阅读说明：本技术 树脂成型体 (Resin molded article ) 是由 片山弘 上田隆史 于 2019-10-02 设计创作，主要内容包括：本发明涉及一种树脂成型体,其是由含有(A)热塑性树脂、(B)阻燃剂、及(C)金属纤维的树脂组合物得到的,在上述树脂成型体中含有(B)阻燃剂15～30质量％、(C)金属纤维2.5～7.5质量％,其余部分是使合计为100质量％的(A)成分,上述树脂成型体的基于UL94V试验法的燃烧试验判定结果在1.5mm厚度的试验片时为V-0或V-1,且该树脂成型体满足下述(I)～(IV)的要件：(I)厚度为1.5～8.0mm；(II)在基于下述燃烧试验E法的燃烧试验结束后5分钟以内自熄；(III)在基于下述燃烧试验E法的燃烧试验后在成型体上没有开孔；(IV)在频率范围1～100MHz内基于KEC法电场的电磁波屏蔽性为超过30dB的值。燃烧试验E法：使用由上述成型体制成的平板(150×150×2.0mm),使用200mm长度的火焰从上述平板的上方对着上述平板的中心接触火焰130秒钟,从上述平板的接触火焰位置至燃烧嘴的距离为150mm。(The present invention relates to a resin molded article obtained from a resin composition containing (A) a thermoplastic resin, (B) a flame retardant, and (C) a metal fiber, wherein the resin molded article contains 15 to 30 mass% of (B) a flame retardant and 2.5 to 7.5 mass% of (C) a metal fiber, and the balance is 100 mass% of the component (A), and the resin molded article has a flame test determination result by a UL94V test method of V-0 or V-1 in a test piece having a thickness of 1.5mm, and satisfies the following requirements (I) to (IV): (I) the thickness is 1.5-8.0 mm; (II) self-extinguishment within 5 minutes after completion of a combustion test by the following combustion test method E; (III) no open pores were formed in the molded article after the combustion test based on the following combustion test method E; (IV) the electromagnetic wave shielding property based on the KEC method electric field is a value exceeding 30dB in the frequency range of 1-100 MHz. Combustion test method E: a flat plate (150X 2.0mm) made of the molded article was used, and a flame having a length of 200mm was applied for 130 seconds from above the flat plate toward the center of the flat plate, and the distance from the flame-contacting position of the flat plate to the burner tip was 150 mm.)

1. A resin molded article obtained from a resin composition containing (A) a thermoplastic resin, (B) a flame retardant, and (C) a metal fiber,

the resin molded body contains 15 to 30 mass% of (B) a flame retardant and 2.5 to 7.5 mass% of (C) a metal fiber, the balance being the component (A), and the total of the components being 100 mass%,

the flame test result of the resin molded article by the UL94V test method is V-0 or V-1 in a test piece with a thickness of 1.5mm, and the resin molded article satisfies the following requirements (I) to (IV):

(I) the thickness of the resin forming body is 1.5-8.0 mm;

(II) the resin molded body is self-extinguished within 5 minutes after the end of a combustion test by the method of combustion test E described below;

(III) the resin molded body has no open pores in the molded body after a combustion test by the following combustion test method E;

(IV) the electromagnetic wave shielding property of the resin molded body based on the KEC method electric field in the frequency range of 1-100 MHz is a value exceeding 30dB,

combustion test method E: using a flat plate (150X 2.0mm) made of the molded article, a flame having a length of 200mm was contacted from above the flat plate toward the center of the flat plate for 130 seconds, and the distance from the flame-contacting position of the flat plate to the burner tip was 150 mm.

2. A resin molded article obtained from a resin composition containing (A) a thermoplastic resin, (B) a flame retardant, (C) metal fibers, and (D) glass fibers,

the resin molded body contains 15 to 30 mass% of a flame retardant (B), 2.5 to 7.5 mass% of a metal fiber (C), and 5 to 50 mass% of a glass fiber (D), the balance being the component (A), and the total of the components being 100 mass%,

the flame test result of the resin molded article by the UL94V test method is V-0 or V-1 in a test piece with a thickness of 1.5mm, and the resin molded article satisfies the following requirements (I) to (IV):

(I) the thickness of the resin forming body is 1.5-8.0 mm;

(II) the resin molded body is self-extinguished within 5 minutes after the end of a combustion test by the method of combustion test E described below;

(III) the resin molded body has no open pores in the molded body after a combustion test by the following combustion test method E;

(IV) the electromagnetic wave shielding property of the resin molded body based on the KEC method electric field in the frequency range of 1-100 MHz is a value exceeding 30dB,

combustion test method E: using a flat plate (150X 2.0mm) made of the molded article, a flame having a length of 200mm was contacted from above the flat plate toward the center of the flat plate for 130 seconds, and the distance from the flame-contacting position of the flat plate to the burner tip was 150 mm.

3. A resin molded article obtained from a resin composition containing (A) a thermoplastic resin, (B) a flame retardant, (C) metal fibers, (D) glass fibers, and (E) at least one carbonization promoter selected from the group consisting of magnesium hydrogencarbonate, zinc oxide, titanium oxide, magnesium oxide and silicon oxide,

the molded article contains 15 to 30 mass% of a flame retardant (B), 2.5 to 7.5 mass% of a metal fiber (C), 5 to 50 mass% of a glass fiber (D), and 0.7 to 5.0 mass% of a carbonization accelerator (E), the balance being the component (A), and the total of the components being 100 mass%,

the flame test result of the resin molded article by the UL94V test method is V-0 or V-1 in a test piece with a thickness of 1.5mm, and the resin molded article satisfies the following requirements (I) to (IV):

(I) the thickness of the resin forming body is 1.5-8.0 mm;

(II) the resin molded body is self-extinguished within 5 minutes after the end of a combustion test by the method of combustion test E described below;

(III) the resin molded body has no open pores in the molded body after a combustion test by the following combustion test method E;

(IV) the electromagnetic wave shielding property of the resin molded body based on the KEC method electric field in the frequency range of 1-100 MHz is a value exceeding 30dB,

combustion test method E: using a flat plate (150X 2.0mm) made of the molded article, a flame having a length of 200mm was contacted from above the flat plate toward the center of the flat plate for 130 seconds, and the distance from the flame-contacting position of the flat plate to the burner tip was 150 mm.

4. The resin molded body according to claim 2 or 3, which further satisfies the following requirements (V) and (VI):

(V) Total exotherm measured by cone calorimeter exotherm test of the following method was 8MJ/m after 130 seconds from the start of heating²The following;

(VI) when the total heat release is measured by a cone calorimeter heat release test by the method described below, no hole is formed in the aluminum foil covering the self-extinguishing resin molded body after 5 minutes has elapsed from the start of heating;

cone calorimeter exothermicity test: a sample was prepared by covering the surface of a flat plate-shaped molded article having a size of 100mm X100 mm and a thickness of 2.0mm except the heating surface with an aluminum foil (thickness of 12 μm) according to ISO5660-1, and the radiation heat intensity was 50kW/m²Heating was carried out for 5 minutes.

5. The resin molded body according to any one of claims 1 to 4,

(C) the metal fiber of component (a) or the glass fiber of component (D) is a fiber in the form of a long fiber bundle to which resin is attached, in which the thermoplastic resin of component (a) is attached in a molten state to a metal fiber bundle or a glass fiber bundle, and the metal fiber bundle or the glass fiber bundle is cut into a length of 1 to 15mm, and the metal fiber bundle or the glass fiber bundle is a fiber bundle in which metal fibers or glass fibers are bundled in a state aligned in the longitudinal direction.

