidants, heat stabilizers, lubricants, antistatic agents, and colorants. In addition, the flame retardant resin composition of the present invention may further contain one or more glass fibers, glass powders, glass beads, glass flakes, alumina, alumina fibers, carbon fibers, graphite fibers, stainless steel fibers, whiskers, potassium titanate fibers, wollastonite, asbestos, hard clay, fired clay, talc, kaolin, mica, calcium carbonate, magnesium carbonate, alumina and minerals and other inorganic fillers, hindered phenols, sulfur-containing compounds or phosphorus-containing organic compounds and other antioxidants as needed without damaging the purpose of the present invention. The present invention also includes general additives such as oxidizing agents, heat stabilizers such as phenols and acrylates, ultraviolet absorbers such as benzotriazoles, benzophenones or salicylates, lubricants and plasticizers such as higher fatty acids, acid esters and acid amides, higher alcohols, mold release agents such as montanic acid and its salts, its esters, its half esters, stearyl alcohol, stearamide and ethylene wax, flame retardant additives, anti-coloring agents such as phosphites and hypophosphites, neutralizers such as phosphoric acid, monosodium phosphate, maleic anhydride and anhydrous succinic acid, nucleating agents, antistatic agents such as amines, sulfonic acids and polyethers, colorants such as carbon black, pigments and dyes.

[0074] In the case of using recycled resin as a styrene resin, it is difficult to select heterogeneous materials in the manufacturing process of recycled resin, so there are cases where different types of resins are included in the recycled resin. Therefore, it is believed that, with respect to a flame retardant resin composition comprising a plurality of resins, the degree of difficulty of dripping during combustion changes, so the flame retardancy is different. The crystalline resin contained in the flame retardant resin composition has a large viscosity change near the melting point. Therefore, in the UL flame retardancy test, the flame retardant resin composition melts due to the heat during combustion, and the viscosity becomes lower. Thus, it is easier to drip, and the fire is extinguished due to the extinguishing of the fire. In particular, with respect to a flame retardant resin composition comprising a crystalline resin with a higher melting point, the temperature rise during combustion causes a viscosity change, so it is easy to drip. In contrast, a flame retardant resin composition comprising a lower melting point crystalline resin is easier to drip, but the fire is easier to remain and becomes difficult to extinguish. On the other hand, in the case of amorphous resins, the viscosity changes due to the temperature rise, and the effect is small due to the small amount of change.

[0075] [Molding products]

[0076] The flame retardant resin composition of the present invention can be used to prepare molded products. A flame retardant product can be obtained by the molded product. When manufacturing the molded product, the flame retardant resin composition can be melted in various molding machines to form it. The molding method can be appropriately selected according to the form and purpose of the molded product. Examples of the molding method include injection molding, extrusion molding, compression molding, blow molding, calendering molding, and inflation molding. In addition, the sheet-like or film-like molded products obtained by extrusion molding and calendering molding can also be subjected to secondary molding such as vacuum molding and compressed air molding.

[0077] The type of molded article formed from the flame retardant resin composition of the present invention is not particularly limited. Examples of the types of molded articles include electrical and electronic components, electrical components, external packaging components, and internal decorative components in the fields of home appliances and vehicles, as well as various packaging materials, household goods, office supplies, piping, and agricultural materials.

[0078] The present invention can provide an electronic device using a molded product as a component. The type of electronic device is not particularly limited. Examples of electronic devices include computers, scanners, copiers, printers, fax machines, OA equipment such as so-called multifunction machines (MFPs) having these functions, and digital printing systems for commercial printing.

[0079] Example

[0080] (Preparation of flame-retardant resin composition 1)

[0081] 3735 g of H350 (Toyo Styrene Co., Ltd.) as a styrene resin, 500 g of TRN-MTJ (Teijin Ltd.) as a PET resin, 750 g of PX-200 (Daihachi Chemical Industry Co., Ltd.) as a phosphorus flame retardant, and 15 g of Flamestab NOR116FF (BASF) as a hindered amine light stabilizer were weighed separately, and then kneaded in a twin-screw kneader TEX-25 (manufactured by The Japan Steel Works) at a temperature of 200° C. and a rotation speed of 200 rpm to obtain a flame retardant resin composition 1.

[0082] (Preparation of flame-retardant resin compositions 2 to 17)

[0083] Flame-retardant resin compositions 2 to 17 were prepared in the same manner as in the preparation of the flame-retardant resin composition 1, except that the materials and blending amounts shown in Tables 1 and 2 were changed.

