Resin composition and molding

Abstract

To provide a resin composition which is excellent in flame retardance and dripping prevention property during combustion, and is also excellent in flowability.SOLUTION: A resin composition contains (a) (a-1) a polyphenylene ether-based resin, (a-2) a styrenic resin and (a-3) one or more compounds selected from a phosphate-based compound and a phosphazene compound, or (a-1) a polyphenylene ether-based resin, and (a-3) one or more compounds selected from a phosphate-based compound and a phosphazene compound, and (b) a polyarylate resin, wherein the number average molecular weight of (a-1) the component is 1.5×104 to 2.5×104, the glass transition temperature of the component (a) is 100°C to 145°C, and with respect to 100 pts.mass of the component (a-1), or 100 pts.mass of the total of the component (a-1) and the component (a-2), the amount of the component (a-3) is 5 to 40 pts.mass, and the amount of the component (b) is 1 to 12 pts.mass.SELECTED DRAWING: None

Description

[Technical Field]

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

[0002] Polyphenylene ether resins have excellent electrical insulation properties as well as heat resistance, hydrolysis resistance, and flame retardancy, and are therefore widely used in home appliances, office equipment, automobile parts, etc. Materials used in these applications must have high flame retardancy due to fire and other issues, and polyphenylene ether resins can achieve flame retardancy by adding phosphorus compounds without using halogen compounds, making them increasingly useful from a safety perspective.

[0003] Furthermore, in recent years, parts have become smaller and more complex in structure, and these materials are required to have good flowability (moldability) and mechanical properties during injection molding.

[0004] In response to this, for example, Patent Document 1 discloses a polyphenylene ether resin composition that is excellent in flowability and moldability. [Prior art documents] [Patent documents]

[0005] [Patent Document 1] Japanese Patent Application Publication No. 8-20717 Summary of the Invention [Problem to be solved by the invention]

[0006] As polyphenylene ether resins become more fluid, there is a problem that test specimens tend to burn and drip during UL flammability tests (UL94). To obtain a high level of flame retardancy in the UL flammability test (UL94) regulated by Underwriter Laboratories, it is necessary that the absorbent cotton does not ignite due to dripping during the UL flammability test. Therefore, the drip-prevention properties of the resin are an important issue in preventing the spread of fire in an actual fire. However, with regard to the resin composition described in Patent Document 1, no consideration has been given to preventing dripping.

[0007] Therefore, an object of the present invention is to provide a resin composition and a molded article thereof which are excellent in flame retardancy, anti-dripping properties during combustion, and flowability. [Means for solving the problem]

[0008] As a result of intensive research into solving the above-mentioned problems, the present inventors have found that the above-mentioned problems can be solved by using a composition comprising (a) (a-1) a polyphenylene ether resin, (a-2) a styrene resin, and (a-3) one or more compounds selected from phosphate ester compounds and phosphazene compounds, or (a-1) a polyphenylene ether resin, and (a-3) one or more compounds selected from phosphate ester compounds and phosphazene compounds, and (b) a polyarylate resin, wherein the component (a-1) has a specific molecular weight and the component (a) has a specific glass transition temperature, and the components are each present in a specific amount. This finding led to the completion of the present invention.

[0009] That is, the present invention is as follows. [1] (a) (a-1) one or more compounds selected from a polyphenylene ether resin, (a-2) a styrene resin, and (a-3) a phosphate ester compound and a phosphazene compound, or (a-1) a polyphenylene ether resin, and (a-3) one or more compounds selected from a phosphate ester compound and a phosphazene compound, and (b) polyarylate resin, Including, The number average molecular weight of the (a-1) component is 1.5 × 10 4 ~2.5×10 4and The glass transition temperature of the component (a) is 100°C to 145°C, per 100 parts by mass of the component (a-1) or the total of the components (a-1) and (a-2), the amount of the component (a-3) is 5 to 40 parts by mass, The amount of the component (b) is 1 to 12 parts by mass. Resin composition.

[0010] [2] When the component (a) contains the component (a-1) and the component (a-2), In 100 parts by mass of the total of the components (a-1) and (a-2), the amount of the component (a-1) is 45 to 85 parts by mass, the amount of the (a-2) component is 15 to 55 parts by mass, The resin composition according to [1], wherein the amount of the (a-3) component is 10 to 35 parts by mass per 100 parts by mass of the total of the (a-1) component and the (a-2) component.

[0011] [3] The resin composition according to [1] or [2], wherein the component (a-3) is a phosphate ester compound represented by the following general formula (I) or general formula (II): [ka] [ka] (In general formula (I), Q1, Q2, Q3, and Q4 independently represent an alkyl group having 1 to 6 carbon atoms, R11 and R12 independently represent a methyl group, and R13 and R14 independently represent a hydrogen atom or a methyl group. In general formula (II), Q1, Q2, Q3, and Q4 independently represent an alkyl group having 1 to 6 carbon atoms, and R11 and R12 represent a methyl group. In general formula (I) and general formula (II), y is an integer of 1 or more, n1 and n2 independently represent an integer of 0 to 2, and m1, m2, m3, and m4 independently represent an integer of 0 to 3.

[0012] [4] The resin composition according to any one of [1] to [3], further comprising (c) an elastomer.

[0013] [5] The resin composition according to any one of [1] to [4], further comprising (d) a compatibilizer.

[0014] [6] The resin composition according to any one of [1] to [5], which has a melt flow rate of 10 g / 10 min or more as measured in accordance with ISO1133 at a temperature of 250° C. under a load of 10 kg.

[0015] [7] The resin composition according to any one of [1] to [6], wherein the amount of the component (a) is 70 to 99 parts by mass per 100 parts by mass of the resin composition.

[0016] [8] The resin composition according to any one of [1] to [7], wherein the total amount of the component (a) and the component (b) is 70 to 100 parts by mass per 100 parts by mass of the resin composition.

[0017] [9] A molded article comprising the resin composition according to any one of [1] to [8]. [Effects of the Invention]

[0018] According to the present invention, it is possible to provide a resin composition and a molded article that are excellent in flame retardancy, anti-dripping properties during combustion, and flowability. DETAILED DESCRIPTION OF THE INVENTION

[0019] Hereinafter, a mode for carrying out the present invention (hereinafter referred to as "the present embodiment") will be described in detail. The following present embodiment is an example for explaining the present invention, and is not intended to limit the present invention to the following content. The present invention can be carried out by appropriately modifying it within the scope of its gist.