6. The resin molded body according to any one of claims 1 to 5, wherein,

(B) the component is a phosphorus flame retardant.

7. The resin molded body according to any one of claims 1 to 5, wherein,

(A) the component is polypropylene resin.

8. The resin molded body according to any one of claims 1 to 7, which is a case member of a battery module for a vehicle or a peripheral member thereof.

Technical Field

The present invention relates, in one embodiment, to a resin molded body that can be used for a battery pack case member or a peripheral member of a battery-powered electric transportation device such as an electric vehicle or an electric motorcycle.

Background

In a rechargeable energy storage system (REESS) such as a battery that can be mounted on a battery-type electric transportation device such as an Electric Vehicle (EV) or a plug-in hybrid vehicle (PHV), each member constituting the system is required to have higher flame retardancy and self-extinguishing properties than conventional vehicle-mounted resin members. For example, the electrical safety-related regulations such as European ECE-R100 must be satisfied.

Jp 2014-133808 a describes a resin molded article for a charger connector for an electric vehicle, a holder for a battery capacitor, a case for a battery capacitor, and a case for a charging holder for an electric vehicle, which has a high flame retardancy and a leakage resistance for securing safety against ignition by an electric load. The flame retardant is a halogen-based flame retardant.

In Journal of Composite Materials 2018, Vol.52(4) 519-.

Disclosure of Invention

An object of one aspect of the present invention is to provide a resin molded body having flame retardancy that satisfies the standard for being mounted on a battery-type electric transportation device, and having good mechanical strength and electromagnetic wave shielding properties.

The present invention provides a resin molded article obtained from a resin composition containing (A) a thermoplastic resin, (B) a flame retardant, and (C) a metal fiber,

the resin molded body contains 15 to 30 mass% of (B) a flame retardant, 2.5 to 7.5 mass% of (C) a metal fiber, and the balance being the component (A), the total of which is 100 mass%,

the flame test result of the resin molded article by the UL94V test method was V-0 or V-1 in a test piece having a thickness of 1.5mm, and the resin molded article satisfied the following requirements (I) to (IV).

(I) The thickness of the resin molded body is 1.5 to 8.0 mm.

(II) the resin molded article self-extinguishes within 5 minutes after the end of a combustion test by the method of Combustion test E described below.

(III) the resin molded article has no open pores in the molded article after a combustion test by the method of the following combustion test E.

(IV) the electromagnetic wave shielding property of the resin molded body based on the KEC method electric field in the frequency range of 1-100 MHz is more than 30 dB.

Combustion test method E: a flat plate (150X 2.0mm) made of the above molded body was used. The flame was contacted from above the plate, facing the center of the plate, for 130 seconds using a flame having a length of 200 mm. The distance from the flame-contacting position of the flat plate to the burner tip was 150 mm.

In another embodiment, the present invention provides a resin molded article obtained from a resin composition containing (A) a thermoplastic resin, (B) a flame retardant, (C) metal fibers, and (D) glass fibers,

the resin molded body contains 15 to 30 mass% of (B) a flame retardant, (C) 2.5 to 7.5 mass% of a metal fiber, and (D) 5 to 50 mass% of a glass fiber, the balance being the component (A), and the total of the components being 100 mass%,

the flame test result of the resin molded article by the UL94V test method was V-0 or V-1 in a test piece having a thickness of 1.5mm, and the resin molded article satisfied the following requirements (I) to (IV).

(I) The thickness of the resin molded body is 1.5 to 8.0 mm.

(II) the resin molded article self-extinguishes within 5 minutes after the end of a combustion test by the method of Combustion test E described below.

(III) the resin molded article has no open pores in the molded article after a combustion test by the method of the following combustion test E.

(IV) the electromagnetic wave shielding property of the resin molded body based on the KEC method electric field in the frequency range of 1-100 MHz is more than 30 dB.

Combustion test method E: a flat plate (150X 2.0mm) made of the above molded body was used. The flame was contacted from above the plate, facing the center of the plate, for 130 seconds using a flame having a length of 200 mm. The distance from the flame-contacting position of the flat plate to the burner tip was 150 mm.

In another embodiment, the present invention provides a resin molded article obtained from a resin composition containing (A) a thermoplastic resin, (B) a flame retardant, (C) metal fibers, (D) glass fibers, and (E) at least one carbonization accelerator selected from the group consisting of magnesium hydrogencarbonate, zinc oxide, titanium oxide, magnesium oxide, and silicon oxide,

the molded article contains 15 to 30 mass% of (B) a flame retardant, (C) 2.5 to 7.5 mass% of a metal fiber, (D) 5 to 50 mass% of a glass fiber, and (E) 0.7 to 5.0 mass% of a carbonization accelerator, the balance being the component (A), and the total of the components being 100 mass%,

the flame test result of the resin molded article by the UL94V test method was V-0 or V-1 in a test piece having a thickness of 1.5mm, and the resin molded article satisfied the following requirements (I) to (IV).

(I) The thickness of the resin molded body is 1.5 to 8.0 mm.

(II) the resin molded article self-extinguishes within 5 minutes after the end of a combustion test by the method of Combustion test E described below.

(III) the resin molded article has no open pores in the molded article after a combustion test by the method of the following combustion test E.

(IV) the electromagnetic wave shielding property of the resin molded body based on the KEC method electric field in the frequency range of 1-100 MHz is more than 30 dB.

Combustion test method E: a flat plate (150X 2.0mm) made of the above molded body was used. The flame was contacted from above the plate, facing the center of the plate, for 130 seconds using a flame having a length of 200 mm. The distance from the flame-contacting position of the flat plate to the burner tip was 150 mm.

The resin molded article of the example of the present invention has flame retardancy satisfying the standards (ECE-R100 and the like) that can be mounted on a battery-type electric transportation device, has good mechanical strength, and has high electromagnetic wave shielding properties, in addition to self-extinguishing properties that exhibit fire extinguishing performance at the time of a fire accident.

Detailed Description

< resin composition >

Hereinafter, several examples of the resin composition used for the resin molded article according to the embodiment of the present invention will be described.

[ (A) thermoplastic resin ]

As the thermoplastic resin of the component (a), for example, polyolefin resin can be used. In some examples, there can be used a polyethylene resin (high density polyethylene (HDPE), Low Density Polyethylene (LDPE), Linear Low Density Polyethylene (LLDPE), very low density polyethylene (VLDPE, ULDPE), etc.), a polypropylene resin, an alpha-C2-20 chain olefin resin such as a methylpentene resin, a cyclic olefin resin, etc. These polyolefin resins may be used alone, or two or more kinds may be used in combination. In one embodiment of the present invention, a polypropylene-based resin is particularly preferably used.

According to several specific examples, the polypropylene-based resin may be a homopolymer of propylene or a copolymer of propylene and another copolymerizable monomer. Examples of other copolymerizable monomers include: olefin monomers (e.g., α -C2-20 chain olefins such as ethylene, 1-butene, isobutylene, 1-pentene and 4-methyl-1-pentene, cyclic olefins, etc.), vinyl ester monomers (e.g., vinyl acetate and vinyl propionate), (meth) acrylic monomers [ e.g., vinyl cyanide monomers such as (meth) acrylic acid, alkyl (meth) acrylates and (meth) acrylonitrile ], diene monomers (e.g., butadiene), unsaturated polycarboxylic acids and anhydrides thereof (e.g., maleic acid, itaconic acid, citraconic acid and anhydrides thereof), imide monomers [ e.g., N-substituted maleimides such as maleimide and N-alkylmaleimide (e.g., N-C1-4 alkylmaleimide) ], and the like. These copolymerizable monomers may be used alone or in combination of two or more.