[0084] The materials shown in Tables 1 and 2 are as follows.

[0085] As acrylonitrile-butadiene-styrene resin of a styrene-based resin, Toyolac (registered trademark) 700 314U (Toray Corporation) was used.

[0086] As the acrylonitrile-butadiene-styrene resin of the styrene-based resin, GAR-011 (KINGFA Co., Ltd.) was used. The ratio of recycled resin in GAR-011 was 95%.

[0087] As the polystyrene resin of the styrene-based resin, TOYO STYRENE HI H350 (Toyo Styrene Co., Ltd.) was used.

[0088] As polyethylene terephthalate (PET) of a crystalline resin, TRN-MTJ (produced by Teijin Ltd.) was used. The melting point of TRN-MTJ is 254°C.

[0089] As the crystalline nylon resin, AMILAN (registered trademark) U310 (Toray Co., Ltd.) was used. The melting point of AMILAN U310 is 260°C.

[0090] As polyethylene terephthalate (PET) of a crystalline resin, KS710B-8S (KURARAY CO., LTD.) was used. The melting point of KS710B-8S is 233°C.

[0091] As polypropylene (PP) of crystalline resin, PRIME POLYPRO (registered trademark) J105G (PRIME POLYMER CO., LTD.) was used. The melting point of PRIME POLYPRO J105G is 170°C.

[0092] As the polycarbonate (PC) of the amorphous resin, STYRON 301-10 (manufactured by SUMIKA POLYCARBONATE CO., LTD.) was used.

[0093] As the aromatic condensed phosphate ester of the phosphorus-based flame retardant, PX-200 (Daihachi Chemical Industry Co., Ltd.) was used.

[0094] As the aromatic condensed phosphate ester of the phosphorus-based flame retardant, CR741 (Daihachi Chemical Industry Co., Ltd.) was used.

[0095] As the NH type hindered amine compound of the hindered amine light stabilizer, Tinuvin 770DF (BASF) was used.

[0096] As the NM type hindered amine compound of the hindered amine light stabilizer, Tinuvin 765 (BASF) was used.

[0097] As a NOR type hindered amine compound of the hindered amine light stabilizer, Flamestab NOR 116FF (BASF) was used.

[0098] Classification No. (number), flame retardant resin composition No. (number), blending amount of various materials, and thermal decomposition temperature are shown in Tables 1 and 2. In addition, in Tables 1 and 2, the blending amount is shown when the entire flame retardant resin composition is taken as 100 mass%.

[0099] [Table 1]

[0100]

[0101] [Table 2]

[0102]

[0103] [evaluate]

[0104] (Preparation of test piece)

[0105] Each of the prepared kneaded products was dried at 80° C. for 4 hours, and then molded at a molding temperature of 220° C. using an injection molding machine JSW-AD110 (manufactured by The Japan Steel Works, Ltd.) to obtain each test piece.

[0106] (Evaluation of flame retardancy)

[0107] The flame retardancy of the flame retardant resin composition was evaluated by performing a UL94V test. The evaluation criteria are as follows, and the cases of ○ and △ were considered to be acceptable in the following evaluation criteria.

[0108] ○: Fire extinguished within 10 seconds

[0109] △: Fire extinguishing within 30 seconds and exceeding 10 seconds

[0110] ×: Burning

[0111] (Evaluation of impact strength)

[0112] The evaluation of the flowability of the flame-retardant resin composition was performed based on JIS K 7111-1. The evaluation criteria are as follows, and the cases of ○ and △ in the following evaluation criteria were considered to be acceptable.

[0113] ○:10kJ / m 2 above

[0114] △: 5kJ / m 2 Above and below 10kJ / m 2

[0115] ×: less than 5 kJ / m 2

[0116] (Evaluation of flexural modulus)

[0117] The evaluation of the flexural modulus of the flame-retardant resin composition was performed in accordance with JIS K 7171. The evaluation criteria are as follows, and the cases of ○ and △ in the following evaluation criteria were considered to be acceptable.

[0118] ○: 2400MPa or more

[0119] △: 2000MPa or more and less than 2400MPa

[0120] ×: less than 2000MPa

[0121] Table 3 shows the classification No., flame retardant resin composition No., and evaluation results.