[0020] <Definition> In this specification, (a-1) polyphenylene ether resin, (a-2) styrene resin, (a-3) one or more compounds selected from phosphate ester compounds and phosphazene compounds, (b) polyarylate resin, (c) elastomer, and (d) compatibilizer may be referred to as component (a-1), component (a-2), component (a-3), component (b), component (c), and component (d), respectively. In addition, in this specification, component (a-1), component (a-2), and component (a-3) may be collectively referred to as component (a).

[0021] <Resin composition> The resin composition of the present embodiment is (a) (a-1) one or more compounds selected from a polyphenylene ether resin, (a-2) a styrene resin, and (a-3) a phosphate ester compound and a phosphazene compound, or (a-1) a polyphenylene ether resin, and (a-3) one or more compounds selected from a phosphate ester compound and a phosphazene compound, and (b) polyarylate resin, Including, The number average molecular weight of the (a-1) component is 1.5 × 10 4 ~2.5×10 4 and The glass transition temperature of the component (a) is 100°C to 145°C, per 100 parts by mass of the component (a-1) or the total of the component (a-1) and the component (a-2), the amount of the component (a-3) is 5 to 40 parts by mass, The amount of the component (b) is 1 to 12 parts by mass. The resin composition has excellent flame retardancy and anti-dripping properties during combustion, as well as excellent fluidity.

[0022] The resin composition of this embodiment preferably has a melt flow rate (MFR) of 5 g / 10 min or more, measured in accordance with ISO 1133 at a measurement temperature of 250°C under a load of 10 kg. A resin composition having a melt flow rate of 5 g / 10 min or more has excellent fluidity. From the same viewpoint, the resin composition of this embodiment more preferably has a melt flow rate of 10 g / 10 min or more, even more preferably has a melt flow rate of 15 g / 10 min or more, and even more preferably has a melt flow rate of 20 g / 10 min or more. The melt flow rate may also be 60 g / 10 min or less, or 50 g / 10 min or less.

[0023] From the viewpoint of impact resistance, the resin composition of the present embodiment has a Charpy impact strength of 10 kJ / m 2 From the same viewpoint, the Charpy impact strength is preferably 15 kJ / m or more. 2 More preferably, it is 20 kJ / m or more. 2 It is more preferable that the Charpy impact strength is 50 kJ / m or more. 2 It may be the following: The Charpy impact strength of the resin composition is a value measured in accordance with ISO-179 using a test piece having dimensions specified in the ISO-179 standard with a notch.

[0024] (a) (a-1) one or more compounds selected from a polyphenylene ether resin, (a-2) a styrene resin, and (a-3) a phosphate ester compound and a phosphazene compound, or (a-1) a polyphenylene ether resin and (a-3) one or more compounds selected from a phosphate ester compound and a phosphazene compound (component (a))) The component (a) of this embodiment is one or more compounds selected from (a-1) a polyphenylene ether resin, (a-2) a styrene resin, and (a-3) a phosphate ester compound and a phosphazene compound, or one or more compounds selected from (a-1) a polyphenylene ether resin and (a-3) a phosphate ester compound and a phosphazene compound. In other words, the component (a) is a component containing (a-1) a polyphenylene ether resin, (a-2) a styrene resin, and (a-3) one or more compounds selected from a phosphate ester compound and a phosphazene compound, or a component containing (a-1) a polyphenylene ether resin and (a-3) one or more compounds selected from a phosphate ester compound and a phosphazene compound. The component (a) may be of only two types or a combination of two or more types.

[0025] In this embodiment, the glass transition temperature of component (a) is 100° C. to 145° C., preferably 100° C. to 140° C., and more preferably 100° C. to 135° C. The lower the glass transition temperature, the better the fluidity but the easier the dripping tends to be; a glass transition point of 100° C. or higher tends to provide excellent anti-dripping properties, while a glass transition point of 145° C. or lower tends to provide excellent fluidity. The glass transition temperature of component (a) was measured using a DSC measuring device by heating from 50°C to 300°C at a heating rate of 20°C per minute in a nitrogen atmosphere, then cooling to 50°C at a rate of 20°C per minute, and then increasing the temperature at a rate of 20°C per minute thereafter.

[0026] -(a-1) Polyphenylene ether resin (component (a-1))- As the component (a-1) contained in the resin composition of this embodiment, either a homopolymer consisting of a structural unit of the following general formula (III) or a copolymer having a structural unit of the general formula (III) (hereinafter, sometimes simply referred to as "polyphenylene ether") can be used. [ka] In general formula (III), O represents an oxygen atom, and R21 to R24 independently represent any one selected from the group consisting of a hydrogen atom, a halogen atom, a primary or secondary alkyl group having 1 to 8 carbon atoms, a phenyl group, a haloalkyl group, an aminoalkyl group, a hydrocarbonoxy group, and a halohydrocarbonoxy group (provided that at least two carbon atoms separate the halogen atom from the oxygen atom).

[0027] Examples of homopolymers of polyphenylene ether resins include, but are not limited to, poly(2,6-dimethyl-1,4-phenylene ether), poly(2-methyl-6-ethyl-1,4-phenylene ether), poly(2-methyl-6-phenyl-1,4-phenylene ether), and poly(2,6-dichloro-1,4-phenylene ether).

[0028] Examples of copolymers of polyphenylene ether resins include, but are not limited to, copolymers of 2,6-dimethylphenol with other phenols (e.g., copolymers with 2,3,6-trimethylphenol, copolymers with 2-methyl-6-butylphenol).

[0029] Among these, the polyphenylene ether resin is preferably poly(2,6-dimethyl-1,4-phenylene ether), a copolymer of 2,6-dimethylphenol and 2,3,6-trimethylphenol, or a mixture thereof, from the viewpoint of balance of mechanical properties and productivity.

[0030] Methods for producing the polyphenylene ether resin used in the present embodiment include, but are not limited to, known production methods described in, for example, U.S. Pat. Nos. 3,306,874, 3,306,875, 3,257,357, and 3,257,358, JP-A-50-51197, JP-B-52-17880, and JP-A-63-152628.