In more detailed examples, as the polypropylene-based resin, in addition to the homopolypropylene as a homopolymer, for example: propylene- α 2 to 20 chain olefin copolymers (random copolymers, block copolymers, etc.) having a propylene content of 80 mass% or more, such as propylene-ethylene copolymers, propylene-butene-1 copolymers, and propylene-ethylene-butene-1 copolymers.

Of these polypropylene resins, homopolypropylene and a propylene- α 2 to 6 chain olefin copolymer (random copolymer, block copolymer, etc.) are preferable in one embodiment of the present invention, and homopolypropylene and a propylene-ethylene copolymer (random copolymer, block copolymer) are preferable in another embodiment of the present invention. These polypropylene resins may be used alone or in combination of two or more.

[ (B) flame retardant ]

In one preferred embodiment of the present invention, the flame retardant of component (B) is a phosphorus-based flame retardant from the viewpoint of self-extinguishing properties after a combustion test and suppression of the occurrence of pores in the molded article, and in another preferred embodiment of the present invention, the flame retardant may be (B-1) an organic phosphoric acid compound or (B-2) an organic phosphate compound, or a mixture thereof, but does not contain a halogen atom.

Examples of the (B-1) organophosphoric acid compound include: phosphoric acid, melamine orthophosphate, melamine pyrophosphate, melamine polyphosphate, melamine phosphate and the like, and of these, melamine polyphosphate is preferable, and melamine pyrophosphate is particularly preferable.

Examples of the organic phosphate compound (B-2) include: piperazine orthophosphate, piperazine pyrophosphate, piperazine polyphosphate, and the like, and among these, piperazine polyphosphate is used in one preferred embodiment of the present invention, and piperazine pyrophosphate is used in another preferred embodiment of the present invention.

When the component (B) is a mixture of the component (B-1) and the component (B-2), the mass ratio of the component (B-1) to the component (B-2) is 1:99 to 99:1 in one preferred embodiment of the present invention, 10:90 to 90:10 in another preferred embodiment of the present invention, and 30:70 to 70:30 in yet another preferred embodiment of the present invention. When the mass ratio is in the range of 1:99 to 99:1, the flame retardant effect is good.

Examples of the component (B) include ADEKASTAB FP-2100JC, FP-2200S and FP-2500S available from ADEKA, Inc.

The average particle diameter of the component (B) is 40 μm or less in one preferred embodiment of the present invention, and may be 10 μm or less in another preferred embodiment of the present invention from the viewpoint of flame retardancy. When the average particle diameter is 40 μm or less, the component (A) has good dispersibility in the thermoplastic resin, high flame retardancy can be obtained, and the mechanical strength of the resin molded article is also good.

The flame retardant of component (B) may contain, if necessary, a conventionally known flame retardant auxiliary, a blowing agent, other non-halogen flame retardants, and the like, within a range not impairing the object of the present invention. In addition, the flame retardant of the component (B) may contain a carbonization accelerator corresponding to the component (E) described later.

The flame retardant auxiliary may be selected from condensates of pentaerythritol with at least two dimers and esters thereof in one preferred embodiment of the present invention, and may be 1 or 2 or more selected from pentaerythritol and esters thereof, dipentaerythritol and esters thereof, tripentaerythritol and esters thereof in another preferred embodiment of the present invention. The flame-retardant auxiliary may contain a condensate of pentaerythritol or the like as a main component (80% by mass or more in a preferred embodiment of the present invention) and other flame-retardant auxiliary as the rest.

Examples of other flame retardant aids include: polyols such as pentaerythritol, cellulose, maltose, glucose, arabinose, ethylene glycol, propylene glycol, polyethylene glycol, and ethylene-vinyl alcohol copolymer; or ester compounds produced by reacting these polyol components with carboxylic acids; melamine, other melamine derivatives, guanamine or other guanamine derivatives, melamine (2,4, 6-triamino-1, 3, 5-triazine), isocyanuric acid, tris (2-hydroxyethyl) isocyanurate, tris (hydroxymethyl) isocyanurate, tris (3-hydroxypropyl) isocyanurate, tris (4-hydroxyphenyl) isocyanurate, and other triazine derivatives.

In some embodiments of the present invention, the blowing agent may be selected from melamine derivatives such as melamine, melamine formaldehyde resins, methylolmelamine having 4 to 9 carbon atoms, melamine cyanurate, urea derivatives such as urea, thiourea, urea (thiourea) -formaldehyde resins, methylolurea (thiourea) having 2 to 5 carbon atoms, guanamines such as benzoguanamine, phenylguanamine, acetoguanamine, succinoguanamine, reaction products of guanamines with formaldehyde, and nitrogen-containing compounds such as dicyandiamide, guanidine sulfamate, and the like.

In some embodiments of the present invention, other non-halogen flame retardants include phosphate flame retardants, ammonium polyphosphate, red phosphorus, magnesium hydroxide, aluminum hydroxide, and expanded graphite. Examples of the phosphate-based flame retardant include triphenyl phosphate, tricresyl phosphate, trixylenyl phosphate, tri (isopropylphenyl) phosphate, tri (o-or p-phenylphenyl) phosphate, trinaphthyl phosphate, tolyldiphenyl phosphate, ditolyl diphenyl phosphate, diphenyl (2-ethylhexyl) phosphate, di (isopropylphenyl) phenyl phosphate, o-phenylphenylditolyl phosphate, tri (2, 6-dimethylphenyl) phosphate, resorcinol tetraphenyl diphosphate, hydroquinone tetraphenyl diphosphate, phenyl resorcinol polyphosphate, bisphenol a-bis (diphenyl phosphate), bisphenol a-polyphenyl phosphate, and biphenol hypophosphate. In addition, examples of the fatty acid/aromatic phosphate ester include orthophosphoric acid esters such as diphenyl (2-ethylhexyl) phosphate, diphenyl-2-acryloyloxyethyl phosphate, diphenyl-2-methacryloyloxyethyl phosphate, phenylpivalyl phosphate, pentaerythritol diphenyl diphosphate and ethyl catechol phosphate, and mixtures thereof.

In one embodiment, the flame retardant auxiliary may be used alone or in combination in the flame retardant of component (B). The addition of the flame retardant aid can reduce the amount of the flame retardant to be blended or can provide flame retardancy that cannot be obtained by the flame retardant alone, and therefore, the flame retardant can be used in combination as appropriate depending on the type and application of the resin to which the flame retardant is blended. The particle diameter, melting point, viscosity, and the like of the flame retardant aid can be selected so as to be excellent in flame retardancy effect and powder characteristics.

For example, the amount of the flame retardant auxiliary is 10 to 60 parts by mass in one preferred embodiment of the present invention, 15 to 50 parts by mass in another preferred embodiment of the present invention, and 15 to 45 parts by mass in yet another preferred embodiment of the present invention, based on 100 parts by mass of the total content of (B-1) and (B-2). When the amount is within the above range, the mechanical strength of the molded article is good, the surface is not sticky, and a strong carbonized layer is formed to improve the flame retardancy, thereby improving the flame retardancy.

