TWI680154B - Flame retardant resin composition, molded article, insulating wire, cable and optical fiber cable using the same - Google Patents

Abstract

The present invention discloses a flame-retardant resin composition containing at least a polyolefin resin (A), a phosphate compound (B), and an organic phosphorus compound (C). The phosphate compound (B) is a salt containing a phosphoric acid represented by the following general formula (1) and an amine compound having at least one amine group in the molecule, and the organic phosphorus compound (C) is represented by the following general formula (2) , (In the above general formula (1), m represents an integer from 1 to 100), (In the above general formula (2), X ¹ and X ² are the same or different and are represented by the following general formula (3)), (In the above general formula (3), AL is a branched or linear aliphatic hydrocarbon group having 1 to 5 carbon atoms, Ar is a phenyl group, a naphthyl group or an anthryl group which may have a substituent, and is bonded to any of AL Carbon atom. N represents an integer of 1 to 3).

Description

Flame-retardant resin composition, formed body using the same, insulated wire, cable, and optical fiber cable

The present invention relates to a flame-retardant resin composition, a molded body using the same, insulated wires, cables, and optical fiber cables.

In recent years, the viewpoint of fire prevention for OA equipment, building materials, automotive interior materials, electronic components, metal cables, and fiber optic cables, such as televisions, notebook computers, and photocopiers, has become more stringent than the requirements for flame resistance. Therefore, materials with higher flame resistance tend to be used.

Such a material having high flame resistance is known as a flame retardant resin composition obtained by adding a phosphate compound to a polyolefin resin (see Patent Document 1 below). Prior Art Literature Patent Literature

Patent Document 1: Japanese Patent Application Laid-Open No. 2014-65822

Problems to be solved by the invention

The flame-retardant resin composition described in the above Patent Document 1 has excellent flame retardancy. However, the flame retardant resin composition described in Patent Document 1 has room for improvement in terms of processability.

Therefore, there is a need for a flame-retardant resin composition that can improve processability while ensuring excellent flame-retardant properties.

In view of the foregoing, it is an object of the present invention to provide a flame-retardant resin composition that improves the processability while ensuring excellent flame retardancy, and uses a molded article, insulated wire, cable, and optical fiber cable. Problem solving

In order to solve the above-mentioned problems, the present inventors have intensively reviewed and found that the flame-retardant resin composition obtained by adding a specific proportion of a specific phosphate compound and a specific organic phosphorus compound to the polyolefin resin can solve the above-mentioned problems.

That is, the present invention contains a polyolefin resin (A), a phosphate compound (B), and an organic phosphorus compound (C). The phosphate compound (B) contains a phosphoric acid represented by the following general formula (1), and a molecule A salt of an amine compound having at least one amine group therein, and the organic phosphorus compound (C) is a flame-retardant resin composition represented by the following general formula (2), (In the above general formula (1), m represents an integer of 1 to 100), (In the above general formula (2), X ¹ and X ² are the same or different, and are represented by the following general formula (3)), (In the above general formula (3), AL is a branched or linear aliphatic hydrocarbon group having 1 to 5 carbon atoms, Ar is a phenyl group, a naphthyl group, or an anthryl group which may have a substituent, and is optionally bonded to AL Carbon atom. N represents an integer of 1 to 3).

The flame retardant resin composition of the present invention can improve processability while ensuring excellent flame retardant properties.

The inventors have inferred that the reason why the excellent flame retardancy can be ensured by the flame retarded resin composition of the present invention is as follows.

That is, since the phosphate compound is a salt containing an phosphoric acid represented by the following general formula (1) and an amine compound having at least one amine group in the molecule, a fine foaming heat insulation is generated when the flame-retardant resin composition is burned. Floor. Therefore, it is possible to suppress the combustion of the polyolefin resin and impart self-extinguishing properties to the flame-retardant resin composition. In this case, when other flame retardants such as a metal hydroxide or a polysiloxane compound are used in combination with the above-mentioned phosphate compound, the formation of a fine foamed heat-insulating layer is hindered. Relatively, it is inferred that the organophosphorus compound represented by the general formula (2) can suppress the combustion of polyolefin resin by capturing radicals in a solid phase. In addition, since the above-mentioned organic phosphorus compound holds a phosphonic acid compound in the skeleton, it is inferred that the organic phosphorus compound has good compatibility with a flame retardant formed from a phosphate compound. In addition, the above-mentioned organic phosphorus compound has the function of promoting carbonization when the skeleton is burned. Therefore, it is different from other flame retardants such as metal hydroxides and polysiloxane compounds, and will not hinder fine foam insulation. Layer generation. In addition, it is inferred that the temperature at which the flame-retardant resin composition of the present invention generates a trap for radicals is extremely close to the formation temperature of the fine foamed heat-insulating layer. Therefore, it is inferred that the excellent flame retardancy can be ensured by the flame retardant resin composition of the present invention.