[0031] From the viewpoint of the balance between anti-dripping properties and fluidity, the reduced viscosity of the polyphenylene ether resin is preferably in the range of 0.25 to 0.70 dL / g. The reduced viscosity is more preferably in the range of 0.30 to 0.65 dL / g, and even more preferably in the range of 0.40 to 0.60 dL / g. When the reduced viscosity is 0.25 dL / g or more, the anti-dripping properties are excellent. Furthermore, when the reduced viscosity is 0.65 dL / g or less, the fluidity is excellent. In this embodiment, the reduced viscosity of the polyphenylene ether resin is a value measured using a 0.5 g / dL chloroform solution at 30°C using an Ubbelohde viscometer. In this embodiment, a mixture of two or more polyphenylene ether resins having different reduced viscosities can also be preferably used.

[0032] Furthermore, the polyphenylene ether resin (a-1) of this embodiment may contain a modified polyphenylene ether that has been completely or partially modified. The modified polyphenylene ether referred to here refers to a polyphenylene ether modified with a modifying compound (hereinafter sometimes simply referred to as a "modifying compound") that has at least one carbon-carbon double bond or triple bond in the molecule and at least one group selected from the group consisting of a carboxylic acid group, an acid anhydride group, an amino group, a hydroxyl group, and a glycidyl group. Only one type of modifying compound may be used, or two or more types may be used in combination.

[0033] Methods for producing modified polyphenylene ether include, but are not limited to, (1) a method of reacting with a modifying compound at a temperature in the range of 100°C or higher and lower than the glass transition temperature of polyphenylene ether, (2) a method of melt-kneading and reacting with a modifying compound at a temperature in the range of higher than the glass transition temperature of polyphenylene ether and lower than 360°C, and (3) a method of reacting polyphenylene ether with a modifying compound in a solution at a temperature lower than the glass transition temperature of polyphenylene ether, in the presence or absence of a radical initiator. Among these methods for producing modified polyphenylene ether, method (1) or (2) is preferred from the viewpoint of productivity.

[0034] Next, the modifying compound used to produce the modified polyphenylene ether will be described. The modifying compound used to produce the modified polyphenylene ether is a modifying compound having at least one carbon-carbon double bond or triple bond in the molecule and at least one group selected from the group consisting of a carboxylic acid group, an acid anhydride group, an amino group, a hydroxyl group, and a glycidyl group.

[0035] Examples of the modifying compound having a carbon-carbon double bond in the molecule and a carboxylic acid group or an acid anhydride group include, but are not limited to, unsaturated dicarboxylic acids such as maleic acid, fumaric acid, chloromaleic acid, and cis-4-cyclohexene-1,2-dicarboxylic acid, as well as their acid anhydrides. In particular, from the viewpoint of reactivity with the polyphenylene ether resin, fumaric acid, maleic acid, and maleic anhydride are preferred as the modifying compound, and fumaric acid and maleic anhydride are more preferred.

[0036] Furthermore, compounds in which one or two of the two carboxyl groups of the above unsaturated dicarboxylic acid are esterified can also be used as modified compounds.

[0037] Examples of modified compounds having a carbon-carbon double bond and a glycidyl group in the molecule include, but are not limited to, allyl glycidyl ether, glycidyl acrylate, glycidyl methacrylate, epoxidized natural fats and oils, etc. Among these, glycidyl acrylate and glycidyl methacrylate are preferred.

[0038] The modified compound having a carbon-carbon double bond and a hydroxy group in the molecule includes, but is not limited to, compounds represented by the general formula C, such as allyl alcohol, 4-penten-1-ol, and 1,4-pentadiene-3-ol. n H 2n-1 O.H., C. n H 2n-3 unsaturated alcohols of formula C n H 2n-5 O.H., C. n H2n-7 OH (wherein n is a positive integer) and other unsaturated alcohols.

[0039] The above-mentioned modifying compounds may be used either alone or in combination of two or more.

[0040] The amount of the modifying compound added when producing the modified polyphenylene ether is, for example, preferably 0.1 to 10 parts by mass, more preferably 0.3 to 5 parts by mass, and even more preferably 0.5 to 3 parts by mass, per 100 parts by mass of the polyphenylene ether, from the viewpoint of modification efficiency.

[0041] When producing modified polyphenylene ether using a radical initiator, the amount of the radical initiator added is preferably 0.001 to 1 part by mass, more preferably 0.01 to 0.5 parts by mass, and even more preferably 0.05 to 0.3 parts by mass, per 100 parts by mass of polyphenylene ether, from the viewpoint of the balance between the modification rate and physical properties.

[0042] The addition rate of the modifying compound to the modified polyphenylene ether is preferably 0.01 to 5 mass %, more preferably 0.05 to 3 mass %, and even more preferably 0.1 to 1 mass %, relative to 100 mass % of the modified polyphenylene ether.

[0043] The modified polyphenylene ether may contain unreacted modifying compounds and polymers of the modifying compounds, and the amount of unreacted modifying compounds and polymers of the modifying compounds remaining is preferably less than 5% by mass, more preferably 3% by mass or less, and even more preferably 1% by mass or less.

[0044] In this embodiment, the number average molecular weight of the (a-1) component is 1.5 × 10 4 ~2.5×10 4 and preferably 1.6 × 10 4 ~2.4×10 4 and more preferably 1.8 × 10 4 ~2.3×10 4The lower the molecular weight, the better the fluidity but the easier it is to drip. 4 2.5 x 10 or more provides excellent drip prevention. 4 The following tend to have good liquidity: The number average molecular weight of the component (a-1) is a value determined by gel permeation chromatography.

[0045] -(a-2) styrene-based resin (component (a-2))- In this embodiment, the (a-2) styrene-based resin (component (a-2)) is a copolymer obtained by polymerizing a styrene-based compound or a compound copolymerizable with a styrene-based compound (hereinafter, a "compound copolymerizable with a styrene-based compound" may be simply referred to as a "copolymerizable compound") in the presence or absence of a rubber polymer. Styrenic resins that also fall under the category of (c) elastomer and (d) compatibilizer, described below, are referred to as component (c) and component (d), respectively, rather than component (a-2).