In some embodiments of the present invention, the resin composition may include a resin mixture containing a flame retardant as the component (B), and the content ratio of the total content of the components (B-1) and (B-2) in the resin mixture as the flame retardant of the component (B) is 50 to 80% by mass in a preferred embodiment of the present invention, 55 to 75% by mass in another preferred embodiment of the present invention, and 60 to 70% by mass in yet another preferred embodiment of the present invention.

The resin mixture may contain a thermoplastic resin of the component (A) as the rest of the above-mentioned content ratio. The resin mixture may contain a conventionally known antioxidant and a lubricant as needed within a range not impairing the object of the present invention. The thermoplastic resin as the component (a) is specifically a polypropylene resin in one preferred embodiment of the present invention, and is a homopolypropylene or a propylene-ethylene copolymer (random copolymer, block copolymer) in another preferred embodiment of the present invention.

Examples of the antioxidant include antioxidants selected from phosphorus antioxidants, sulfur antioxidants, phenol antioxidants (for example, antioxidants described in paragraphs 0015 to 0025 of Japanese patent application laid-open No. 7-76640 such as phosphite antioxidants and thioether antioxidants), allyl phosphites such as tris (2, 4-di-t-butylphenyl) phosphite and triisodecyl phosphite, and amine antioxidants known as antioxidants for resins. Examples of commercially available products include "Irganox 1010" manufactured by BASF JAPAN corporation and "ADEKASTAB PEP 36" manufactured by ADEKA corporation.

The lubricant may be a conventionally known lubricant, for example: examples of the lipid, wax, silicone resin and the like include lubricants selected from the lubricants described in paragraphs 0068 to 0073 of Japanese patent laid-open No. 2009-167270. As a commercially available product, "Alflow H-50S" manufactured by Nichisu oil Co., Ltd.

[ (C) Metal fibers ]

(C) Component (c) as the metal fiber, in one preferred embodiment of the present invention, it is selected from, for example, stainless steel (SUS) fiber, copper fiber, silver fiber, gold fiber, aluminum fiber, and brass fiber, and in another preferred embodiment of the present invention, it may be stainless steel fiber.

According to an embodiment of the present invention, component (C) may use a metal fiber bundle to which a resin is attached, and the metal fiber bundle to which a resin is attached can be obtained as follows: the resin component of the thermoplastic resin containing the component (a) is melted, and if necessary, the melted resin is adhered to and integrated with a metal fiber bundle in which metal fibers are bundled in a state of being aligned in the longitudinal direction in a state in which the flame retardant of the component (B) is dispersed, and then cut into a predetermined length.

(C) The metal fiber of component (A) has a fiber diameter of 5 to 20 μm in one preferred embodiment of the present invention, 7 to 16 μm in another preferred embodiment of the present invention, and 10 to 13 μm in yet another preferred embodiment of the present invention, and may be a long fiber or a short fiber.

According to an embodiment of the present invention, when the metal fibers of the component (C) are in the form of a metal fiber bundle to which a resin is attached, the metal fibers in the metal fiber bundle to which a resin is attached are the component (C), and the resin component is contained in the component (a).

According to an embodiment of the present invention, the metal fiber bundle with the resin attached thereto described herein includes: a fiber bundle in which a resin is impregnated (impregnated) into the central portion of the metal fiber bundle in the adhered state, and the resin enters between fibers constituting the central portion of the fiber bundle (hereinafter referred to as "resin-impregnated metal fiber bundle"); a fiber bundle in which only the surface of the reinforcing fiber bundle is covered with a resin ("metal fiber bundle whose surface is covered with a resin"); the fiber bundle interposed therebetween (the fiber bundle in which the surface of the fiber bundle is covered with the resin, only the vicinity of the surface is impregnated with the resin, and the resin does not enter the center portion) ("the metal fiber bundle partially impregnated with the resin"), preferably "the metal fiber bundle impregnated with the resin".

According to the embodiment of the present invention, the metal fiber bundle to which the resin is attached can be manufactured by a known manufacturing method as described in paragraph 0043 of japanese patent No. 5959183, for example. The number of the metal fibers in the metal fiber bundle can be adjusted from, for example, 100 to 30000.

In some embodiments of the present invention, the content of the metal fiber in the metal fiber bundle to which the resin is attached is 20 to 70% by mass in one preferred embodiment of the present invention, 30 to 60% by mass in another preferred embodiment of the present invention, and 40 to 50% by mass in yet another preferred embodiment of the present invention, in 100% by mass of the metal fiber bundle to which the resin is attached. The remainder may be a resin component containing the thermoplastic resin of component (a), and the thermoplastic resin of component (a) is a polypropylene resin in one preferred embodiment of the present invention, and is homopolypropylene or a propylene-ethylene copolymer (random copolymer or block copolymer) in another preferred embodiment of the present invention. The resin component of the thermoplastic resin containing the component (a) may contain a resin additive such as a stabilizer, but does not include a flame retardant represented by the component (B).

According to an embodiment of the present invention, the length of the metal fiber bundle to which the resin is attached (i.e., the length of the metal fiber of component (C)) is 1 to 15mm in one preferred embodiment of the present invention, 2 to 10mm in another preferred embodiment of the present invention, 3 to 7mm in yet another preferred embodiment of the present invention, and 5 to 7mm in another preferred embodiment of the present invention. The diameter of the metal fiber bundle to which the resin is attached is not particularly limited, and may be, for example, in the range of 0.5 to 5 mm.

[ (D) glass fiber ]

Further, the resin composition may contain glass fibers as the component (D) in view of, for example, improvement in rigidity and strength (tensile strength, flexural strength, impact strength).

(D) The component (B) may be a resin mixture containing glass fibers, and the content of the glass fibers in 100% by mass of the resin mixture is 10 to 70% by mass in a preferred embodiment of the present invention, 20 to 65% by mass in another preferred embodiment of the present invention, and 30 to 60% by mass in another preferred embodiment of the present invention. The remainder may be a resin component containing the thermoplastic resin of component (a), which is a polypropylene resin in one preferred embodiment of the present invention, and a homopolypropylene or a propylene-ethylene copolymer (random copolymer or block copolymer) in another preferred embodiment of the present invention.

(D) When the glass fiber of component (a) is a resin mixture containing component (a), the glass fiber in the resin mixture is component (C), and the resin component is included in component (a).

(D) The glass fiber of component (A) has a fiber diameter of 9 to 20 μm in one preferred embodiment of the present invention, 10 to 17 μm in another preferred embodiment of the present invention, and 13 to 17 μm in yet another preferred embodiment of the present invention, and may be a long fiber or a short fiber.

(D) When the glass fiber of the component (b) is a long fiber, a long glass fiber bundle to which a resin is attached can be used, and the long glass fiber bundle to which a resin is attached can be obtained as follows: the resin component of the thermoplastic resin containing the component (a) is adhered in a molten state to and integrated with a long glass fiber filler bundle in which glass fibers are bundled while being aligned in the longitudinal direction, and then cut into a predetermined length. The resin component of the thermoplastic resin containing the component (a) may contain a resin additive such as a stabilizer, but does not include a flame retardant represented by the component (B). (D) When the glass fiber of component (a) is in the form of a long glass fiber filler bundle to which a resin adheres, the glass fiber in the long glass fiber filler bundle to which a resin adheres is component (D), and the resin component is included in component (a).

The long glass fiber filler bundle to which a resin adheres as described herein includes a "long glass fiber filler bundle impregnated with a resin" classified according to the adhesion state, as in the case of the above-mentioned [ (C) metal fiber ]; "a long glass fiber filler strand coated with a resin on the surface thereof"; the "long glass fiber filler strand partially impregnated with resin" is preferably used.

