JP2011252114A - Reinforced resin composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a filler-containing reinforced resin composition which improves mold contamination in injection molding, excels in balance of heat resistance and flowability, mechanical characteristics and moisture resistance, and excels in flame retardancy.SOLUTION: The resin composition includes: a sum total of 10-90 mass% of (a) a polyphenylene ether resin and (b) a styrenic resin; 1-30 mass% of (c) a phosphorus compound; and 1-60 mass% of (d) a filler, wherein a mass ratio ((a)/(b)) of the component (a) to the component (b) is 10/90-100/0, and the component (c) is a phosphorus compound expressed by a specific formula (I).

Description

  The present invention relates to a reinforced polyphenylene ether resin composition containing a filler excellent in flame retardancy.

  A mixed resin (hereinafter also referred to as “m-PPE resin”) based on a polyphenylene ether (hereinafter also referred to as “PPE”) resin and a styrene resin has a mixing ratio of the PPE resin and the styrene resin. Accordingly, it is a polymer alloy having a unique glass transition point over the entire range from a styrene resin alone to a PPE resin alone. Such m-PPE resin has improved moldability and exhibits predetermined heat resistance. Furthermore, m-PPE resin is excellent in electrical characteristics, dimensional stability, impact resistance, acid resistance, alkali resistance, low water absorption, low specific gravity and the like. Furthermore, m-PPE resin is improved in strength and dimensional characteristics by blending various fillers, and is used in a wide range of applications.

  Moreover, since m-PPE resin can achieve flame retardancy without using harmful halogen compounds or antimony compounds, it is excellent in terms of environment and safety and health. Flame-retardant m-PPE resin is widely used for various electric / electronic parts, office equipment parts, automobile parts, building materials, other various exterior materials and industrial products.

  On the other hand, in order to make the m-PPE resin flame retardant, an organic phosphate is generally used without using a halogen-containing compound. Such organic phosphates include monophosphates such as triphenyl phosphate, cresyl diphenyl phosphate, tricresyl phosphate, phenols such as resorcinol and bisphenol A, and condensed phosphoric acid obtained from a phosphorus trichloride compound. Examples include esters.

  However, the resin compositions flame-retarded with these organic phosphoric acid esters have poor heat resistance, physical properties, moisture absorption characteristics under high temperature and high humidity, smoke generation during injection molding, mold contamination during molding. In addition, problems such as defects in molded products due to adhering substances have been pointed out. Among them, it is said that a resin composition flame-retarded with a condensed phosphate ester obtained from a phenol compound such as bisphenol A and a phosphorus compound has relatively few problems (for example, Patent Document 1, Patent Reference 2 and Patent Document 3).

  In addition, a reinforced resin composition containing a filler is a material having a reduced flame retardancy, particularly a large variation in flame retardancy compared to a resin composition not containing a filler, resulting in inferior flame retardant performance. Therefore, an improvement technique has been proposed (see, for example, Patent Document 4, Patent Document 5, and Patent Document 6).

Japanese Patent Laid-Open No. 55-118957 JP 05-186681 A Japanese Patent Application Laid-Open No. 07-053876 JP-A-61-108658 JP 09-291208 A JP 09-291209 A

  In recent years, in m-PPE resin applications, parts can be made lighter and thinner, with excellent durability under high-temperature use, and excellent moldability (fluidity, releasability, low volatility, etc.) There is a need for materials. In order to obtain such a high heat-resistant material, it is necessary to increase the ratio of PPE resin.

  Thus, in the resin composition having a high ratio of the PPE resin, in order to obtain flame retardancy, when the condensed phosphate esters described in Patent Documents 1 to 3 are blended, (1) heat resistance and machine (2) Mold contamination (molding) during molding under severe injection molding conditions (for example, when molding temperature is high or injection speed is fast) to cope with recent reductions in weight and thickness. There are problems such as deposits, transfer of flame retardants to molds, and defects (appearance, stress cracks, etc.) of molded products due to the deposits.

  Further, in the m-PPE resin, there is a problem that fluidity decreases when a large amount of filler is blended or the ratio of the PPE resin is increased.

  Moreover, in the technique of patent documents 4-6, the moisture absorption characteristic resulting from a flame retardant is not enough. Since the moisture absorption property adversely affects electrical properties, mechanical properties, and heat resistance, development of a resin composition having excellent moisture absorption properties is desired.

  The present invention provides a filler-containing polyphenylene ether resin composition that suppresses mold contamination during injection molding, has an excellent balance between heat resistance and fluidity, and has excellent mechanical properties, moisture absorption properties, and flame retardancy. For the purpose.

  As a result of intensive studies to solve the above-mentioned problems, the present inventor controls the content of each component in the filler-containing m-PPE resin composition and uses a specific phosphorus compound as a flame retardant. Thus, the present inventors have found that the above-mentioned problems can be solved and have completed the present invention.

  That is, the present invention is as follows.

[1]
10 to 90% by mass of the total of (a) polyphenylene ether resin and (b) styrene resin,
(C) 1-30 mass% of phosphorus compound and (d) 1-60 mass% of filler,
The mass ratio ((a) / (b)) between the component (a) and the component (b) is 10/90 to 100/0,
The resin composition whose said component (c) is a phosphorus compound represented by the following general formula (I).

[In the formula (I),
Each A independently represents an alkyl group having 1 to 8 carbon atoms, an aryl group having 6 to 10 carbon atoms, or an aralkyl group having 7 to 12 carbon atoms;
R ¹ , R ² , R ³ and R ⁴ are each independently an alkyl group having 1 to 8 carbon atoms, a cycloalkyl group having 5 to 6 carbon atoms, an aryl group having 6 to 20 carbon atoms, or carbon. Represents an aralkyl group having 7 to 12 atoms,
x and y are each independently 0, 1, 2, 3 or 4;
n is each independently 0 or 1,
N is 1-30. ]
[2]
The resin composition according to [1], wherein a mass ratio ((a) / (b)) between the component (a) and the component (b) is 20/80 to 99/1.

[3]
The resin composition according to [1] or [2], wherein the acid value of the component (c) is 0.5 or less.

[4]
The resin composition according to any one of [1] to [3], wherein the component (c) is a phosphorus compound represented by the formula (II).

[In formula (II), N is 1-10. ]
[5]
The resin composition according to any one of [1] to [4], wherein the component (d) contains a plate-like filler.

[6]
The resin composition according to any one of [1] to [5], wherein the component (d) contains a plate-like filler in an amount of 50% by mass or more based on the total amount of the component (d).

[7]
The resin composition according to any one of [1] to [6], wherein the component (d) contains one or more selected from the group consisting of glass flakes, mica, chlorite, and talc.

  According to the present invention, a novel resin composition that suppresses mold contamination during injection molding, has an excellent balance of flame retardancy, heat resistance and fluidity, and is excellent in mechanical properties, moisture absorption properties, and flame retardancy. Can be provided.

  Hereinafter, a mode for carrying out the present invention (hereinafter referred to as “the present embodiment”) will be specifically described. In addition, this invention is not restrict | limited to the following embodiment, A various deformation | transformation can be implemented within the range of the summary.

≪Resin composition≫
The resin composition according to the present embodiment includes (a) a polyphenylene ether resin and (b) a styrene resin in a total amount of 10 to 90% by mass, (c) a phosphorus compound in an amount of 1 to 30% by mass, and (d) a filler. 1 to 60% by mass, the mass ratio ((a) / (b)) of the component (a) to the component (b) is 10/90 to 100/0, and the component (c ) Is a phosphorus compound represented by the specific formula (I).