[0046] Examples of the styrene-based compound include, but are not limited to, styrene, α-methylstyrene, 2,4-dimethylstyrene, monochlorostyrene, p-methylstyrene, p-tert-butylstyrene, ethylstyrene, etc. Among these, styrene is preferred as the styrene-based compound.

[0047] Examples of styrene-based compounds and compounds copolymerizable with styrene-based compounds (copolymerizable compounds) include, but are not limited to, methacrylic acid esters such as methyl methacrylate and ethyl methacrylate; unsaturated nitrile compounds such as acrylonitrile and methacrylonitrile; and acid anhydrides such as maleic anhydride.

[0048] The amount of the copolymerizable compound is preferably 20% by mass or less, and more preferably 15% by mass or less, relative to 100% by mass of the total amount of the styrene-based compound and the copolymerizable compound.

[0049] Examples of the rubbery polymer include conjugated diene rubber, copolymer of conjugated diene and aromatic vinyl compound, ethylene-propylene copolymer rubber, etc. Among them, preferred rubbery polymers are polybutadiene, styrene-butadiene random copolymer, styrene-butadiene block copolymer, and rubber components obtained by partially, substantially completely, or completely hydrogenating these (for example, rubber components with a hydrogenation rate of 50 to 100%).

[0050] Examples of the component (a-2) include, but are not limited to, homopolystyrene, rubber-modified polystyrene (HIPS), styrene-acrylonitrile copolymer (AS resin), styrene-rubber polymer-acrylonitrile copolymer (ABS resin), other styrene-based copolymers, etc. Among these, from the viewpoint of compatibility with polyphenylene ether-based resins, the component (a-2) is preferably at least one selected from the group consisting of homopolystyrene and rubber-modified polystyrene (HIPS).

[0051] ((a-3) One or more compounds selected from phosphate ester compounds and phosphazene compounds (component (a-3))) The resin composition of the present embodiment contains (a-3) one or more compounds selected from phosphate ester compounds and phosphazene compounds. The component (a-3) may be used alone or in combination of two or more.

[0052] As the component (a-3), a phosphate ester compound and / or a phosphazene compound can be used, but among these, it is preferable to include a phosphate ester compound from the viewpoint of the balance between flame retardancy and fluidity.

[0053] Examples of phosphate ester compounds include, but are not limited to, triphenyl phosphate, trisnonylphenyl phosphate, resorcinol bis(diphenyl phosphate), resorcinol bis[di(2,6-dimethylphenyl)phosphate], 2,2-bis{4-[bis(phenoxy)phosphoryloxy]phenyl}propane, and 2,2-bis{4-[bis(methylphenoxy)phosphoryloxy]phenyl}propane. Further, examples of the phosphoric acid ester compounds include phosphoric acid ester compounds such as trimethyl phosphate, triethyl phosphate, tributyl phosphate, trioctyl phosphate, tributoxyethyl phosphate, tricresyl phosphate, cresyl phenyl phosphate, octyl diphenyl phosphate, and diisopropyl phenyl phosphate; diphenyl-4-hydroxy-2,3,5,6-tetrabromobenzyl phosphate, dimethyl-4-hydroxy-3,5-dibromobenzyl phosphate, and diphenyl-4-hydroxy-3,5-dibromo Examples of suitable phosphate esters include monophosphate ester compounds such as benzyl phosphate, tris(chloroethyl)phosphate, tris(dichloropropyl)phosphate, tris(chloropropyl)phosphate, bis(2,3-dibromopropyl)-2,3-dichloropropylphosphate, tris(2,3-dibromopropyl)phosphate, bis(chloropropyl)monoctylphosphate hydroquinonyldiphenylphosphate, phenylnonylphenylhydroquinonylphosphate, and phenyldinonylphenylphosphate; and aromatic condensed phosphate ester compounds. Among these, aromatic condensed phosphate ester compounds are preferred because they generate less gas during processing and have excellent thermal stability.

[0054] Aromatic condensed phosphate ester compounds are commercially available, and examples thereof include, but are not limited to, trade names "CR741," "CR733S," "PX200," and "E890" from Daihachi Chemical Industry Co., Ltd., and trade names "FP600," "FP700," and "FP800" from ADEKA Corporation.

[0055] The component (a-3) used in this embodiment is preferably an aromatic condensed phosphate ester represented by the following general formula (I) or the following general formula (II), and more preferably an aromatic condensed phosphate ester represented by the general formula (I). [ka] [ka] In general formula (I), Q1, Q2, Q3, and Q4 independently represent an alkyl group having 1 to 6 carbon atoms, R11 and R12 independently represent a methyl group, and R13 and R14 independently represent a hydrogen atom or a methyl group. In general formula (II), Q1, Q2, Q3, and Q4 independently represent an alkyl group having 1 to 6 carbon atoms, and R11 and R12 represent a methyl group. In general formula (I) and general formula (II), y is an integer of 1 or more, n1 and n2 independently represent an integer of 0 to 2, and m1, m2, m3, and m4 independently represent an integer of 0 to 3. In general formula (I) and general formula (II), y is preferably an integer of 1, 2 or 3, and more preferably 1.

[0056] In one preferred example of general formula (I), m1, m2, m3, m4, n1, and n2 are 0, R13 and R14 are methyl groups, and y is 1, 2, or 3. In another preferred example of general formula (I), Q1, Q2, Q3, Q4, R13, and R14 are methyl groups, n1 and n2 are 0, m1, m2, m3, and m4 are 1, 2, or 3, and y is 1, 2, or 3.

[0057] The component (a-3) preferably contains 50 to 100% by mass of the aromatic condensed phosphate ester of formula (I) relative to 100% by mass of the component (a-3).

[0058] In one preferred example of general formula (II), m1, m2, m3, m4, n1, and n2 are 0, and y is 1, 2, or 3. In another preferred example of general formula (II), Q1, Q2, Q3, and Q4 are methyl groups, n1 and n2 are 0, m1, m2, m3, and m4 are 1, 2, or 3, and y is 1, 2, or 3.

[0059] The component (a-3) preferably contains 50 to 100% by mass of the aromatic condensed phosphate ester of formula (II) relative to 100% by mass of the component (a-3).