The number of glass fibers in the long glass fiber bundle is adjusted, for example, from 500 to 10000, and the long glass fiber bundle can be produced by the "method for producing a metal fiber bundle to which a resin is attached" described in the above [ (C) metal fiber ].

According to an embodiment of the present invention, the length of the long glass fiber filler strand to which the resin is attached (i.e., the length of the glass fiber of component (D)) is 5 to 50mm in one preferred embodiment of the present invention, 7 to 25mm in another preferred embodiment of the present invention, and 9 to 15mm in yet another preferred embodiment of the present invention. The diameter of the fiber bundle to which the resin is attached is not particularly limited, and may be, for example, in the range of 0.5 to 5 mm.

According to an embodiment of the present invention, when the glass fiber of component (D) is a short fiber, the glass fiber has a length in a range of 1 to 4mm in one preferred embodiment of the present invention, and the glass fiber has a length in a range of 2 to 3mm in another preferred embodiment of the present invention. The glass short fibers may be chopped strands or the like, or may be surface-treated fibers.

According to an embodiment of the present invention, when the glass fiber of the component (D) is a short fiber, a resin mixture in which the glass short fiber is dispersed in a resin component containing the thermoplastic resin of the component (a) may be used, and the resin component may contain a resin additive such as a stabilizer and a flame retardant of the component (B). In some embodiments, the glass fiber of component (D) may be a combination of the long fibers (long glass fiber bundles to which resin is attached) and short glass fibers.

In some embodiments, the component (D) may be a glass short fiber in terms of electromagnetic wave shielding properties. By using a glass short fiber as the component (D), the electromagnetic wave shielding property of the molded article containing the resin composition of the present invention can be improved without preventing the metal fibers from coming into contact with each other.

[ carbonation accelerator ]

According to an embodiment of the present invention, examples of the carbonization accelerator include: an organic metal complex compound such as ferrocene, a metal hydroxide such as cobalt hydroxide, magnesium hydroxide or aluminum hydroxide, an alkaline earth metal borate salt such as magnesium borate or calcium magnesium borate, a metal oxide such as manganese borate, zinc metaborate, antimony trioxide, alumina trihydrate, magnesium hydrogen carbonate, alumina, magnesium oxide, silicon oxide, zirconium oxide, vanadium oxide, molybdenum oxide, nickel oxide, manganese oxide, titanium oxide, silicon oxide, cobalt oxide or zinc oxide, an aluminosilicate such as zeolite, a silicate-type solid acid such as silica titanium dioxide, a metal phosphate such as calcium phosphate, magnesium phosphate, aluminum phosphate or zinc phosphate, a clay mineral such as hydrotalcite, kaolin, sericite, pyrophyllite, bentonite or talc.

Among these, in view of the effect as a carbonization promoter, the carbonization promoter is, for example, at least one selected from the group consisting of magnesium hydrogencarbonate, zinc oxide, titanium oxide, magnesium oxide, and silicon oxide in one preferred embodiment of the present invention, and is zinc oxide in another preferred embodiment of the present invention. Optionally, any of other carbonization accelerators than those described above may be further contained.

In some embodiments, the resin composition may also contain carbon black. Examples of the carbon black include known furnace black, channel black, acetylene black, and ketjen black. The carbon black contained in the resin composition of the present invention may be a resin mixture (master batch) containing carbon black, and the content of carbon black in 100% by mass of the resin mixture is 0.01 to 40% by mass in one preferred embodiment of the present invention, and 0.01 to 30% by mass in another preferred embodiment of the present invention. The remainder may be a resin component containing the thermoplastic resin of component (a), and as the thermoplastic resin of component (a), specifically, for example: polypropylene resins, polyethylene resins, and mixtures thereof.

[ other ingredients ]

In some embodiments, the resin composition may contain a heat stabilizer, a lubricant, a light stabilizer, an antioxidant, a colorant, a mold release agent, and the like, as long as the problems of the present invention can be solved.

According to several embodiments of the present invention, the resin composition can be prepared by, for example, mixing the components other than the components (C) and (D) using a mixer such as a drum mixer, a henschel mixer, a ribbon mixer, or a kneader. Further, the method of preparing pellets by mixing the components (C) and (D) together and then kneading the mixture with an extruder such as a single-screw or twin-screw extruder, or the method of preparing pellets by melt-kneading the mixture with a kneader such as a heated roll or a Banbury mixer may be employed.

< resin molded article >

The resin molded article according to several embodiments of the present invention will be described below.

A resin molded article according to exemplary embodiment 1 is obtained from a resin composition containing the above-mentioned components (A) to (C) (not containing the component (D) and the component (E)), wherein the resin molded article contains 15 to 30% by mass of a flame retardant (B) and 2.5 to 7.5% by mass of a metal fiber (C), and the balance is the component (A) in a total amount of 100% by mass, and the resin molded article has a flame test result according to the UL94V test method of V-0 or V-1 in a test piece having a thickness of 1.5mm, and satisfies the following requirements (I) to (IV).

(I) The thickness of the resin molded body is 1.5 to 8.0 mm.

(II) the resin molded article self-extinguishes within 5 minutes after the end of a combustion test by the method of Combustion test E described below.

(III) the resin molded article has no open pores in the molded article after a combustion test by the method of the following combustion test E.

(IV) the electromagnetic wave shielding property of the resin molded body based on the KEC method electric field in the frequency range of 1-100 MHz is more than 30 dB.

Combustion test method E: a flat plate (150X 2.0mm) made of the above molded body was used. The flame was contacted from above the plate, facing the center of the plate, for 130 seconds using a flame having a length of 200 mm. The distance from the flame-contacting position of the flat plate to the burner tip was 150 mm.

According to the embodiment of the present invention, the flame test judgment result of the UL94V test method in a test piece having a thickness of 1.5mm is V-0 or V-1, and in a preferred embodiment of the present invention is V-0.

The size and shape of the resin molded article can be appropriately adjusted depending on the application within the range satisfying the following requirement (I). In one embodiment of the present invention, the thickness of the resin molded article is 1.5 to 8.0mm, 2.0 to 6.0mm in one preferred embodiment of the present invention, and 2.0 to 4.0mm in another preferred embodiment of the present invention (requirement (I)).

The resin molded article has self-extinguishing property of extinguishing a fire without applying a fire extinguishing treatment from the outside within 2 minutes after the end of the combustion test by the combustion test method E (requirement (II)). "self-extinguishing" refers to the property of burning in a flame when in contact with the flame, but extinguishing the flame itself for a period of time if away from the flame. According to some embodiments of the present invention, in addition to the method E described above, the self-extinguishing property may be exhibited within 2 minutes after the completion of the combustion test by any one or more of the methods a to D described below.

In the combustion tests a to E in the present invention, the method a is the most mild combustion condition, and then the methods B and C are tests in which the combustion conditions are relatively strict, and the methods D and E are tests in which the combustion conditions are strict.

Combustion test method A: a flat plate (150X 2.0mm) made of the above molded body was used. The flame was contacted from below the plate against the center of the plate for 130 seconds using a 20mm flame in UL 94. The distance from the flame-contacting position of the flat plate to the burner tip was 10 mm.

Method B of combustion test: a flat plate (150X 2.0mm) made of the above molded body was used. The flame was contacted from below the plate against the center of the plate for 130 seconds using a 38mm flame in UL 94. The distance from the flame-contacting position of the flat plate to the burner tip was 20 mm.