  Hereinafter, each component of the resin composition will be described in detail.

1. Raw material [(a) Polyphenylene ether resin]
(A) Polyphenylene ether resin (hereinafter also referred to as “(a) PPE resin” or “component (a)”). ) Is preferably a polymer in which structural units represented by the following formulas (III) and / or (IV) are repeated. (A) The PPE resin may be a homopolymer (homopolymer) or a copolymer (copolymer).

  In the above formulas (III) and (IV), R1, R2, R3, R4, R5 and R6 are each independently hydrogen, halogen, an alkyl group having 1 to 4 carbon atoms or 6 to 12 carbon atoms. An aryl group.

  Examples of the homopolymer of PPE resin include, but are not limited to, poly (2,6-dimethyl-1,4-phenylene) ether and poly (2-methyl-6-ethyl-1,4-phenylene) ether. Poly (2,6-diethyl-1,4-phenylene) ether, poly (2-ethyl-6-n-propyl-1,4-phenylene) ether poly (2,6-di-n-propyl-1, 4-phenylene) ether, poly (2-methyl-6-n-butyl-1,4-phenylene) ether, poly (2-ethyl-6-isopropyl-1,4-phenylene) ether, poly (2-methyl- 6-chloroethyl-1,4-phenylene) ether, poly (2-methyl-6-hydroxyethyl-1,4-phenylene) ether, and poly (2-methyl-6-chloroethyl-1) 4-phenylene) ether. From the viewpoint of availability and cost, poly (2,6-dimethyl-1,4-phenylene) ether is preferable.

  In this homopolymer, some structural units in the repeating unit structure are 2- (dialkylaminomethyl) -6-methylphenylene ether structural unit and / or 2- (N-alkyl-N-phenylamino). Those having a structure substituted with a methyl) -6-methylphenylene ether structural unit are also included.

  Most preferably, some structural units of poly (2,6-dimethyl-1,4-phenylene) ether are 2- (dialkylaminomethyl) -6-methyl from the viewpoint of ease of molecular weight adjustment during processing. It is a copolymer substituted with a phenylene ether structural unit and / or 2- (N-alkyl-N-phenylaminomethyl) -6-methylphenylene ether structural unit.

  On the other hand, the copolymer of PPE resin is a copolymer having a phenylene ether structure as a main structural unit, and the copolymer is not limited to the following, but for example, the above-described formula (III) and / or What consists of a structural unit represented by (IV) is mentioned.

  Specific examples of the copolymer include, but are not limited to, a copolymer of 2,6-dimethylphenol and 2,3,6-trimethylphenol, and a copolymer of 2,6-dimethylphenol and o-cresol. And a (ternary) copolymer of 2,6-dimethylphenol, 2,3,6-trimethylphenol and o-cresol.

  From a practical viewpoint, the reduced viscosity (ηsp / c) of (a) PPE resin is preferably 0.3 to 0.7, more preferably 0.4 to 0.6. In the present embodiment, the “practical viewpoint” means judgment in actual use of the resin composition (compound product). The judgment criteria are molding processability, mechanical properties, chemical resistance, flame retardancy, and the like. The reduced viscosity (ηsp / c) is a value measured with a chloroform solution having a concentration of 0.5 g / dl at 30 ° C. using an Ubbelohde viscosity tube.

  Moreover, (a) The ratio of [weight average molecular weight / number average molecular weight] of the PPE resin is preferably 1.8 to 5.0, more preferably 2.2 to 3.5. In addition, the weight average molecular weight and number average molecular weight in this specification are values calculated on the basis of the molecular weight in terms of polystyrene measured by gel permeation chromatography (GPC).

  (A) The PPE resin is preferably a polyphenylene ether having the above physical properties and characteristics from the viewpoint of molding fluidity. Among these, poly (2,6-dimethyl-1,4-phenylene) ether having the above physical properties and characteristics is particularly preferable.

  Furthermore, in the present embodiment, (a) a modified polyphenylene ether obtained by modifying a part or all of a polyphenylene ether with an unsaturated carboxylic acid or a derivative thereof can be used as the PPE resin.

  Such modified polyphenylene ethers are described in JP-A-2-276823, JP-A-63-108059, JP-A-59-59724, etc., for example, in the presence or absence of a radical initiator. Under the condition, an unsaturated carboxylic acid or a derivative thereof is melt-kneaded with polyphenylene ether, and these are reacted. The modified polyphenylene ether can also be obtained by dissolving polyphenylene ether and an unsaturated carboxylic acid or a derivative thereof in an organic solvent in the presence or absence of a radical initiator and reacting in such a solution. A polyphenylene ether modified with an unsaturated carboxylic acid or a derivative thereof is preferable because it has good adhesion to an unmodified polyphenylene ether with an inorganic filler.

  Said (a) PPE-type resin may be used individually by 1 type, and may be used in combination of 2 or more type.

[(B) Styrenic resin]
(B) The styrene resin (hereinafter also referred to as “component (b)”) is preferably a homopolymer of a styrene compound or a copolymer of a compound copolymerizable with a styrene compound. Moreover, the polymer obtained by superposing | polymerizing these 1 or more types of styrene-type compounds in rubber polymer presence may be sufficient.

  Examples of the styrene compound include, but are not limited to, styrene, α-methylstyrene, 2,4-dimethylstyrene, monochlorostyrene, p-methylstyrene, p-tert-butylstyrene, and ethylstyrene. Of these, styrene is preferred.

  Moreover, as a compound copolymerizable with said styrenic compound, although it does not restrict | limit, For example, Methacrylic acid esters, such as methyl methacrylate, ethyl methacrylate, butyl methacrylate; Unsaturated nitrile compounds, such as acrylonitrile and methacrylonitrile And maleic acid derivatives such as maleic anhydride and phenylmaleimide. These compounds are used together with the above-mentioned styrenic compound as described above. The amount of the compound copolymerizable with the styrenic compound is preferably 20% by mass or less, more preferably 15% by mass or less, based on the total amount with the styrenic compound.

  Examples of the rubbery polymer include, but are not limited to, conjugated diene rubbers, copolymers of conjugated dienes and aromatic vinyl compounds, and ethylene-propylene copolymer rubbers. Specific examples of the rubbery polymer include, but are not limited to, polybutadiene, styrene-butadiene random copolymer, and styrene-butadiene block copolymer, and rubber components obtained by partially or almost completely hydrogenating them. Can be mentioned.

  Specific examples of (b) styrene resins available on the market include (homo) polystyrene (atactic polystyrene), syndiotactic polystyrene, high impact polystyrene (rubber-modified polystyrene), styrene-acrylonitrile copolymer, ABS resin, and the like. Rubber modified styrene-acrylonitrile copolymer, styrene- (meth) acrylate copolymer, styrene-maleic anhydride copolymer, styrene-maleimide copolymer, and the like.

  Preferred (b) styrenic resin is polystyrene and / or rubber-modified polystyrene. Moreover, it is preferable that a styrene-acrylonitrile copolymer contains 7-15 mass% of acrylonitrile. By setting the content of such a styrene-acrylonitrile copolymer to a maximum of 80% by mass, preferably 20 to 70% by mass with respect to 100% by mass of the total styrene-based resin (b), further molding flow is achieved. Resin composition excellent in balance between heat resistance and heat resistance can be obtained.

The component (b) described above may be used alone or in combination of two or more.
[(C) Phosphorus compound]
(C) The phosphorus compound (hereinafter also referred to as “component (c)”) is a phosphorus compound represented by the following general formula (I).