The reason that the processability can be improved by the flame-retardant resin composition of the present invention has not been determined, but the inventors have inferred the following.

That is, the molecular structure of the organic phosphorus compound is a planar structure, so there are few steric obstacles. Therefore, it is estimated that the use of the phosphate compound and the organic phosphorus compound in combination can improve the fluidity when the flame-retardant resin composition is processed. Therefore, it is inferred that the workability of the flame-retardant resin composition can be improved.

In the flame-retardant resin composition, it is preferable to add the phosphate compound (B) in a proportion of more than 0 parts by mass and 120 parts by mass or less with respect to 100 parts by mass of the polyolefin resin (A).

At this time, when the addition ratio of the phosphate compound to 100 parts by mass of the polyolefin resin (A) is 0 parts by mass, more excellent flame retardancy can be obtained in the flame-retardant resin composition. In addition, when the addition ratio of the phosphate compound to 100 parts by mass of the polyolefin resin (A) exceeds 120 parts by mass, processability can be further improved.

In the flame-retardant resin composition, the organic phosphorus compound (C) is preferably added in a proportion of more than 0 parts by mass and 50 parts by mass or less with respect to 100 parts by mass of the polyolefin resin (A).

At this time, when the addition ratio of the organic phosphorus compound (C) to 100 parts by mass of the polyolefin resin (A) is 0 parts by mass, or when it is more than 50 parts by mass, the processing of the flame-retardant resin composition can be further improved. And flame retardant.

In the flame-retardant resin composition, X ¹ and X ² in the general formula (2) are preferably a benzyl group.

At this time, the flame-retardant resin composition can have better processability than when X ¹ and X ² in the general formula (2) are not benzyl.

In the flame-retardant resin composition, m in the general formula (1) is 1 to 2, and the amine compound is preferably an amine compound containing a triazine ring, an amine compound containing a piperazine ring, and an amine containing a triazine ring. A mixture of compounds, ammonia or urea urea.

In this case, the flame retardancy of the flame retarded resin composition can be effectively improved.

In the flame-retardant resin composition, the amine compound is preferably composed of a mixture of a piperazine ring-containing amine compound and a triazine ring-containing amine compound.

In this case, the flame retardancy of the flame-retardant resin composition can be further improved compared to when the amine compound is not composed of the above-mentioned mixture.

In the flame-retardant resin composition, the fluorine-based anti-drip agent (D) is preferably added in a proportion of more than 0 parts by mass and 5 parts by mass or less with respect to 100 parts by mass of the polyolefin resin (A).

At this time, when the addition ratio of the fluorine-based anti-dripping agent (D) to 100 parts by mass of the polyolefin resin (A) is 0 parts by mass, the anti-dripping performance can be found. Compared with the fluorine-based anti-dripping agent (D), ) When the addition ratio is more than 5 parts by mass with respect to 100 parts by mass of the polyolefin resin (A), excessively increasing the melt viscosity of the flame retardant resin composition can be more sufficiently suppressed, and the processability of the flame retardant resin composition can be further improved.

In the flame-retardant resin composition, the polyolefin resin (A) preferably contains a polypropylene resin.

At this time, the flame-retardant resin composition can have more excellent heat resistance than when the polyolefin resin (A) does not contain a polypropylene resin.

In the flame-retardant resin composition, the polyolefin resin (A) preferably contains an elastomer.

At this time, the flame retardant resin composition can have more excellent impact resistance and cold resistance than when the polyolefin resin (A) does not contain an elastomer.

In the flame-retardant resin composition, the content of the elastomer in the polyolefin resin (A) is preferably 60% by mass or less.

At this time, when the content of the elastomer in the polyolefin resin (A) exceeds 60% by mass, the flame retardancy of the flame-retardant resin composition can be further improved.