Method for combustion test C: a flat plate (150X 2.0mm) made of the above molded body was used. The flame was contacted from below the plate against the center of the plate for 130 seconds using a 125mm flame in UL 94. The distance from the flame-contacting position of the flat plate to the burner tip was 100 mm.

Method for burning test D: a flat plate (150X 2.0mm) made of the above molded body was used. The flame was contacted from below the plate against the center of the plate for 130 seconds using a 125mm flame in UL 94. The distance from the flame-contacting position of the flat plate to the burner tip was 40 mm.

The above-mentioned various burning test methods assume the spontaneous combustibility test in European ECE-R100, and the resin molded article of the present invention having self-extinguishing properties in the above-mentioned various burning test methods can satisfy the regulations of European ECE-R100.

After the combustion test by the above-described combustion test method E, the resin molded article is not perforated (not perforated) by melting of the fired portion of the molded article due to the combustion heat in the fired portion of the molded article, specifically, the fired portion on the surface of the molded article (requirement (III)). The term "open pores" as used herein means pores that penetrate through the surface of the fired molded article in the thickness direction of the molded article, and excludes pores having a maximum diameter of 3mm or less, and non-penetrating pores or depressions. In one embodiment, it is preferable that the molded article has no open pores after the combustion test by at least one of the methods a to D, in addition to the method E.

A resin molded article according to an exemplary embodiment 2 is obtained from a resin composition containing the above components (A) to (D) (without the component (E)), wherein the resin molded article contains 15 to 30% by mass of (B) a flame retardant, (C) 2.5 to 7.5% by mass of a metal fiber, and (D) 5 to 50% by mass of a glass fiber, and the balance is 100% by mass of the component (A), and the resin molded article has V-0 or V-1 in a test piece having a thickness of 1.5mm as determined by a UL94V test method, and satisfies the requirements (I) to (IV).

An exemplary resin molded article of embodiment 3 is obtained from a resin composition containing the above components (A) to (E), wherein the resin molded article contains 15 to 30% by mass of (B) a flame retardant, (C) 2.5 to 7.5% by mass of a metal fiber, (D) 5 to 50% by mass of a glass fiber, and (E) a carbonization accelerator, 0.7 to 5.0% by mass, and the balance is 100% by mass of the component (A), and the resin molded article has a flame test result according to the UL94V test method of V-0 or V-1 in a test piece having a thickness of 1.5mm, and satisfies the requirements of the above components (I) to (IV).

Further, in another exemplary embodiment, embodiment 2 and embodiment 3 may be resin molded bodies satisfying the following requirements (V) and (VI) in addition to the above requirements (I) to (IV).

(V) Total exotherm measured by cone calorimeter exotherm test of the following method was 8MJ/m after 130 seconds from the start of heating²The following.

(VI) when the total heat release was measured by a cone calorimeter heat release test by the following method, no hole was formed in the aluminum foil covering the self-extinguishing resin molded body after 5 minutes had elapsed from the start of heating.

Cone calorimeter exothermicity test: a flat plate-shaped molded article having a size of 100mm X100 mm and a thickness of 2.0mm, which was coated with an aluminum foil (thickness of 12 μm) on the surface other than the heated surface, was used as a sample in accordance with ISO5660-1, and the intensity of radiant heat was measuredDegree of 50kW/m²Heating was carried out for 5 minutes. As the test apparatus, a cone calorimeter C4 (manufactured by Toyo Seiki Seisaku-Sho Ltd.) can be used, for example.

The requirement (V) is 8MJ/m after 130 seconds from the start of heating in a preferred embodiment of the present invention²Hereinafter, in another preferred embodiment of the present invention, the heat resistance is 7.5MJ/m after 130 seconds from the start of heating²The following.

The term "hole" in the element (VI) means a hole penetrating through the aluminum foil in the thickness direction, and does not include a hole having a maximum diameter of 3mm or less, a hole not penetrating, a recess, or the like. In the cone calorimeter exothermic test, the surface of the sample other than the heating surface was coated with an aluminum foil, and therefore, heat was mainly transferred to the coated portion of the surface opposite to the heating surface, and the aluminum foil melted and holes were formed when the temperature exceeded the melting point of aluminum, that is, approximately 660 ℃.

According to some embodiments of the present invention, the electromagnetic wave shielding property of the resin molded body measured using a flat plate (150 mm in length, 150mm in width, 2.0mm in thickness) made of the above molded body based on the KEC method electric field in the frequency range of 1 to 100MHz shows a value exceeding 30dB (requirement (IV)). The method for measuring the electromagnetic wave shielding property can be, for example, the method described in examples.

According to some embodiments of the present invention, the content of each of the components (B), (C) and (D) in the molded article may be within the following range, and a resin mixture (compound) such as a Masterbatch (MB) containing a resin component of a thermoplastic resin containing at least one of the components (B), (C) and (D) and the component (a) may be used.

The resin molded article containing components (A) to (C) (not containing components (D) and (E)) contains 15 to 30% by mass of a flame retardant as component (B) in one embodiment, 17 to 28% by mass in one preferred embodiment of the present invention, 18.5 to 25% by mass in another preferred embodiment of the present invention, and 19 to 25% by mass in yet another preferred embodiment of the present invention. The resin molded article contains 2.5 to 7.5% by mass of the metal fiber as the component (C) in another embodiment, 2.5 to 7.0% by mass in one preferred embodiment of the present invention, 2.5 to 6.0% by mass in another preferred embodiment of the present invention, 3.0 to 5.0% by mass in another preferred embodiment of the present invention, and 3.0 to 4.5% by mass in another preferred embodiment of the present invention. And the sum of them and the rest of the component (A) is 100% by mass.

The resin molded article containing components (a) to (D) (not containing component (E)) contains 15 to 30% by mass of the flame retardant as component (B) in one embodiment, 17 to 28% by mass in one preferred embodiment of the present invention, 18.5 to 25% by mass in another preferred embodiment of the present invention, and 19 to 25% by mass in yet another preferred embodiment of the present invention. The resin molded article contains 2.5 to 7.5% by mass of the metal fiber as the component (C) in another embodiment, 2.5 to 7.0% by mass in one preferred embodiment of the present invention, 2.5 to 6.0% by mass in another preferred embodiment of the present invention, 3.0 to 5.0% by mass in another preferred embodiment of the present invention, and 3.0 to 4.5% by mass in another preferred embodiment of the present invention. In another embodiment, the resin molded article contains 5 to 50% by mass of the glass fiber as the component (D), 10 to 45% by mass in one preferred embodiment of the present invention, and 20 to 40% by mass in another preferred embodiment of the present invention. And the sum of them and the rest of the component (A) is 100% by mass.

The resin molded article containing components (A) to (E) contains 15 to 30% by mass of a flame retardant as component (B) in one embodiment, 17 to 28% by mass in one preferred embodiment of the present invention, 18.5 to 25% by mass in another preferred embodiment of the present invention, and 19 to 25% by mass in yet another preferred embodiment of the present invention. The resin molded article contains 2.5 to 7.5% by mass of the metal fiber as the component (C) in another embodiment, 2.5 to 7.0% by mass in one preferred embodiment of the present invention, 2.5 to 6.0% by mass in another preferred embodiment of the present invention, 3.0 to 5.0% by mass in another preferred embodiment of the present invention, and 3.0 to 4.5% by mass in another preferred embodiment of the present invention. In another embodiment, the resin molded article contains 5 to 50% by mass of the glass fiber as the component (D), 10 to 45% by mass in one preferred embodiment of the present invention, and 20 to 40% by mass in another preferred embodiment of the present invention. In another embodiment, the resin molded article contains 0.7 to 5.0% by mass of a carbonization accelerator as the component (E), 0.7 to 4.0% by mass in one preferred embodiment of the present invention, and 0.8 to 3.5% by mass in another preferred embodiment of the present invention. And the sum of them and the rest of the component (A) is 100% by mass.