In the formula (I), each A independently represents an alkyl group having 1 to 8 carbon atoms, an aryl group having 6 to 10 carbon atoms, or an aralkyl group having 7 to 12 carbon atoms, and R ¹ , R ² , R ³ and R ⁴ are each independently an alkyl group having 1 to 8 carbon atoms, a cycloalkyl group having 5 to 6 carbon atoms, an aryl group having 6 to 20 carbon atoms, or the number of carbon atoms. 7 to 12 aralkyl groups, x and y are each independently 0, 1, 2, 3 or 4, n is each independently 0 or 1, and N is 1 to 30 is there.

In the formula (I), each A is preferably independently a methyl group or a phenyl group, and more preferably a methyl group. R ¹ , R ² , R ³ and R ⁴ are preferably each independently an aryl group having 6 to 20 carbon atoms, more preferably a phenyl group, a xylenyl group or a cresyl group. x and y are each independently preferably 0 or 1, and more preferably 0. n is preferably 1. N is preferably 1 to 20, more preferably 1 to 10, and particularly preferably 1 to 5.

  The phosphorus compound represented by the general formula (I) is generally a mixture of N different phosphorus compounds. In this case, N is expressed as an average value, and the average value may be within the above range. Therefore, it is not excluded that phosphorus compounds having N outside the above range are included as impurities. When N = 0, it represents a monophosphorus compound and is generally contained as an impurity.

The component (c) is preferably a phosphorus compound represented by the following formula (II) or the following formula (II) ′.

  In said formula (II) or said formula (II) ', N is 1-30, it is preferable that it is 1-10, and it is especially preferable that it is 1-5.

  The phosphorus compound represented by the general formula (II) or the formula (II) 'is generally a mixture of N different phosphorus compounds. In this case, N is expressed as an average value, and the average value may be within the above range. Therefore, it is not excluded that phosphorus compounds having N outside the above range are included as impurities. When N = 0, it represents a monophosphorus compound and is generally contained as an impurity.

  These phosphorus compounds can be produced by the methods described in Patent Publications WO2003-089442A1 and JP2008-202009. Moreover, it is generally marketed, for example, FP800 of ADEKA Corporation is known.

  The component (c) described above may be used alone or in combination of two or more.

  The acid value of the component (c) is preferably 0.5 or less, more preferably 0.1 or less, and particularly preferably 0.05 or less. When the acid value of the component (c) is within the above range, there is little mold contamination in the resin composition and characteristics such as moisture resistance tend to be good. The acid value is a value obtained according to JIS K2501.

  The crude product of component (c) usually has a high acid value due to the influence of impurities. The acid value of the component (c) can be lowered by dissolving the component (c) in toluene and washing with an aqueous solution containing an acid or a base. The acid value can be controlled by the degree of washing.

  In the resin composition according to the present embodiment, the component (c) described above acts as a flame retardant. A known flame retardant may be used together with the component (c) as such a flame retardant. Examples of the known flame retardant include phosphate ester compounds other than the above component (c), phosphazene compounds, phosphinic acid metal salt compounds, polyphosphates, red phosphorus, and the like. One or more known flame retardants selected from these can be used in combination with the above-described component (c) in the range of 50% by mass or less of the total amount of the flame retardants.

  Specific examples of the phosphoric acid ester compound other than the component (c) that can be used in combination include triphenyl phosphate, trisnonylphenyl phosphate, resorcinol bis (diphenyl phosphate), resorcinol bis [di (2,6-dimethylphenyl). ) Phosphate], 2,2-bis {4- [bis (phenoxy) phosphoryloxy] phenyl} propane, 2,2-bis {4- [bis (methylphenoxy) phosphoryloxy] phenyl} propane, and the like. It is not limited to these. In addition to the above, phosphorus flame retardants include, for example, trimethyl phosphate, triethyl phosphate, tributyl phosphate, trioctyl phosphate, tributoxyethyl phosphate, tricresyl phosphate, cresyl phenyl phosphate, octyl diphenyl phosphate, diisopropyl phenyl phosphate. Phosphate ester flame retardant such as diphenyl-4-hydroxy-2,3,5,6-tetrabromobenzyl phosphonate, dimethyl-4-hydroxy-3,5-dibromobenzyl phosphonate, diphenyl- 4-hydroxy-3,5-dibromobenzyl phosphate, tris (chloroethyl) phosphate, tris (dichloropropyl) phosphate, tris (chloropropyl) phosphate, bis ( , 3-dibromopropyl) -2,3-dichloropropyl phosphate, tris (2,3-dibromopropyl) phosphate, and bis (chloropropyl) monooctyl phosphate hydroquinonyl diphenyl phosphate, phenylnonylphenyl hydroquinonyl phosphate, phenyl Monophosphate compounds such as dinonylphenyl phosphate, and bisphenol A bis (diphenyl phosphate), bisphenol A bis (dicresyl phosphate), resorcin bis (diphenyl phosphate), resorcin bis (dixylenyl phosphate), etc. Aromatic condensed phosphate ester compounds and the like can be mentioned.

  Among these, aromatic condensed phosphoric ester compounds are preferably used because they generate less gas during molding and are excellent in thermal stability. These aromatic condensed phosphate ester compounds are generally commercially available, and for example, CR741, CR733S, PX200 from Daihachi Chemical Industry Co., Ltd. are known. Particularly preferred is an aromatic condensed phosphate ester compound having an acid value of 0.1 or less (value obtained according to JIS K2501).

  As the phosphazene compound, phenoxyphosphazene and a cross-linked product thereof are preferable, and a phenoxyphosphazene compound having an acid value of 0.1 or less (a value obtained in accordance with JIS K2501) is particularly preferable.

  Examples of phosphinic acid metal salt compounds include phosphinic acid salts, diphosphinic acid salts and condensates thereof, such as calcium dimethylphosphinate, aluminum dimethylphosphinate, zinc dimethylphosphinate, calcium ethylmethylphosphinate, ethylmethylphosphinic acid. Aluminum, zinc ethylmethylphosphinate, calcium diethylphosphinate, aluminum diethylphosphinate, and zinc diethylphosphinate are preferred.

  The resin composition according to the present embodiment may contain polytetrafluoroethylene, a phenol resin, a silicone resin, a cyclic nitrogen compound such as melon or melem as a flame retardant aid. The content of the flame retardant aid is preferably in the range of 0.01 to 10 parts by mass, more preferably 0.02 to 5 parts by mass with respect to 100 parts by mass in total of the component (a) and the component (b). It is.

  The polytetrafluoroethylene has a molecular weight of 100,000 or more, preferably about 200,000 to 3,000,000. For this reason, the dripping at the time of combustion is suppressed in the resin composition containing polytetrafluoroethylene. Furthermore, when polytetrafluoroethylene and a silicone resin are used in combination, drip can be further suppressed and the combustion time can be shortened as compared with the case of polytetrafluoroethylene alone.

  Various conventionally known flame retardants and flame retardant aids, for example, hydroxides such as magnesium hydroxide and aluminum hydroxide, zinc borate compounds, zinc stannate compounds, and inorganics such as silica and silica alumina It is possible to further improve flame retardancy by adding a silicon compound or the like.

[(D) Filler]
Specific examples of the filler (d) (hereinafter also referred to as “component (d)”) used in the present embodiment include glass fiber, glass flake, glass bead, carbon fiber, potassium titanate fiber, talc, mica, black Examples include natural minerals and artificial fillers such as light, wollastonite, kaolinite, calcined clay, calcium carbonate, heavy calcium carbonate, and shirasu balloon. These components (d) may be used individually by 1 type, and may be used together 2 or more types.