[0060] The aromatic condensed phosphate ester compound more preferably has an acid value of 0.1 or less (a value obtained in accordance with JIS K2501).

[0061] ((b) Polyarylate resin (component (b))) The resin composition of the present embodiment contains (b) a polyarylate resin (component (b)). The (b) polyarylate resin (component (b)) of this embodiment is a polymer containing an aromatic ring and an ester bond in the structural unit, and is also called a polyaryl ester.

[0062] As the polyarylate resin, a polyarylate having a repeating unit represented by the following general formula (IV), which is made of bisphenol A and terephthalic acid and / or isophthalic acid, is preferably used. [ka]

[0063] Furthermore, as the polyarylate resin of component (b), a commercially available product can also be used, for example, "U Polymer" manufactured by Unitika Ltd.

[0064] The molecular weight of the (b) polyarylate resin is preferably a number average molecular weight, in terms of polystyrene, measured by gel permeation chromatography (GPC), of 5,000 to 300,000, more preferably 10,000 to 300,000, and even more preferably 10,000 to 100,000. When the number average molecular weight of the polyarylate resin is 5,000 or more, the heat resistance of the molded article tends to be good and the mechanical strength of the resin tends to be high, and when it is 300,000 or less, the fluidity of the resin tends to be good. Specifically, the polystyrene-equivalent number average molecular weight is determined from the detection time-molecular weight curve of a standard polystyrene previously measured under the same conditions using GPC, chloroform as the solvent, and a column temperature of 40°C. The concentration of the chloroform solution of the polyarylate resin is 1 g / L. The measurement is preferably performed using an ultraviolet absorption detector at about 280 nm.

[0065] ((c) Elastomer ((c) component)) The resin composition of the present embodiment may further contain (c) an elastomer. A preferred elastomer (c) is a block copolymer of an aromatic vinyl compound (e.g., styrene) and a conjugated diene compound, and more preferably a hydrogenated block copolymer obtained by hydrogenating the block copolymer. As mentioned above, styrene compounds included in the elastomer are not included in component (a-2).

[0066] The hydrogenation rate (hydrogenation rate) of unsaturated bonds derived from the conjugated diene compound by hydrogenation is preferably 60% or more, more preferably 80% or more, and even more preferably 95% or more, from the viewpoint of heat resistance stability.

[0067] When the block copolymer is a block copolymer of styrene and a conjugated diene compound, examples of the structure of the block copolymer before hydrogenation include SBS, SBSB, (SB-)-S, and SBSBS, where S represents the styrene block chain and B represents the diene compound block chain. The microstructure of the polymer block of the conjugated diene compound (bonding form of the conjugated diene compound) can be selected arbitrarily. The vinyl bond content (total of 1,2-vinyl bonds and 3,4-vinyl bonds) of the conjugated diene compound polymer block is preferably 2 to 60%, more preferably 8 to 40%, of the total bond content of the conjugated diene compound polymer (total of 1,2-vinyl bonds, 3,4-vinyl bonds and 1,4-conjugated bonds).

[0068] The number average molecular weight of component (c) is preferably 100,000 to 400,000, more preferably 150,000 to 350,000, and even more preferably 200,000 to 300,000. When the number average molecular weight of component (c) is 100,000 or more, the resin composition has superior impact resistance. When the number average molecular weight of component (c) is 400,000 or less, the resin composition has superior fluidity. Specifically, the polystyrene-equivalent number average molecular weight can be determined from the detection time-molecular weight curve of a standard polystyrene previously measured under the same conditions using GPC with chloroform as the solvent and a column temperature of 40°C.

[0069] When component (c) has styrene polymer block chains, it is preferable that at least one of the styrene polymer block chains has a number average molecular weight of 15,000 or more. The number average molecular weight of at least one of the styrene polymer block chains is more preferably 20,000 to 50,000. It is even more preferable that all of the styrene polymer block chains have a number average molecular weight of 15,000 or more.

[0070] When component (c) has a styrene polymer block chain, the proportion of the styrene polymer block chain in component (c) is not particularly limited as long as the number average molecular weight of the styrene polymer block chain is within the above-mentioned range. From the viewpoint of impact resistance, however, it is preferably 10 to 70 mass %, more preferably 20 to 50 mass %, and even more preferably 30 to 40 mass %.

[0071] Two or more hydrogenated block copolymers with different compositions or structures may be used in combination as component (c), for example, a hydrogenated block copolymer having a bound styrene polymer block content of 50% by mass or more and a hydrogenated block copolymer having a bound styrene polymer block content of 30% by mass or less, a hydrogenated block copolymer having different molecular weights, or a hydrogenated random block copolymer obtained by hydrogenating a block copolymer containing a random copolymer block of styrene and a conjugated diene compound, as described above. The "bound styrene polymer block content" refers to the proportion of styrene polymer block chains in component (c).

[0072] ((d) Compatibilizer (Component (d))) The resin composition of this embodiment may further contain a compatibilizer (d) from the viewpoint of finely dispersing component (b) in component (a). By including component (d), the resin composition of this embodiment becomes a resin composition with even more excellent anti-dripping properties and impact resistance.

[0073] (d) The compatibilizer may be, but is not limited to, a styrene copolymer having a glycidyl group.

[0074] The glycidyl group-containing styrene copolymer is not limited, but examples thereof include copolymers of a glycidyl group-containing unsaturated monomer and a styrene monomer. Examples of glycidyl group-containing unsaturated monomers include unsaturated carboxylic acid glycidyl esters and unsaturated glycidyl ethers. Examples of unsaturated carboxylic acid glycidyl esters include glycidyl acrylate, glycidyl methacrylate, and monoglycidyl itaconic acid ester. Examples of unsaturated glycidyl ethers include vinyl glycidyl ether, allyl glycidyl ether, 2-methylallyl glycidyl ether, and methacrylic glycidyl ether. Examples of the styrene-based monomer include styrene, methylstyrene, dimethylstyrene, and ethylstyrene. These glycidyl group-containing styrene copolymers may be used alone or in combination of two or more.

[0075] From the viewpoint of improving miscibility with component (a), the styrene copolymer preferably contains 65% by weight or more, and more preferably 75 to 95% by weight, of styrene monomer units.