According to another embodiment of the present invention, the blending amount of the carbonization accelerator may be 1 to 30 parts by mass, 0.5 to 10 parts by mass in another preferred embodiment of the present invention, 0.5 to 6 parts by mass in another preferred embodiment of the present invention, or 2 to 5 parts by mass in yet another preferred embodiment of the present invention, with respect to 100 parts by mass of the total content of (B-1) and (B-2). When the amount is within the above range, the flame retardant effect is good, extrusion during molding is stable, and further, the mechanical properties of the molded article are good, and the flame retardancy is good.

According to some embodiments, the glass fiber of the component (D) and the carbonization promoter of the component (E) are contained in an amount of 2 to 13% by mass, [ (E)/((D) + (E)) × 100], in a total amount of the component (D) and the component (E), of 2.5 to 10% by mass in another preferred embodiment of the present invention.

According to some embodiments, the content ratio of the component (E) [ (E)/((a) + (B) + (E)) × 100] in the total amount of the polyolefin-based resin of the component (a), (the phosphorus-based flame retardant of the component (B), and the carbonization accelerator of the component (E)) is 1 to 8% by mass in one preferred embodiment of the present invention, 1 to 6% by mass in another preferred embodiment of the present invention, and 3.1 to 6% by mass in another preferred embodiment of the present invention.

The resin molded article containing components (A) to (D) and carbon black (not containing component (E)) contains 15 to 30% by mass of a flame retardant as component (B) in one embodiment, 17 to 28% by mass in one preferred embodiment of the present invention, 18.5 to 25% by mass in another preferred embodiment of the present invention, and 19 to 25% by mass in yet another preferred embodiment of the present invention. The resin molded article contains 2.5 to 7.5% by mass of the metal fiber as the component (C) in another embodiment, 2.5 to 7.0% by mass in one preferred embodiment of the present invention, 2.5 to 6.0% by mass in another preferred embodiment of the present invention, 3.0 to 5.0% by mass in another preferred embodiment of the present invention, and 3.0 to 4.5% by mass in another preferred embodiment of the present invention. In another preferred embodiment, the resin molded article contains 0 to 50% by mass of the glass fiber as the component (D), 5 to 45% by mass in one preferred embodiment of the present invention, 10 to 40% by mass in another preferred embodiment of the present invention, and 20 to 40% by mass in another preferred embodiment of the present invention. In another preferred embodiment, the resin molded article contains 0.03 to 3% by mass of carbon black, 0.1 to 1% by mass in one preferred embodiment of the present invention, and 0.2 to 0.7% by mass in another preferred embodiment of the present invention. And the sum of them and the rest of the component (A) is 100% by mass.

According to some embodiments, the content ratio (% by mass) of the component (B) to the total content of the component (a) and the component (B) in the resin molded article, which is determined by the following formula (B)/[ (a) + (B) ] × 100, is 18 to 40% by mass in a preferred embodiment of the present invention, 20 to 38% by mass in another preferred embodiment of the present invention, 23 to 35% by mass in another preferred embodiment of the present invention, and 28 to 30% by mass in yet another preferred embodiment of the present invention.

According to some embodiments, the content ratio (% by mass) of the component (B) to the total content of the components (a), (C) and (D) in the resin molded article, which is determined by the following formula (B)/[ (a) + (C) + (D) ] × 100, is 23 to 40% by mass in one preferred embodiment of the present invention, 23 to 30% by mass in another preferred embodiment of the present invention, and 23 to 25% by mass in yet another preferred embodiment of the present invention.

According to some embodiments of the present invention, the resin molded article can be molded into various molded articles by a known technique, for example, Injection molding, extrusion molding, vacuum molding, profile molding, foam molding, Injection molding (Injection Press), Press molding, blow molding, gas Injection molding, or the like, using the above resin composition. For example, various molded articles can be formed by injection molding from the viewpoint that the advantages of the present invention as described above can be further shared.

The embodiments and combinations thereof in the embodiments are merely examples, and additions, omissions, substitutions, and other modifications of the embodiments can be appropriately made without departing from the spirit of the present invention. The present invention is not limited to the embodiments, but is defined only by the claims.

Examples

As the component (a), polyolefin resins (a1) to (a6) shown below were used. A

(A1) homopolypropylene, MFR (melt flow Rate) 7, product name "PM 600A", manufactured by Sun Allomer K.K.)

(A3) high-fluidity homopolypropylene, MFR70, product name "PMB 02A", manufactured by Sun Allomer K.K.

(A5) high-flowability propylene-ethylene Block copolymer, MFR60, product name "PMB 60A", manufactured by Sun Allomer K.K.

Maleic anhydride-modified Polypropylene (A6), MFR10(190 ℃ C.. times.0.325 kg), product name "OREVAC CA 100", manufactured by Arkema K.K.

(A7) propylene-ethylene random copolymer, MFR25, product name "PM 921V", manufactured by Sun Allomer K.K.

The following materials were used as component (B).

(B-1) phosphorus flame retardant, product name "FP-2500S", manufactured by ADEKA K.K

(B-2) phosphorus flame retardant, product name "FP-2100 JC", manufactured by ADEKA K.K.)

Resin mixture containing phosphorus flame retardant (B-1) prepared in production example 11

(C) The components: long resin-impregnated stainless Steel fiber bundle prepared in production example 12

(D) The components: chopped glass fibers (ECS03T-480, manufactured by Nippon Denko K.K.) having an average diameter of 13 μm and an average length of 3mm

(E) The components: zinc oxide, Zinc oxide type II, manufactured by Sakai Chemical Industry Co., Ltd

As other components, the following materials were used.

Chopped carbon fibers (HT C413, manufactured by Diko K.K.), the fibers having an average diameter of 7 μm and an average length of 6mm

Carbon black master batch (hereinafter, CBMB), product name "EPP-K-22771", available from POLYCOL corporation (containing 30% by mass of carbon black, and the balance being a mixture of polypropylene and polyethylene)

Stabilizer 1, product name "Irganox 1010", manufactured by BASF JAPAN Co., Ltd

Stabilizer 2, product name "ADEKASTAB PEP 36", manufactured by ADEKA K.K.

Lubricant, product name "Alflow H-50S", manufactured by Nichii oil Co., Ltd. (ethylene bis stearamide)

The evaluation items were measured as follows.

(1)MFR(g/10min)

The measurements were carried out according to ISO1133 at a temperature of 230 ℃ and a load of 2.16 kg.

(2) Tensile Strength (MPa)

The measurement was carried out according to ISO 527.

(3) Flexural Strength (MPa)

Measured according to ISO 178.

(4) Flexural modulus of elasticity (MPa)

Measured according to ISO 178.

(5) Charpy impact strength (kJ/m)²)

The notched Charpy impact strength was determined in accordance with ISO179/1 eA.

(flame retardancy)

A test was conducted on a test piece of 1.5mm in thickness made of the resin compositions of examples and comparative examples by a 20mm flame vertical burning test (V test) of a UL94 bar-shaped test piece (125 mm. times.13 mm. times.1.5 mm).

(electromagnetic wave shielding property)

Electromagnetic wave shielding properties in a frequency range of 1 to 100MHz were evaluated by the KEC method (electric field) using molded articles (150 mm in the vertical direction, 150mm in the horizontal direction, and 2.0mm in thickness).