  In addition, the shape of the filler (d) may be any of a fiber shape, a plate shape (including a scale shape and a layer shape), a needle shape, and a spherical shape.

  The component (d) preferably contains a plate-like filler. Further, the component (d) is preferably 10% by mass or more, more preferably 20% by mass or more, and further preferably 30% by mass or more, in particular, with respect to the total amount of the component (d). Preferably it contains 50 mass% or more.

  In the present embodiment, by including at least one plate-like filler as the filler (d), a significant advantage can be obtained in terms of dimensional characteristics over conventional resin compositions. (D) As the filler, mica is preferably used from the balance between strength and dimensionality, and chlorite is preferably used in terms of flame retardancy.

  The glass fiber preferably has an average diameter of 20 μm or less, and more preferably 5 to 15 μm from the viewpoint of a balance between mechanical properties and dimensional properties. The fiber length of the glass fiber is not specified, and uncut glass roving can also be used as a so-called long fiber glass fiber, but a chopped strand of about 3 to 15 mm is generally commercially available and is easy to handle. Is also preferable. In this case, the number of focusing is preferably 100 to 5000. The composition of the raw glass is preferably non-alkali, and E glass is one example. If the average diameter of the glass fibers exceeds 20 μm, the degree of improvement in mechanical strength tends to be small and the amount of molding warp tends to be large. From the viewpoint of dimensional characteristics, glass fibers having a fiber length of about 0.1 to 0.5 mm, which are commercially available as cut fibers, and powdered glass fibers having a fiber length of 0.1 mm or less, which are commercially available as milled fibers, are used. It is done. When placing importance on the strength of the resin composition, long fibers and chopped strands of glass roving are preferably used, and when placing importance on the appearance and dimensional anisotropy, cut fibers and milled fibers are preferably used. These various glass fibers are available from many glass manufacturers. As the type of glass, E glass is generally used, but C glass and ECR glass can also be used.

  Although glass fiber can be used as it is, it is generally preferable to use it after treating with a surface treatment agent for improving the adhesion to the resin and a sizing agent for improving the handleability. The sizing agent is usually composed of a film forming agent, a surfactant, a softening agent, an antistatic agent, a lubricant and the like. Various coupling agents as surface treatment agents can also be used for the purpose of enhancing the affinity between the resin component and the glass fiber or the interfacial bonding force (adhesion). The coupling agent usually includes a coupling agent such as silane, chrome, and titanium. Among these, those containing a silane coupling agent such as epoxy silane such as γ-glycidoxypropyltrimethoxysilane; vinyltrichlorosilane; aminosilane such as γ-aminopropyltriethoxysilane are preferable. In this case, the treatment with various surfactants such as nonionic, cationic and anionic types and dispersants such as fatty acids, metal soaps and various resins may be performed in terms of improving mechanical strength and kneadability. preferable.

  As the carbon fiber, Toray (registered trademark) cut fiber or milled fiber manufactured by Toray Industries, Inc., Pyrofil (registered trademark) chopped fiber manufactured by Mitsubishi Rayon Co., Ltd., or the like can be used.

  As the potassium titanate fiber, Tismo (registered trademark) manufactured by Otsuka Chemical Co., Ltd. can be used as a commercial product.

  The resin composition according to the present embodiment preferably contains a plate-like or scale-like inorganic filler as the component (d) when the dimensional anisotropy of the molded product is particularly important. The plate-like or scale-like inorganic filler is preferably at least one selected from the group consisting of glass flakes, mica, chlorite and talc.

  The glass flakes used in the present embodiment are not particularly limited as long as they are plate-shaped. Known methods for producing plate-like glass flakes include a balloon method for crushing a balloon made of molten glass and a span method using ultracentrifugal force. Generally, those having a weight average diameter by sieving of 0.05 mm to 2 mm and a thickness of 1 to 10 μm are used, the major axis in the resin composition is 1000 μm or less, preferably 1 to 500 μm, and the weight average aspect ratio ( The ratio of the weight average major axis to the weight average thickness is 5 or more, preferably 10 or more, more preferably 30 or more. When a glass flake is mixed with other components to prepare a resin composition, the glass flake is broken and its size is reduced. The measurement of the major axis and thickness of the glass flakes in the resin composition can be performed by dissolving the resin, filtering out the glass flakes, and observing with an optical microscope or a scanning electron microscope.

  When the glass flake exceeds 2 mm in major axis, uniform mixing with the resin becomes difficult when blended into the resin, and the physical properties of the molded product may be uneven. On the other hand, when the aspect ratio is less than 5, the heat distortion temperature of the molded product is insufficiently improved, and the Izod impact strength and rigidity tend to decrease. The glass flakes are preferably treated with a surface treatment agent and a sizing agent in the same manner as the glass fibers described above. For the purpose of improving the affinity with the resin, for example, silane-based (for example, aminosilane-based), titanate-based, etc. Glass flakes surface-treated with various coupling agents can also be used.

  Examples of commercially available glass flakes include micro glass flakes (trademark of glass flakes) manufactured by Nippon Sheet Glass and glass flakes manufactured by GLASS FLAKE Limited (UK). Although commercially available glass flakes can be used as they are, they may be used after appropriately pulverized before blending with the resin.

The mica used in the present embodiment is a scale-like aluminum silicate-based mineral such as KAl ₂ (AlSi ₃ O ₁₀ ) (OH) ₂ (white mica), K (Mg, Fe) ₃ (AlSi ₃ O ₁₀ ). (OH) ₂ (black mica), KMg ₃ (AlSi ₃ O ₁₀ ) (OH) ₂ (gold mica), KLi ₂ Al (Si ₄ O ₁₀ ) (OH) ₂ (scale mica), NaAl ₂ (AlSi ₃ O ₁₀ ) (OH) ₂ (soda mica), KMg ₃ (AlSi ₃ O ₁₀ ) F ₂ (fluorine gold mica), and various mica. These mica have cleavage properties. In the present embodiment, any mica can be used regardless of the above type. From the viewpoint of the balance between the rigidity and dimensional characteristics of the resin composition, the average particle diameter of mica is preferably 3 to 200 μm (sieving method), more preferably 5 to 150 μm, and particularly preferably 10 to 100 μm. When the average particle size is 3 μm or more, the reinforcing effect and the dimensional property are remarkable, and when the average particle size is 200 μm or less, the decrease in the weld strength and the deterioration of the surface appearance are small.

  The talc used in this embodiment is generally composed of magnesium silicate as a main component and containing impurities such as calcium, iron, sodium, potassium, etc. as impurities.

The talc used in the present embodiment is preferably a pulverized and classified natural talc, and is preferably a scale-like or tabular mineral. The talc preferably has a chemical composition represented by 4SiO ₂ .3MgO.H ₂ O as hydrous magnesium silicate. The hydrous magnesium silicate usually comprises 55 to 63% by mass of SiO ₂ , 25 to 33% by mass of MgO, and about 5% by mass of loss on ignition (H ₂ O), although it varies depending on the production area. As other minor components, it contains 0.1 to 5% by mass of Fe ₂ O ₃ , 0.1 to 3% by mass of Al ₂ O ₃ , 0.1 to 5% by mass of CaO, and the like.