[0076] (Other flame retardants) The resin composition of the present embodiment may contain various conventionally known flame retardants and flame retardant auxiliaries, such as phosphinates, alkaline earth metal hydroxides such as magnesium hydroxide, aluminum hydroxide, alkali metal hydroxides, zinc borate compounds, and zinc stannate compounds.

[0077] (additives) To impart other properties to the resin composition of the present embodiment, additives such as resins other than component (a) and component (b), plasticizers, antioxidants, stabilizers such as ultraviolet absorbers, antistatic agents, release agents, dyes, pigments, fillers, reinforcing materials, and spreading agents may be added within a range that does not impair the effects of the present invention.

[0078] (Content of each ingredient) In the resin composition of this embodiment, the amounts of the (a-3) component and the (b) component are 5 to 40 parts by mass of the (a-3) component and 1 to 12 parts by mass of the (b) component, relative to 100 parts by mass of the (a-1) component or 100 parts by mass of the total of the (a-1) component and the (a-2) component.

[0079] The constituent components of component (a) may be a mixed resin of components (a-1) and (a-2) and component (a-3), or may be component (a-1) and component (a-3).

[0080] When the component (a) is a mixed resin of the components (a-1) and (a-2), the amounts of the components (a-1) and (a-2) are, per 100 parts by mass of the total of the components (a-1) and (a-2), preferably 45 to 85 parts by mass of the component (a-1) and 15 to 55 parts by mass of the component (a-2), more preferably 50 to 75 parts by mass of the component (a-1) and 25 to 50 parts by mass of the component (a-2), and even more preferably 50 to 70 parts by mass of the component (a-1) and 30 to 50 parts by mass of the component (a-2). When the amount of the component (a-1) is 45 parts by mass or more per 100 parts by mass of the total of the components (a-1) and (a-2), better anti-dripping properties tend to be obtained, and when it is 85 parts by mass or less, better fluidity tends to be obtained.

[0081] As described above, the amount of component (a-3) is 5 to 40 parts by mass per 100 parts by mass of component (a-1) or 100 parts by mass of the combined total of components (a-1) and (a-2). The amount of component (a-3) is preferably 10 to 35 parts by mass, more preferably 15 to 30 parts by mass, per 100 parts by mass of component (a-1) or 100 parts by mass of the combined total of components (a-1) and (a-2). When the amount of component (a-3) is 5 parts by mass or more, the resin composition tends to have excellent flame retardancy and flowability, and when it is 40 parts by mass or less, the resin composition tends to have even better anti-dripping properties.

[0082] As described above, the amount of component (b) is 1 to 12 parts by mass per 100 parts by mass of component (a-1) or 100 parts by mass of the combined total of components (a-1) and (a-2). The amount of component (b) is preferably 1.5 to 10 parts by mass, more preferably 2 to 8 parts by mass, and even more preferably 2 to 5 parts by mass per 100 parts by mass of component (a-1) or 100 parts by mass of the combined total of components (a-1) and (a-2). When the amount of component (b) is 1 part by mass or more, the resin composition tends to have better anti-dripping properties, and when it is 12 parts by mass or less, the resin composition tends to have better fluidity and impact resistance.

[0083] Furthermore, from the viewpoint of achieving excellent flame retardancy and anti-dripping properties, the amount of component (a) is preferably 70 to 99 parts by mass, more preferably 75 to 99 parts by mass, and even more preferably 80 to 99 parts by mass per 100 parts by mass of the resin composition of this embodiment. Furthermore, the total amount of components (a) and (b) per 100 parts by mass of the resin composition of this embodiment is preferably 70 to 100 parts by mass, more preferably 75 to 100 parts by mass, and even more preferably 80 to 100 parts by mass. By adopting the above-described embodiment, the content of the crystalline resin that tends to drip in a temperature range higher than the melting point can be reduced, and the resin composition has excellent flame retardancy and anti-dripping properties.

[0084] When component (c) is contained, the amount of component (c) is preferably 50 parts by mass or less, more preferably 40 parts by mass or less, and even more preferably 30 parts by mass or less, per 100 parts by mass of component (a-1) or the combined total of components (a-1) and (a-2). When the amount of component (c) is 50 parts by mass or less, the resin composition tends to have better flame retardancy. When component (c) is contained, the total amount of components (a), (b), and (c) is preferably 80 to 100 parts by mass, more preferably 85 to 100 parts by mass, and even more preferably 90 to 100 parts by mass, per 100 parts by mass of the resin composition of this embodiment. By adopting the above-mentioned embodiment, excellent flame retardancy and anti-dripping properties are achieved.

[0085] When component (d) is contained, the amount of component (d) is preferably 8 parts by mass or less, more preferably 5 parts by mass or less, and even more preferably 3 parts by mass or less, per 100 parts by mass of component (a-1) or the combined total of components (a-1) and (a-2). When the amount of component (d) is 8 parts by mass or less, the resin composition tends to have better fluidity. When component (d) is contained, the total amount of components (a), (b), and (d) is preferably 70 to 100 parts by mass, more preferably 75 to 100 parts by mass, and even more preferably 80 to 100 parts by mass, per 100 parts by mass of the resin composition of this embodiment. By adopting the above-mentioned embodiment, excellent flame retardancy and anti-dripping properties are achieved.

[0086] When the resin composition of the present embodiment contains the components (c) and (d), the total amount of the components (a), (b), (c), and (d) is preferably 80 to 100 parts by mass, more preferably 85 to 100 parts by mass, and even more preferably 90 to 100 parts by mass, per 100 parts by mass of the resin composition of the present embodiment. By adopting the above-mentioned embodiment, excellent flame retardancy and anti-dripping properties are achieved.

[0087] When other flame retardants are contained, the amount of the other flame retardants is, from the viewpoint of fluidity and appearance, preferably 40 parts by mass or less, more preferably 30 parts by mass or less, and even more preferably 20 parts by mass or less, per 100 parts by mass of component (a-1) or the total of components (a-1) and (a-2). When the amount of the other flame retardants is 40 parts by mass or less, the fluidity and appearance tend to be excellent.