(evaluation of self-extinguishing property and opening hole based on plate Combustion test)

As the molded article, a flat plate-shaped molded article having a size of 150mm × 150mm and a thickness of 2.0mm was used as a sample, and a case where self-extinguishing occurred in the resin molded article of the present invention within 2 minutes after completion of the combustion test by the above-described combustion test method E was evaluated as "presence (self-extinguishing property)", and a case where self-extinguishing did not occur within 2 minutes was evaluated as "absence (self-extinguishing property)".

Further, the case where the resin molded body had a through hole with a maximum diameter of more than 3mm after self-extinguishing or after extinguishing by blocking air (oxygen) by capping or the like was evaluated as "having (opening)", and the case where no through hole was opened was evaluated as "not having (opening)". In the table, "-" indicates "notV" which is an evaluation out of the UL94 standard in the UL94 burning test, and therefore, the flat plate burning test was not achieved.

(Total exotherm)

A flat plate-shaped molded article having a size of 100mm X100 mm and a thickness of 2.0mm was used as a sample based on ISO5660-1, and a total heat generation amount was measured using a cone calorimeter C4 (manufactured by Toyo Seiki Seisaku-Sho Ltd.) as a test device. The radiant heat intensity was set to 50kW/m²Heating was performed for 5 minutes. The surface of the sample other than the heating surface was coated with aluminum foil (thickness: 12 μm). The total heat release [ MJ/m ] after 130 seconds from the start of heating²]And the presence or absence of the opening of the aluminum foil (visual observation) are shown in table 4.

Production examples 1 to 10 (production of flame-retardant fiber-containing polypropylene composite)

A resin mixture containing a thermoplastic resin of component (A), a flame retardant of component (B), a zinc oxide of component (E), carbon black (master batch) and other additives shown in Table 1 was mixed in a tumbler according to the formulation shown in Table 1, and then fed from a hopper of a twin-screw extruder ("TEX 30. alpha." manufactured by Nippon Steel Co., Ltd., 230 ℃ C.), and further, a chopped glass fiber and a chopped carbon fiber of component (D) were fed from a side feeder, and melt-kneaded and shaped to obtain a resin mixture (pellet having a diameter of 3.0 mm. times.length of 3.0 mm) shown in Table 1.

Production example 11 (production of resin mixture containing phosphorus flame retardant (B-1))

After dry-blending 30 parts by mass of component (A7), 0.20 part by mass of stabilizer 1, 0.20 part by mass of stabilizer 2, and 2.50 parts by mass of a lubricant, the dry-blended components were fed from a hopper of a twin-screw extruder ("TEX 30. alpha." manufactured by Nippon Steel Co., Ltd., 230 ℃). Further, 70 parts by mass of the component (B-1) was fed from a side feeder, and melt-kneaded and shaped to obtain a resin mixture (pellets 3.0mm in diameter. times.3.0 mm in length) containing the phosphorus-based flame retardant (B-1) shown in Table 2.

Production example 12 (production of resin-impregnated stainless Steel fiber bundle)

Stainless steel fiber bundles (about 7000 fiber bundles) as component (C) were passed through a crosshead die, and a mixture of component (a5) (component (a 6): stabilizer 1: stabilizer 2 ═ 48.0:1.50:0.25:0.25 (parts by mass) was melted and supplied to impregnate the stainless steel fiber bundles, thereby obtaining resin-impregnated stainless steel long fiber bundles. Then, the resin-impregnated fiber bundle (pellet) containing 50 mass% of stainless steel fibers (C) was obtained by shaping the resin with a shaping nozzle at the outlet of a crosshead die (diameter: 3.5mm), shaping the resin with a shaping roller, and cutting the shaped resin into 7mm pieces with a pelletizer. As a result of cutting and confirming the resin-impregnated fiber bundle thus obtained, the stainless steel fibers were substantially parallel in the longitudinal direction, and the resin was impregnated into the central portion.

Examples 1 and 2

The fiber-containing polypropylene flame-retardant composite of production example 1 and the resin-impregnated fiber bundle of production example 12 were mixed in a tumbler according to the formulation shown in Table 2, and then charged into an injection molding machine (FANUC ROBOSHOT. alpha. -S150iA, manufactured by FANUC corporation, mold 50 ℃ C., molding temperature 220 ℃ C.) to obtain a resin molded article.

Example 3

A resin molded article was obtained by mixing the component (a), the resin mixture containing the flame retardant (B) of production example 11, and the resin-impregnated long metal fiber strand of production example 12 in a tumbler according to the compounding ingredients shown in table 2, and then by the same production method as in example 1.

Comparative example 1

A resin molded article was obtained by a production method similar to that of example 1, after mixing the fiber-containing polypropylene flame-retardant composite of production example 1 and the resin-impregnated fiber bundle of production example 12 in a tumbler according to the compounding ingredients shown in table 2.

Comparative examples 2 to 8

The fiber-containing polypropylene flame-retardant composites of production examples 1 to 7 were put into an injection molding machine (FANUC ROBOSHOT. alpha. -S150iA, manufactured by FANUC corporation, mold 50 ℃ C., molding temperature 220 ℃ C.) to obtain resin moldings. The evaluation results of examples 1 to 3 and comparative examples 1 to 8 are shown in Table 2.

In examples 1 to 3, resin molded bodies having high mechanical strength in addition to high self-extinguishing properties, flame retardancy, and electromagnetic wave shielding properties were obtained, and in examples 1 and 2, resin molded bodies having higher specific tensile strength (tensile strength/density), specific flexural strength (flexural strength/density), and specific elastic modulus (flexural elastic modulus/density) were obtained. In example 3, a resin molded article was obtained which was lighter in weight, i.e., lower in density, than those of examples 1 and 2 containing glass fibers, and which had self-extinguishing properties, flame retardancy, and electromagnetic wave shielding properties equivalent to those of examples 1 and 2.

Examples 4 to 6

The fiber-containing polypropylene flame-retardant compounds of production examples 8 to 10 shown in Table 1 and the resin-impregnated fiber bundles of production example 12 were mixed in a tumbler according to the formulation shown in Table 3, and then charged into an injection molding machine (FANUC ROBOSHOT. alpha. -S150iA, manufactured by FANUC corporation, mold 50 ℃ C., molding temperature 220 ℃ C.), to obtain resin molded articles. The evaluation results are shown in Table 3.

[ Table 3]

In table 3, CF denotes carbon fiber, and SF denotes stainless steel fiber.

[ Table 4]

Industrial applicability

The resin molded article of the present invention has flame retardancy and self-extinguishing properties that satisfy the standards relating to the fire resistance test such as ECE-R100, and therefore can be used for all or part of the case of a battery module, a peripheral part (a connecting part or the like), a charger connector for an electric vehicle, a holder for a battery capacitor, a case for a battery capacitor, or a case for a charging stand for an electric vehicle in a battery-type electric transportation device such as an electric vehicle, an electric bus, an electric truck, an electric motorcycle, an electric wheelchair, or a stand-up two-wheeled electric vehicle, particularly an electric transportation device using a stationary battery that cannot be attached and detached.

Further, since the resin molded article according to the example of the present invention has electromagnetic wave shielding properties, it is possible to prevent noise of the car radio from being generated by unnecessary radio waves generated from the case or the member. Further, the resin molded body exemplified in the present invention can be used for a housing of an electric/electronic device other than a vehicle, and the like.