  The average particle diameter of the talc is not particularly limited, but is usually preferably 0.5 μm to 20 μm (sieving method), more preferably 1 μm to 15 μm, and particularly preferably 1.5 μm to 10 μm. When the average particle size of the talc is 0.5 μm or more, the effect on the reinforcing effect and dimensionality is remarkable, and when the average particle size of the talc is 20 μm or less, the weld strength of the molded product is reduced. The deterioration of the surface appearance tends to be small.

  The chlorite used in the present embodiment is preferably a chlorite group natural ore.

  Chlorite group ore (B) is selected from each group of oxides composed of Mg, Fe, Mn, Ni, etc., oxides composed of Al, Fe, Cr, Ti, etc., oxides composed of Si, Al, etc. The ore containing a predetermined one, and the crystal structure includes a monoclinic system and an orthorhombic system.

  The average particle size of the chlorite group ore is not particularly limited, but is usually preferably 0.5 μm to 30 μm (sieving method), more preferably 1 μm to 20 μm, and particularly preferably 3 μm to 15 μm. When the average particle size of the chlorite group ore is 0.5 μm or more, the effect on the reinforcing effect and dimensionality is remarkable, and when the average particle size of the chlorite group ore is 30 μm or less, a molded product There is a tendency that a decrease in weld strength and a deterioration in surface appearance are reduced.

  In the resin composition according to the present embodiment, it is considered that the inclusion of chlorite group ore not only improves the mechanical properties and dimensional characteristics but also exhibits a flame retardant effect.

  Chlorite group minerals include chlorite, cookite, and nanthite. These may be used alone or in combination of two or more. In particular, chlorite is preferable from the viewpoint of availability. Chlorite products are sold by Fuji Talc Kogyo Co., Ltd. and Sakai Kogyo Co., Ltd.

The wollastonite used in the present embodiment is preferably CaO.SiO ₂ and is a naturally occurring white needle-like crystalline mineral, and may be synthesized. The wollastonite has a shape ranging from a fiber to a lump, and a fiber is preferably used. Further, since wollastonite having a large fiber diameter is easily broken during melt-kneading, it is preferable to use wollastonite containing a component having a fiber diameter of 5 μm or less in an amount of 80% by mass or more, preferably 95% by mass or more. The initial average fiber diameter of wollastonite is preferably 2 to 30 μm, more preferably 3 to 20 μm, and particularly preferably 4 to 15 μm. If the average fiber diameter is less than 2 μm, it tends to break during processing, and if it exceeds 30 μm, the reinforcing effect is small. The initial average fiber length of wollastonite is preferably 20 to 400 μm, more preferably 25 to 300 μm, and particularly preferably 30 to 250 μm. If the average fiber length is less than 20 μm, the reinforcing effect is small, and if it exceeds 400 μm, it tends to break during processing. Furthermore, the value obtained by dividing the initial average fiber length by the initial average fiber diameter (= initial average aspect ratio) is preferably 4 to 50, more preferably 5 to 40, and particularly preferably 6 to 30. is there. If the average aspect ratio is less than 4, the reinforcing effect is small, and if it exceeds 50, it tends to break during processing.

  In the reinforced resin composition excellent in flame retardancy of the present embodiment, particularly when a plate-like filler (including scale-like or layered filler) is used, an aromatic condensation of a conventionally used flame retardant is preferred. When combined with a phosphoric ester compound, smoke suppression and mold contamination during injection molding are improved, and the balance between heat resistance and fluidity, impact resistance, flame retardancy, and moisture absorption properties tend to be excellent. The resin composition having the above characteristics is extremely useful for various thin parts, precision parts and the like that require strict dimensional characteristics.

[Ratio of each component]
The resin composition according to the present embodiment includes (a) a polyphenylene ether resin and (b) a styrene resin in a total amount of 10 to 90% by mass, (c) a phosphorus compound in an amount of 1 to 30% by mass, and (d) a filler. 1 to 60% by mass, and the mass ratio ((a) / (b)) between the component (a) and the component (b) is 10/90 to 100/0.

  In the resin composition according to the present embodiment, the ratio of each component varies depending on the application used, and a desired composition is selected within the above range depending on the required level of heat resistance, mechanical properties, dimensionality, flame retardancy, and the like. .

  In the resin composition according to the present embodiment, the total content of (a) PPE resin and (b) styrene resin is a required characteristic depending on the ratio of (a) PPE resin and (b) styrene resin. Although it is arbitrarily selected according to this, it is usually 10 to 90% by mass, preferably 20 to 80% by mass, and more preferably 30 to 70% by mass. Here, the mass ratio ((a) / (b)) of (a) PPE resin and (b) styrene resin is 10/90 to 100/0, preferably 15/85 to 95/5. Preferably it is the range of 20 / 80-90 / 10, and can select a desired ratio from a viewpoint of heat resistance and a flame retardance. For the recent demand for high heat-resistant materials, the mass ratio ((a) / (b)) of (a) PPE resin and (b) styrene resin is preferably 40/60 to 99/1, More preferably, it is the range of 50 / 50-95 / 5. In the resin composition according to the present embodiment, in such a composition range in which the proportion of the PPE resin is high (that is, in a composition range that requires high-temperature molding), mold contamination (MD or the like) is particularly inferior to conventional materials. ) And the water absorption properties are excellent.

  In the resin composition according to this embodiment, the content of the (c) phosphorus compound is 1 to 30% by mass, more preferably 3 to 25% by mass, and more preferably 5 to 20% by mass. (C) The content of the phosphorus compound is appropriately determined in consideration of the blending ratio of the PPE resin in consideration of the heat resistance depending on the required flame retardant level, but is difficult at 1% by mass or more. A flame effect is exhibited, and the flame retardancy effect is sufficiently exhibited at 30% by mass or less, and heat resistance and mechanical properties can be maintained.

  In the resin composition according to this embodiment, the content of (d) the filler is 1 to 60% by mass, preferably 3 to 55% by mass, and more preferably 5 to 50% by mass. (D) The content of the filler is appropriately determined together with the type of the filler in consideration of dimensionality and mechanical properties, but the strength effect is exhibited at 1% by mass or more, and the dimensionality is sufficient at 60% by mass or less. And mechanical properties and heat resistance are improved.

[Other additives]
The resin composition according to the present embodiment is further described as (e) a specific hydrogenated block copolymer (hereinafter referred to as “component (e)”) for the purpose of further improving impact resistance, releasability and chemical resistance. .) And / or (f) polyolefin resin (hereinafter also referred to as “component (f)”) is preferably added.

  The (e) hydrogenated block copolymer used in the present embodiment is a copolymer obtained by hydrogenating a block copolymer of styrene and a diene compound. A preferred (e) hydrogenated block copolymer has a styrene polymer block chain having a number average molecular weight of 15000 or more, and the block copolymer of styrene and a diene compound is hydrogenated to unsaturate the diene compound polymer block chain. The degree is reduced to 20% or less.

A hydrogenated block copolymer of styrene and a diene compound can be produced by a generally known method, and a styrene polymer block chain (hereinafter also referred to as “A”) and a diene compound polymer block chain (hereinafter referred to as “B”). The block copolymer is formed by hydrogenation of a block copolymer comprising: A-B-A, A-B-A-B, (A-B-) ₄ -Si, A-B It is a hydrogenated product of a styrene-diene compound block copolymer having a bond structure such as -A-B-A. The microstructure of the diene compound polymer block can be arbitrarily selected, but in general, the 1,2-vinyl bond is desirably in the range of 2 to 60%, preferably 8 to 40%. These hydrogenated copolymers are commercially available, and examples thereof include Tough Tech from Asahi Kasei Chemicals Corporation, Septon from Kuraray Co., Ltd., and Kraton from Kraton Polymer Co., Ltd.