[0088] The total amount of the above-mentioned additives is preferably 15% by mass or less, more preferably 10% by mass or less, and even more preferably 5% by mass or less, based on 100% by mass of the resin composition.

[0089] (Method of producing resin composition) The resin composition of the present embodiment can be produced, for example, by melt-kneading the components (a) and (b), and optionally the components (c) and (d), etc., using a twin-screw extruder.

[0090] Examples of twin-screw extruders include the "ZSK" series manufactured by Coperion, the "TEM" series manufactured by Toshiba Machine Co., Ltd., and the "TEX" series manufactured by The Japan Steel Works, Ltd.

[0091] In the method for producing a resin composition of this embodiment, the melt-kneading temperature and the screw rotation speed can be appropriately selected from the ranges of 200 to 370° C. and 100 to 1200 rpm.

[0092] Examples of raw material supply devices for supplying raw materials to a twin-screw extruder include loss-in-weight feeders, single screw feeders, twin screw feeders, table feeders, rotary feeders, etc. Among these, loss-in-weight feeders are preferred from the viewpoint of reducing fluctuation errors in raw material supply.

[0093] When supplying a liquid raw material, the liquid raw material can be kneaded by directly feeding it into the cylinder of the extruder using a liquid addition pump or the like. The liquid addition pump is not particularly limited, and examples thereof include a gear pump and a flange-type pump. Among these, a gear pump is preferred. Furthermore, it is more preferred to heat the parts that serve as the flow path for the liquid raw material, such as a tank for storing the liquid raw material used in the liquid addition pump, the piping between the tank and the pump, and the piping between the pump and the extruder cylinder, using a heater or the like. This reduces the viscosity of the liquid raw material, thereby reducing the load on the liquid addition pump, which is preferred from the standpoint of operability, etc.

[0094] (Application) The resin composition of this embodiment can be used as a material for, for example, electric and electronic parts, home appliances, office automation equipment, and the like.

[0095] <Molded body> The molded article of the present embodiment includes the resin composition of the present embodiment. The molded article of the present embodiment includes the resin composition of the present embodiment, and therefore has excellent flame retardancy and anti-dripping properties during combustion.

[0096] The resin composition of the present embodiment can be molded into a molded article.

[0097] Examples of molding methods that can be used include known molding methods such as injection molding, blow molding, extrusion molding, sheet molding, and film molding, with injection molding being particularly preferred. Examples of injection molding machines include the "PS-40" manufactured by Nissei Plastics Industrial Co., Ltd.

[0098] The melting temperature and mold temperature in the molding method of the resin composition of this embodiment can be appropriately selected from the ranges of 150 to 350°C for the melting temperature and 5 to 150°C for the mold temperature.

[0099] The molded articles can be used in a wide range of applications, including industrial parts, electrical and electronic parts, office equipment housings, automotive parts, and precision parts. [Example]

[0100] The present invention will be described in detail below with reference to specific examples and comparative examples, but the present invention is not limited to the following examples.

[0101] <Raw materials> The raw materials used in the resin compositions of the examples and comparative examples are shown below. Component (a) -(a-1) Component- (a-1-1): Poly(2,6-dimethyl-1,4-phenylene ether) with a reduced viscosity of 0.5 dL / g (a-1-2): Poly(2,6-dimethyl-1,4-phenylene ether) with a reduced viscosity of 0.4 dL / g -(a-2) Component- (a-2-1): Polystyrene (manufactured by PS Japan, product name "GPPS 680") (a-2-2): Rubber-modified polystyrene (Petrochemical, product name "CT60") -(a-3) Component- (a-3-1): Aromatic condensed phosphate ester compound (manufactured by Daihachi Chemical Industry Co., Ltd., product name "E890") (a-3-2): Aromatic phosphate ester compound (manufactured by Daihachi Chemical Industry Co., Ltd., product name: "TPP") (a-3-3): Phosphazene compound (Fushimi Pharmaceutical Co., Ltd., trade name: "Ravitor FP-110")

[0102] ·(b) Component Polyarylate resin (manufactured by Unitika, product name "U Polymer")

[0103] ·(c) Component Hydrogenated block copolymer (manufactured by TSRC, product name "TAIPOL6151")

[0104] ·(d) Component Styrene-based glycidyl methacrylate (NOF Corporation, product name "Marproof G-1005S")

[0105] The equipment used in the examples is shown below. Twin-screw extruder: Coperion, product name "ZSK-25WLE" Small injection molding machine: manufactured by Toshiba Machine, "EC75SXII", manufactured by Nissei Jushi Kogyo, product name "PS-40"

[0106] <Evaluation method> The resin compositions obtained in the examples and comparative examples were evaluated by the following methods and conditions.

[0107] (Number average molecular weight of component (a-1)) Pellets of the resin compositions obtained in the examples and comparative examples were measured using gel permeation chromatography (Shimadzu Corporation, LC-2030C Plus). A calibration curve was prepared using standard polystyrene and ethylbenzene, and the number average molecular weight (Mn) was measured using this calibration curve. Standard polystyrenes with molecular weights of 3,650,000, 2,170,000, 1,090,000, 681,000, 204,000, 52,000, 30,200, 13,800, 3,360, 1,300, and 550 were used. Two Showa Denko K-805L columns connected in series were used. Chloroform was used as the solvent, with a solvent flow rate of 1.0 mL / min and a column temperature of 40°C. A 1 g / L chloroform solution was prepared and used as the measurement sample. The UV wavelength of the detection unit was 254 nm when measuring standard polystyrene and 283 nm when measuring component (a-1).

[0108] (Glass transition temperature of component (a)) The resin composition pellets obtained in the examples and comparative examples were measured using a PerkinElmer DSC measuring device. They were heated from 50°C to 300°C at a temperature increase rate of 20°C per minute in a nitrogen atmosphere, then cooled to 50°C at a temperature increase rate of 20°C per minute, and the glass transition temperature was measured at a temperature increase rate of 20°C per minute.

[0109] (molding fluidity) The molding flowability was evaluated by measuring the melt flow rate. The resin composition pellets obtained in the examples and comparative examples were pre-dried at 80°C for 1 hour, and then the melt flow rate (MFR) (g / 10 min) was measured at 250°C and 10 kg in accordance with ISO 1133. The higher the measured value, the better the molding flowability.