The present invention is a molded article containing the flame-retardant resin composition.

Since this molded article contains a flame retardant resin composition that can improve processability while ensuring excellent flame retardant properties, it is suitable for various applications in which excellent flame retardant properties and excellent processability must be established simultaneously.

The present invention is also provided with a conductor and an insulation layer covering the conductor, and the insulation layer is an insulated wire composed of the flame-retardant resin composition.

Since the insulated wire of the present invention contains an insulating layer composed of a flame retardant resin composition that can ensure excellent flame retardancy and improve processability, it can have excellent flame retardancy and good appearance.

The present invention is an insulated wire including a conductor and an insulating layer covering the conductor, and a covering layer covering the insulated wire, and at least one of the insulating layer and the covering layer is composed of the flame-retardant resin. Cable made of objects.

Since at least one of the insulating layer and the covering layer of the cable of the present invention is made of a flame-retardant resin composition that can ensure excellent flame retardancy and improve processability, it can have excellent flame retardancy and good appearance.

Furthermore, the present invention relates to an optical fiber cable, which is provided with an optical fiber and a covering portion covering the optical fiber, the covering portion is an insulator having the covering optical fiber, and the insulation system is composed of the above-mentioned flame-retardant resin composition.

Among the coated portions of the optical fiber cable system of the present invention, the coated optical fiber insulator is composed of a flame retardant resin composition that ensures excellent flame retardancy and improves processability, so it can have excellent flame retardancy and good appearance. Effect of the invention

According to the present invention, it is possible to provide a flame retardant resin composition that improves the processability while ensuring excellent flame retardancy, a molded body using the composition, an insulated wire, a cable, and an optical fiber cable.

Hereinafter, embodiments of the present invention will be described in detail.

<Flame-resistant resin composition> The flame-retardant resin composition of the present invention contains a polyolefin resin (A) and a flame retardant, and the flame retardant contains a phosphate compound (B) and an organic phosphorus compound (C). At this time, the phosphate compound (B) is a salt containing the phosphoric acid represented by the following general formula (1) and an amine compound having at least one amine group in the molecule, and the organic phosphorus compound (C) is the following general formula (2) As indicated, (In the above general formula (1), m represents an integer of 1 to 100), (In the above general formula (2), X ¹ and X ² are the same or different and are represented by the following general formula (3)), (In the above general formula (3), AL is a branched or linear aliphatic hydrocarbon group having 1 to 5 carbon atoms, Ar is a phenyl group, a naphthyl group, or an anthryl group which may have a substituent, and is optionally bonded to AL Carbon atom. N represents an integer of 1 to 3).

The flame retardant resin composition of the present invention can improve processability while ensuring excellent flame retardant properties.

The polyolefin resin (A), the phosphate compound (B), and the organic phosphorus compound (C) will be described in detail below.

(A) Polyolefin resin Polyolefin resin is a substance having a structural unit derived from an olefin (unsaturated aliphatic hydrocarbon) in the molecule. In addition to a single polymer of an olefin and a copolymer of dissimilar olefins, Contains copolymers of olefins and non-olefins. Specific examples of the polyolefin resin include polyethylene (PE), polypropylene (PP), ethylene-ethyl acrylate copolymer (EEA), ethylene-vinyl acetate copolymer (EVA), ethylene-propylene copolymer, and elastomer. These can be used alone or in combination of two or more.

Elastomers such as styrene-butadiene rubber (SBR), styrene-ethylene-butadiene-styrene copolymer (SEBS copolymer), styrene-propylene-butadiene-styrene copolymer (SPBS copolymerization Material), styrene-butadiene-styrene copolymer (SBS copolymer), olefin crystal-ethylene-butadiene-olefin crystal copolymer (CEBC copolymer), styrene-isoprene-styrene copolymerization Block copolymers of olefins and styrenes such as SIS copolymers, and hydrides (hydrogenated SBR, hydrogenated SEBS copolymer, hydrogenated SPBS copolymer, hydrogenated SBS copolymer, hydrogenated SIS) Copolymer). These can be used alone or in combination of two or more.

The polyolefin resin (A) is preferably a polypropylene resin contained in the above specific examples. At this time, the flame-retardant resin composition has better heat resistance than when the polyolefin resin (A) does not contain a polypropylene resin.