Other hydrogenated block copolymers of styrene and diene compounds include random hydrogenated block copolymers containing a hydrogenated block of a random copolymer block of styrene and diene compound (hereinafter also referred to as “C”). Polymers can also be used. Examples of the structure include A-C, A-C-A, A-C-A-C, (A-C-) ₄ -Si, A-B-C, A-B-C-A, C- Examples thereof include hydrogenated products of styrene-diene compound block copolymers having various bond structures such as AC. This random hydrogenated copolymer is commercially available, and examples thereof include SOE (registered trademark) manufactured by Asahi Kasei Chemicals Corporation.

  In the present embodiment, the styrene polymer block chain requires at least one block chain having a number average molecular weight of 15,000 or more, more preferably 20,000 or more, and even more preferably the number average of all styrene polymer block chains. The molecular weight is desirably 15,000 or more. If the hydrogenated block copolymer used in the present embodiment has a number average molecular weight of 15,000 or more of the styrene polymer block chain, the ratio of the styrene polymer block to the diene compound polymer block is not so problematic. However, the preferable content range of the styrene polymer block component is 30 to 80% by mass, and more preferably 40 to 70% by mass. When the number average molecular weight of the styrene polymer block chain is 15,000 or more, the combined use effect with the polyolefin resin is achieved, and the impact resistance tends to be excellent while improving the releasability.

  (F) Polyolefin resin used in the present embodiment is low density polyethylene, high density polyethylene, linear low density polyethylene, polypropylene, ethylene-propylene copolymer, ethylene-butene copolymer, ethylene-octene copolymer, etc. Is mentioned. Particularly preferred (f) polyolefin-based resins are low density polyethylene and ethylene-propylene copolymer.

  (F) The polyolefin resin may be added alone without adding the (e) hydrogenated block copolymer if the purpose is to improve the releasability, in which case (a) , (B), (c) and (d) are used in an amount of 1 part by mass or less with respect to 100 parts by mass in total.

  The preferable form of the resin composition according to this embodiment is achieved by using (e) a specific hydrogenated block copolymer and (f) a polyolefin-based resin in a specific amount and a specific ratio.

  In the resin composition according to this embodiment, (e) a hydrogenated block copolymer of styrene and a diene compound in which the number average molecular weight of the styrene polymer block chain is 15000 or more, and (f) addition of a polyolefin-based resin The amount is preferably 0.1 to 7 parts by mass, more preferably 0.3 to 5 parts by mass, respectively, with respect to 100 parts by mass in total of the components (a), (b), (c) and (d). Particularly preferably, it is in the range of 0.5 to 3 parts by mass, and the total amount of the component (e) and the component (f) is 10 parts by mass or less, preferably 7 parts by mass or less, more preferably 5 parts by mass or less. It is. The total amount of the component (e) and the component (f) is preferably 5 parts by mass or less, particularly 3 parts by mass or less, from the viewpoint of the rigidity of the resin composition, for example, tensile strength, bending strength, bending elastic modulus and the like.

  The mass ratio ((e) / (f)) of (e) hydrogenated block copolymer and (f) polyolefin resin is preferably in the range of 90/10 to 10/90, more preferably 60. / 40 to 15/85, more preferably 55/45 to 25/75, and particularly preferably 50/50 to 30/70. When the mass ratio ((e) / (f)) between the component (e) and the component (f) is within the above range, the effect of improving the impact resistance can be expected significantly.

  If necessary, stabilizers such as antioxidants (also referred to as heat stabilizers), ultraviolet absorbers, light stabilizers, and the like are added to the resin composition according to the present embodiment, so that the heat stability of the resin composition is improved. And light resistance can be improved.

  Specific examples of the antioxidant include 2,6-di-t-butyl-4-methylphenol and n-octadecyl-3- (4′-hydroxy-3 ′, 5′-di-t-butylphenyl) propionate. 2,2′-methylenebis (4-methyl-6-tert-butylphenol), 2,2′-methylenebis (4-ethyl-6-tert-butylphenol), 2,4-bis [(octylthio) methyl] -0 -Cresol, 2-t-butyl-6- (3-t-butyl-2-hydroxy-5-methylbenzyl) -4-methylphenyl acrylate, 2,4-di-t-amyl-6- [1- Hints such as (3,5-di-t-amyl-2-hydroxyphenyl) ethyl] phenyl acrylate, 2- [1- (2-hydroxy-3,5-di-tert-pentylphenyl)] acrylate Phenolic antioxidants; sulfur-based antioxidants such as dilauryl thiodipropionate, lauryl stearyl thiodipropionate pentaerythritol-tetrakis (β-lauryl thiopropionate); tris (nonylphenyl) phosphite, tris ( Phosphorous antioxidants such as 2,4-di-t-butylphenyl) phosphite can be mentioned, and two or more types are often used in combination.

  In the modified PPE, metal compounds such as zinc oxide, zinc sulfide, magnesium oxide, and calcium oxide may be used as a heat stabilizer.

  Specific examples of ultraviolet absorbers and light stabilizers include 2- (2′-hydroxy-5′-methylphenyl) benzotriazole, 2- (2′-hydroxy-3 ′, 5′-t-butylphenyl) benzo Benzotriazole ultraviolet absorbers such as triazole, 2- (2′-hydroxy-3 ′, 5′-di-t-butylphenyl) -5-chlorobenzotriazole, and benzophenones such as 2-hydroxy-4-methoxybenzophenone An ultraviolet absorber, a hindered amine light stabilizer, etc. can be mentioned, and an ultraviolet absorber and a light stabilizer are often used together.

  The blending ratio of the various stabilizers is not particularly limited, but is generally 0.01 to 5 parts by mass with respect to a total of 100 parts by mass of (a) PPE resin and (b) styrene resin. More preferably, it is the range of 0.02-3 mass parts.

  In addition to the filler (d), various other fillers can be blended in the resin composition according to the present embodiment. Specific examples of other fillers include basic magnesium sulfate, seplite, zonotlite, aluminum borate, colloidal calcium carbonate, soft calcium carbonate, silica, titanium oxide, barium sulfate, zinc oxide, alumina, magnesium hydroxide, hydro Talsite, silica beads, alumina beads, carbon beads, glass balloons, metallic conductive fillers, nonmetallic conductive fillers, magnetic fillers, piezoelectric / pyroelectric fillers, slidable fillers, fillers for sealing materials, UV absorption Examples thereof include fillers, vibration damping fillers, ketjen black, and acetylene black. These various fillers can be added to obtain a composite according to the application.

  The resin composition according to the present embodiment further includes rubber-like substances other than those described above, alicyclic saturated hydrocarbon resins, terpene resins, aliphatic petroleum resins, aromatic petroleum resins and various elastomers thereof, Various additives such as modified products of resins, higher fatty acid esters, higher fatty acid metal salts, various waxes, petroleum hydrocarbons, polyoxyalkylenes, fluororesins, antistatic agents, dyes and pigments as colorants The material can be added to meet the application.

  Examples of rubber-like substances are polymers having a glass transition temperature of −100 ° C. or more and 50 ° C. or less, or copolymers obtained by copolymerizing monomers of the polymer. For example, isoprene-based, butadiene-based, olefin-based, polyester An elastomer type and an acrylic type are mentioned. These rubber-like substances may use homopolymers, but can also be used as copolymers if necessary. Among these rubber-like substances, those generally used include butadiene and olefins. Furthermore, a ternary copolymer with an acid component is also useful. Specifically, acrylic acid-butadiene-styrene copolymer, carboxylic acid / carboxylic anhydride-containing acid compound-butadiene-styrene copolymer, etc. Is mentioned. Further, similarly to the butadiene rubber-like substance, an olefin rubber component modified with an acid component is also useful, and an epoxy group-containing olefin rubber component may also be used.