[0110] (shock resistance) Impact resistance was evaluated by measuring the Charpy impact strength. The resin compositions obtained in the examples and comparative examples were fed into a screw inline injection molding machine (manufactured by Toshiba Machine, "EC75SXII") set at 220 to 280°C, and injection molded at a mold temperature of 60 to 80°C to produce test specimens having dimensions specified in the ISO-179 standard. Using this test piece, the Charpy impact strength (kJ / m 2 The larger the measured value, the better the impact resistance. 2 If it is equal to or greater than this, it is deemed to have excellent impact resistance.

[0111] (Flame retardant and drip-proof) Based on the UL94-5V test (strip sample), flame retardancy and drip prevention were evaluated using injection-molded test pieces with a thickness of 1.5 to 3.0 mm. The resin composition pellets obtained in the examples and comparative examples were dried for 1 hour at 80° C. The dried pellets were fed into a screw inline injection molding machine (manufactured by Nissei Plastic Industrial Co., Ltd., product name "PS-40") set at 185 to 300° C., and injection molded at a mold temperature of 20 to 40° C. to prepare rectangular samples having the dimensions specified by the standard (length 125 mm × width 13 mm × thickness 1.5 to 3.0 mm). The higher the fluidity and the thinner the strip sample, the easier it is to drip, so the thickness of the strip sample must be adjusted to suit the fluidity. The thickness of the strip sample was set to 2.0 mm for samples with an MFR (g / 10 min) of less than 20 g / 10 min, 2.5 mm for samples with an MFR of 20 g / 10 min or more but less than 35 g / 10 min, and 3.0 mm for samples with an MFR of 35 g / 10 min or more. The flame of a gas burner was applied to the test piece, and the degree of combustion was evaluated. Five strip samples were tested and judged as pass or fail. The summary of pass / fail judgment is as follows. Passed: For all five strip samples, the total burning time and glowing time after the fifth flame contact was 60 seconds or less, and no absorbent cotton was ignited by falling material from the bar sample. Failed: Absorbent cotton ignited due to falling material from the bar sample.

[0112] <Preparation of Resin Composition> (Examples 1 to 10 and Comparative Examples 1 to 8) Components (a) to (d) were fed into a twin-screw extruder in the compositions shown in Table 1 or Table 2, and melt-kneaded at an extrusion temperature of 280 to 320°C, a screw rotation speed of 300 rpm, and a discharge rate of 15 kg / hour to obtain pellets of the resin composition of each Example and Comparative Example. The twin-screw extruder was configured as follows: it had 12 barrel blocks, and in the direction of flow of the raw materials, from upstream, an upstream feed port was installed on the first barrel, a liquid addition pump was installed on the seventh barrel, and vacuum vents were installed on the fifth and eleventh barrels. Of the components (a), (b), (c), and (d), only the component (a-3-1) was supplied from the liquid addition pump, and the others were supplied from an upstream supply port. Tables 1 and 2 show the compositions and evaluation results of the resin compositions prepared in the Examples and Comparative Examples.

[0113] [Table 1]

[0114] [Table 2]

[0115] The resin compositions of Examples 1 to 10 all had excellent flame retardancy, drip prevention during combustion, and fluidity, and it can be seen that the resin composition of this embodiment can be used to mold molded articles that have excellent flame retardancy and drip prevention during combustion. [Industrial Applicability]

[0116] The resin composition of the present invention can be used as a material for electric and electronic parts, home appliances, office automation equipment, etc.

Claims

1. (a) (a-1) one or more compounds selected from a polyphenylene ether resin, (a-2) a styrene resin, and (a-3) a phosphate ester compound and a phosphazene compound, or (a-1) a polyphenylene ether resin and (a-3) one or more compounds selected from a phosphate ester compound and a phosphazene compound, and (b) a polyarylate resin; Including, The number average molecular weight of the component (a-1) is 1.5 × 10 ４ ~2.5 x 10 ４ and The glass transition temperature of the component (a) is 100°C to 145°C, per 100 parts by mass of the component (a-1) or the total of the components (a-1) and (a-2), the amount of the component (a-3) is 5 to 40 parts by mass, The amount of the (b) component is 1 to 12 parts by mass. Resin composition.

2. When the (a) contains the component (a-1) and the component (a-2), In a total of 100 parts by mass of the component (a-1) and the component (a-2), the amount of the component (a-1) is 45 to 85 parts by mass, the amount of the component (a-2) is 15 to 55 parts by mass, The resin composition according to claim 1, wherein the amount of the (a-3) component is 10 to 35 parts by mass relative to a total of 100 parts by mass of the (a-1) component and the (a-2) component.

3. The resin composition according to claim 1 or 2, wherein the component (a-3) is a phosphate ester compound represented by the following general formula (I) or general formula (II): 【Chemistry 1】 【Chemistry 2】 (In general formula (I), Q1, Q2, Q3, and Q4 independently represent an alkyl group having 1 to 6 carbon atoms, R11 and R12 independently represent a methyl group, and R13 and R14 independently represent a hydrogen atom or a methyl group. In general formula (II), Q1, Q2, Q3, and Q4 independently represent an alkyl group having 1 to 6 carbon atoms, and R11 and R12 each represent a methyl group. In general formula (I) and general formula (II), y is an integer of 1 or more, n1 and n2 independently represent an integer of 0 to 2, and m1, m2, m3, and m4 independently represent an integer of 0 to 3.

4. The resin composition according to claim 1 or 2, further comprising (c) an elastomer.

5. The resin composition according to claim 1 or 2, further comprising (d) a compatibilizer.

6. 3. The resin composition according to claim 1, wherein the melt flow rate measured in accordance with ISO 1133 at a temperature of 250°C under a load of 10 kg is 10 g / 10 min or more.

7. The resin composition according to claim 1 or 2, wherein the amount of the component (a) is 70 to 99 parts by mass per 100 parts by mass of the resin composition.

8. The resin composition according to claim 1 or 2, wherein the total amount of the component (a) and the component (b) is 70 to 100 parts by mass per 100 parts by mass of the resin composition.

9. A molded article comprising the resin composition according to claim 1 or 2.

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