[0122] [Table 3]

[0123] Table 3

[0124]

[0125] As shown in Tables 1 to 3, in the flame-retardant resin composition No. 10 (Comparative Example 1) not containing a crystalline resin, the impact strength and bending modulus are poor. The flame retardancy is poor in the flame-retardant resin compositions No. 11 and 12 (Comparative Examples 2 and 3) containing a crystalline resin having a melting point below 250°C. In the flame-retardant resin composition No. 13 (Comparative Example 4) containing no crystalline resin and a non-crystalline resin other than a styrene resin, the flame retardancy is poor. It should be noted that in the flame-retardant resin composition No. 10 (Comparative Example 1), the amount of flame retardant is large, so the flame retardancy is good, but the mechanical strength (impact strength and bending modulus) is reduced. In addition, in the flame-retardant resin composition No. 13 (Comparative Example 4), the reduction in mechanical strength is good due to the reduction in the amount of flame retardant. On the other hand, the amount of flame retardant is small, and no crystalline resin is added, so the deviation in the dripping time becomes large, the burning time becomes long, and the flame retardancy is poor. In flame-retardant resin composition No. 14 (Comparative Example 5) in which the phosphorus flame retardant exceeded 15% by mass, the impact strength and bending modulus were poor. In flame-retardant resin composition No. 15 (Comparative Example 6) in which the phosphorus flame retardant was less than 4% by mass, the flame retardancy was poor. In flame-retardant resin composition No. 16 (Comparative Example 7) in which the hindered amine light stabilizer was less than 0.3% by mass, the flame retardancy was poor. In flame-retardant resin composition No. 17 (Comparative Example 8) in which the hindered amine light stabilizer exceeded 3.0% by mass, the flame retardancy was poor.

[0126] As shown in Tables 1 to 3, in the flame retardant resin compositions No. 1 to 9 (Examples 1 to 9) having 74 to 93% by mass of styrene resins, crystalline resins having a melting point of 250°C or more, 4 to 15% by mass of phosphorus flame retardants, and 0.3 to 3.0% by mass of hindered amine light stabilizers, any one of the flame retardancy, impact strength, and flexural modulus is good. In particular, in the flame retardant resin compositions No. 2 to 9 (Examples 2 to 9) containing acrylonitrile-butadiene-styrene resins, the flexural modulus is good compared to the flame retardant resin composition No. 1 (Example 1). In the flame retardant resin compositions No. 4 and 5 (Examples 4 and 5) in which the crystalline resin is a polyester resin or a polyamide resin, the impact strength is good compared to the flame retardant resin composition No. 1 (Example 1). Furthermore, in flame-retardant resin compositions Nos. 7 to 9 (Examples 7 to 9) in which the hindered amine light stabilizer is an NH-type hindered amine compound, the flame retardancy is better than that of flame-retardant resin compositions Nos. 1 to 6 (Examples 1 to 6).

[0127] (Effect)

[0128] As described above, the flame-retardant resin composition of the present embodiment has 74 to 93% by mass of a styrene-based resin, a crystalline resin having a melting point of 250° C. or higher, 4 to 15% by mass of a phosphorus-based flame retardant, and 0.3 to 3.0% by mass of a hindered amine-based light stabilizer, so any one of flame retardancy, impact strength, and flexural modulus is good.

[0129] Industrial Applicability

[0130] According to the present invention, a molded product having excellent flame retardancy, impact strength and flexural modulus can be provided.

Claims

1. A flame retardant resin composition, comprising: 74-93% by mass of styrene resin, Crystalline resin with a melting point of 250°C or above, 4 to 15% by mass of a phosphorus-based flame retardant, and 0.3 to 3.0% by mass of hindered amine light stabilizer.

2. The flame retardant resin composition according to claim 1, wherein The styrene resin is acrylonitrile-butadiene-styrene resin.

3. The flame retardant resin composition according to claim 1 or 2, wherein The styrene resin is a recycled resin.

4. The flame-retardant resin composition according to any one of claims 1 to 3, wherein The crystalline resin is a polyester resin or a polyamide resin.

5. The flame-retardant resin composition according to any one of claims 1 to 4, wherein The content of the crystalline resin is 0.5 to 3.0% by mass.

6. The flame-retardant resin composition according to any one of claims 1 to 5, wherein The hindered amine light stabilizer is an NH type hindered amine compound.

7. The flame-retardant resin composition according to any one of claims 1 to 6, wherein The flame retardant resin composition has a decomposition temperature in the range of 390 to 410° C. obtained based on thermogravimetric analysis. 8 . A molded article formed using the flame-retardant resin composition according to claim 1 .

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