  The alicyclic saturated hydrocarbon resin is a hydrogenated product of an aromatic hydrocarbon resin. Generally, aromatic hydrocarbon resins include C9 hydrocarbon resins, C5 / C9 hydrocarbon resins, indene-coumarone resins, vinyl aromatics. Group resin, terpene-vinyl aromatic resin and the like. The higher the hydrogenation rate, the better, but 30% or more is desirable. When there are many aromatic components, since other physical properties are impaired, it is not preferable.

  As the terpenes, terpenes made from α-pinene, β-pinene and dipentenes are used. Those modified with aromatic hydrocarbons (phenol, bisphenol A, etc.) or hydrogenated terpenes can also be used effectively.

  Higher fatty acid esters, higher fatty acid metal salts and waxes are effective as processing aids for improving fluidity and releasability. As the waxes, olefin wax, montan wax and the like are generally used, and among them, low molecular weight polyethylene is generally used.

  Liquid petroleum fractions are preferably used as petroleum hydrocarbons.

  As the aromatic hydrocarbon petroleum resin, an aromatic hydrocarbon fraction polymer represented by C9 carbons is used.

  The antistatic agent generally has an action of exerting its effect by imparting hygroscopicity to the surface of the molded body. The antistatic agent may be used as an additive in the resin or may be applied as a secondary process such as coating. Examples of the antistatic agent used as an additive include polyalkylene glycol, polyalkylene oxide, and polyalkyl sulfonate.

  Examples of the ultraviolet absorber include hindered amine, benzotriazole, benzophenone, and epoxy. Ultraviolet absorbers may be used alone, but when used in combination, further effects can be expected.

  The addition amount of these other additives is not particularly limited, but is generally preferably 0.01 to 100 parts by mass with respect to a total of 100 parts by mass of (a) PPE resin and (b) styrene resin. It is 5 mass parts, More preferably, it is the range of 0.02-3 mass parts.

[Method for Producing Resin Composition]
The resin composition which concerns on this embodiment can be manufactured by melt-mixing each component mentioned above under a heating. A preferred melt mixer for the melt mixing is preferably an extruder, more preferably a twin screw extruder, and particularly preferably a twin screw extruder in which a screw configuration including a kneading block can be appropriately selected. Although all the components can be supplied from the first supply port and melt-mixed, the mass ratio ((a) / (b)) of (a) PPE resin and (b) styrene resin is 100. Supply from the first supply port in the range of / 0 to 50/50 and knead, and then supply (b) the remainder of the styrenic resin, (c) phosphorus compound, and (d) filler from the second supply port on Then, it is preferable to melt and mix. In addition, using a resin composition pellet obtained by kneading (a) a PPE resin and (b) a styrene resin, or (c) a phosphorus compound in the first extruder, A two-stage melt mixing extrusion method in which (b) a styrenic resin, (c) a phosphorus compound, (d) a filler, and other additives are melt-kneaded is also suitable.

  (D) The blending method of the filler is not particularly limited, but in order to suppress deterioration due to shearing and heat during extrusion, (a) PPE resin, (b) styrene resin and ( c) After melt-kneading the phosphorus compound, it is preferable to add the filler (d) in the second step. In particular, the fibrous or plate-like filler is supplied from the middle of the extruder cylinder in the second step. It is preferable for suppressing the crushing of the filler and enhancing the properties of the resin composition.

  Hereinafter, the present embodiment will be described in more detail with reference to examples, but the present embodiment is not limited to these examples.

[Structural component]
The following components were used as constituent components of the resin composition.

  (A) Polyphenylene ether resin (PPE): The following (a-1) and (a-2) were used as poly (2,6-dimethyl-1,4-phenylene) ether.

  (A-1): Asahi Kasei Chemicals Corporation, product name: Zylon S201A.

  (A-2): Asahi Kasei Chemicals Corporation, product name: Xylon S202A.

  In addition, when (a-1) and (a-2) were used together, mass ratio ((a-1) / (a-2)) was described in the table | surface.

  (B) Styrenic resin: For polystyrene, the following (b-1) HIPS and (b-2) GPPS are mixed at a mass ratio ((b-1) / (b-2)) 50/50. It was.

  (B-1) HIPS (rubber-modified polystyrene): manufactured by PS Japan, product name PSJ-polystyrene H9302.

  (B-2) GPPS (homopolystyrene): PS Japan Co., Ltd., product name PSJ-polystyrene 680.

  (C) The following (c-1) to (c-4) are used as phosphorus compounds, and the following (c-5), (c-6) and (c-7) are used as comparative phosphorus compounds. It was. Each phosphorus compound is shown below.

  (C-1): Phosphorus compound having N = 1 in the following chemical formula (i) as the main component (about 85% in area ratio by liquid chromatography analysis) and an acid value of 0.05 or less.

  (C-2): The same phosphorus compound as (c-1) except that the acid value is 0.7.

  (C-3): The same phosphorus compound as (c-1) except that the acid value is 0.3.

  (C-4): Phosphorus compound having N = 1 in the following chemical formula (ii) as a main component (about 85% in terms of area ratio by liquid chromatography analysis) and an acid value of 0.05 or less.

  (C-5): As a phosphorus flame retardant, product name CR741 (bisphenol A aromatic condensed phosphate ester compound) manufactured by Daihachi Chemical Industry Co., Ltd.

  (C-6): As a phosphorus flame retardant, product name CR733S (resorcin aromatic condensed phosphate ester compound) manufactured by Daihachi Chemical Industry Co., Ltd.

  (C-7): As a phosphorus flame retardant, product name TPP (triphenyl phosphate) manufactured by Daihachi Chemical Industry Co., Ltd.

  (D) The following (d-1) to (d-5) were used as fillers.

  (D-1) Glass fiber: Chopped strand manufactured by Nippon Sheet Glass Co., Ltd., product name RES03-TP1051.

  (D-2) Glass flake: Nippon Sheet Glass Co., Ltd., product name CEF150A.

  (D-3) Mica: manufactured by Kuraray Co., Ltd., product name: Suzolite Mica 200KI.

  (D-4) Talc: Product name Hytron A, manufactured by Takehara Chemical Co., Ltd.

  (D-5) Chlorite: manufactured by Fuji Talc Kogyo Co., Ltd., product name WL-13M.

  (E) Hydrogenated block copolymer (SEBS): As a hydrogenated styrene-butadiene block copolymer, Asahi Kasei Chemicals Corporation, product name Tuftec H1081 was used.

  (F) The following (LDPE) and (EP) were used as polyolefin resin.

  (LDPE): Low density polyethylene. Product name Suntech LD-M2004, manufactured by Asahi Kasei Chemicals Corporation.

  (EP): ethylene-propylene copolymer. Tuffmer P0680 manufactured by Mitsui Chemicals, Inc.

[Characteristic evaluation methods]
Characteristic evaluation of the obtained resin composition was performed by the following methods and conditions.

(1) Mold deposit (MD) test After the obtained resin composition pellets were dried at 80 ° C for 2 hours, IS-100GN molding machine manufactured by Toshiba Machine Co., Ltd. (cylinder temperature was 310 ° C, mold temperature was 80 ° C). When molding a later-described UL94 test piece (thickness 1.6 mm), the mold surface was wiped with ethanol. Next, 100 shot continuous molding was performed at a pressure of about 1 cm short for complete filling. Thereafter, the degree of deposits (cloudiness) produced at the end of the mold cavity of the mold was visually confirmed, and the mold deposit (MD) was evaluated according to the following criteria.

(Standard)
○: Almost no deposit was observed.

      Δ: Some deposits were observed.

      X: A deposit was clearly seen.

(2) Water absorption test, water absorption characteristics Using a tensile test piece of ISO-527, it was immersed in hot water at 120 ° C. (under vapor pressure) for 150 hours, and the mass increase% from the test piece before immersion was measured. Furthermore, the tensile test was performed about the test piece after immersion, and the tensile strength (TY) of the test piece after immersion was measured. The ratio (retention rate) of the tensile strength (TY) of the test piece after immersion to the tensile strength before immersion was calculated.

(3) Material properties Material properties were measured based on ISO standard physical property tests.

(Creation of test piece)
The obtained resin composition pellets were dried at 100 ° C. for 2 hours, and then the ISO-GN molding machine manufactured by Toshiba Machine Co., Ltd. (cylinder temperature was set to 280 ° C. and mold temperature was set to 80 ° C.) was used. A test piece was molded according to 15103.

  -MVR: Resin composition pellets were used, and as a fluidity evaluation, measurement was performed at 300 ° C. and a load of 5 kg in accordance with ISO-1133.

  -HDT: Using the above test piece, as a heat resistance evaluation, it was measured under flat pressure under 1.8 MPa in accordance with ISO-75.

  Charpy Imp: Using the above test piece, the impact resistance was evaluated according to ISO-179 and measured with a notch.

  TS: Using the above test piece, the tensile strength was measured according to ISO-527 at a test speed of 5 mm / min.

  FM: Using the above test piece, the flexural modulus was evaluated according to ISO-178 at a test speed of 2 mm / min.

(4) Mold shrinkage The mold shrinkage was measured as a dimensional characteristic by the following method.

  After the obtained resin composition pellets were dried at 100 ° C. for 2 hours, IS-100FB molding machine manufactured by Toshiba Machine Co., Ltd. (cylinder temperature 280 ° C., mold temperature 80 ° C., injection time 15 seconds, cooling time 20 A flat plate of 150 mm × 150 mm × 2 mm thickness (2 mmφ pin gate) was formed. The plate was conditioned at 23 ° C. and 50% humidity for 24 hours. About this flat plate, the dimension of the flow direction (MD) and the flow right angle direction (TD) was measured, and the shrinkage rate (%) and anisotropy (TD / MD ratio) of each direction from the mold dimensions were calculated. .

(5) Flame retardance Based on the UL-94 vertical combustion test, a combustion test was performed using an injection molded test piece having a thickness of 1.6 mm. Five test pieces were subjected to flame contact twice, a total of 10 times, and displayed as the average number of seconds (Av: sec) and the maximum number of seconds (Max: sec) of the flame extinguishing time.

(6) Releasability When a test piece is molded by injection molding as shown in (3) above, the degree of ease of mold release from the test piece and runner mold is visually determined according to the following criteria: did.

(Standard)
○: The mold release was good.

      (Triangle | delta): Mold release was a little bad.

      X: The mold release was very bad.

[Examples 1-14, Comparative Examples 1-6]
Using a twin-screw co-rotating extruder ZSK-25 manufactured by Werner Pfleiderer, the raw material components having the compositions shown in Tables 1 to 3 were melted and kneaded, and vacuum degassed from the devolatilization port at the subsequent stage to obtain resin composition pellets. Obtained. The raw material components other than the filler were mixed and supplied from the first supply port of the extruder, and the filler was supplied from the second and third supply ports. The melt-kneading conditions were such that the maximum cylinder temperature was set to 300 ° C. and the screw rotation speed was 300 rpm and 15 kg / hr. However, the liquid flame retardants (c-5) and (c-6) and the low melting point (c-7) were supplied and added by a pump from the latter stage after devolatilization. Further, as a stabilizer, 0.1 part by mass of IRGAFOS 168, 0.1 part by mass of IRGAFOS 168, and 0 of IRGANOX 1076 are produced with respect to a total of 100 parts by mass of components (a), (b), (c) and (d) .1 part by mass was added to each raw material component.

  The properties of the obtained resin composition pellets were measured by the evaluation method. The results are shown in Table 1, Table 2 and Table 3.

  The resin composition of the present invention has excellent flame retardancy without using harmful halogen compounds and antimony compounds, and is excellent in terms of environment and safety and health in production and use. Also, the productivity is good, and the deterioration of heat resistance and mechanical properties is small. And there is no malfunction of the molded product due to mold contamination under severe injection molding conditions and its deposits, and it is excellent in moisture absorption characteristics, mechanical characteristics and dimensional characteristics.

  Therefore, the resin composition of the present invention is widely used for various electric / electronic parts, office equipment parts, automobile parts, building materials, other various exterior materials, industrial products, and the like. It is particularly suitable for resin-made mechanical parts for information processing equipment with strict requirements on dimensional characteristics. Examples of resin mechanical parts for information processing equipment include carriages, chassis, gears, shafts, pulleys, etc. in office equipment such as inkjet printers, laser beam printers, copying machines, and fax machines, computers, game machines, music, etc. Optical disc drives for players, video players, AV equipment, etc. (CD-ROM, CD-R, CD-RW, CD-RW, DVD-ROM, DVD-R, DVD-RAM, DVD-RW, DVD + RW, MD, MO) Etc. (pickup chassis, traverse base, sub chassis, base chassis, etc.), trays (disc tray, changer tray, etc.), gears, shafts, pulleys, etc.

Claims (7)

10 to 90% by mass of the total of (a) polyphenylene ether resin and (b) styrene resin,
(C) 1-30 mass% of phosphorus compound and (d) 1-60 mass% of filler,
The mass ratio ((a) / (b)) between the component (a) and the component (b) is 10/90 to 100/0,
The resin composition whose said component (c) is a phosphorus compound represented by the following general formula (I).
[In the formula (I),
Each A independently represents an alkyl group having 1 to 8 carbon atoms, an aryl group having 6 to 10 carbon atoms, or an aralkyl group having 7 to 12 carbon atoms;
R ¹ , R ² , R ³ and R ⁴ are each independently an alkyl group having 1 to 8 carbon atoms, a cycloalkyl group having 5 to 6 carbon atoms, an aryl group having 6 to 20 carbon atoms, or carbon. Represents an aralkyl group having 7 to 12 atoms,
x and y are each independently 0, 1, 2, 3 or 4;
n is each independently 0 or 1,
N is 1-30. ]   The resin composition of Claim 1 whose mass ratio ((a) / (b)) of the said component (a) and the said component (b) is 20 / 80-99 / 1.   The resin composition of Claim 1 or 2 whose acid value of the said component (c) is 0.5 or less. The resin composition according to any one of claims 1 to 3, wherein the component (c) is a phosphorus compound represented by the formula (II).
[In formula (II), N is 1-10. ]   The resin composition as described in any one of Claims 1-4 in which the said component (d) contains a plate-shaped filler.   The resin composition as described in any one of Claims 1-5 in which the said component (d) contains a plate-shaped filler 50 mass% or more with respect to the whole quantity of the said component (d).   The resin composition according to any one of claims 1 to 6, wherein the component (d) contains one or more selected from the group consisting of glass flakes, mica, chlorite, and talc.