The polyolefin resin (A) preferably contains an elastomer in the above specific examples. At this time, the flame-retardant resin composition can have more excellent impact resistance and cold resistance than when the polyolefin resin (A) does not contain an elastomer.

The polyolefin resin (A) preferably contains an elastomer in addition to the polypropylene resin. At this time, the flame-retardant resin composition can have more excellent impact resistance and cold resistance than when the polyolefin resin (A) does not contain an elastomer. When the polyolefin resin (A) does not contain a polypropylene resin, the flame-retardant resin composition can have more excellent heat resistance.

In this case, the content of the elastomer in the polyolefin resin (A) is not particularly limited, but is preferably 60% by mass or less. At this time, when the content of the elastomer in the polyolefin resin (A) exceeds 60% by mass, the flame retardancy of the flame-retardant resin composition can be further improved. It is more preferable that the content of the elastomer in the polyolefin resin (A) is less than 40% by mass. At this time, the flame retardancy of the flame-retardant resin composition can be further improved compared to when the content of the elastomer in the polyolefin resin (A) is 40% by mass or more. The content of the elastomer in the polyolefin resin (A) is particularly preferably 20% by mass or less. At this time, when the content of the elastomer in the polyolefin resin (A) exceeds 20% by mass, the flame retardancy of the flame-retardant resin composition can be further improved. However, the content of the elastomer in the polyolefin resin (A) is preferably 10% by mass or more. At this time, when the content of the elastomer in the polyolefin resin (A) is less than 10% by mass, the processability of the flame-retardant resin composition can be further improved.

(B) Phosphate compound As described above, the phosphate compound is an amine phosphate compound containing a salt of the phosphoric acid represented by the general formula (1) and an amine compound having at least one amine group in the molecule. In this case, the "amine group" includes not only -NH ₂ but also -NH-.

In the general formula (1), m is preferably 1 or 2. In this case, the flame-retardant resin composition can have more excellent flame retardancy than when m is 3 or more.

Specific examples of the phosphoric acid represented by the general formula (1) include polyphosphoric acid such as pyrophosphoric acid and triphosphoric acid, and monophosphoric acid such as orthophosphoric acid.

Examples of the amine compound include an aliphatic diamine, an amine compound containing a piperazine ring, an amine compound containing a triazine ring, ammonia, and pulse urea. These can be used alone or in combination of two or more.

The aliphatic diamine is preferably a substance having 1 to 15 carbon atoms. Such aliphatic diamines are, for example, N, N, N ', N'-tetramethyldiaminomethane, ethylenediamine, N, N'-dimethylethylenediamine, N, N' -Diethyl ethylenediamine, N, N-dimethyl ethylene diamine, N, N-diethyl ethylene diamine, N, N, N ', N'-tetramethyl ethylene Diamine, N, N, N ', N'-diethylethylenediamine, 1,2-propanediamine, 1,3-propanediamine, tetramethylenediamine, pentamethyldiamine , Hexamethyldiamine, 1,7-diaminoheptane, 1,8-diaminooctane, 1,9-diaminononane and 1,10-diaminodecane. In this case, they can be used alone or in combination of two or more.

Piperazine ring-containing amine compounds such as piperazine, trans-2,5-dimethylpiperazine, 1,4-bis (2-aminoethyl) piperazine, 1,4-bis (3-amine Ethylpropyl) piperazine. In this case, they can be used alone or in combination of two or more.

Triazine ring-containing amine compounds such as melamine, methylguanamine, benzoguanamine, acrylic guanamine, 2,4-diamino-6-nonyl-1,3,5-triazine, 2,4 -Diamino-6-hydroxy-1,3,5-triazine, 2-amino-4,6-dihydroxy-1,3,5-triazine, 2,4-diamino-6-methyl Oxy-1,3,5-triazine, 2,4-diamino-6-ethoxy-1,3,5-triazine, 2,4-diamino-6-propoxy-1 , 3,5-triazine, 2,4-diamino-6-isopropoxy-1,3,5-triazine, 2,4-diamino-6-mercapto-1,3,5- Triazine, 2-amino-4,6-dimercapto-1,3,5-triazine and melamine condensates of melam, meleramine, etc. In this case, they can be used alone or in combination of two or more.

When m in the general formula (1) representing a phosphoric acid is 1 to 2, the amine compound is preferably a compound containing a triazine ring, a mixture of a piperazine ring-containing amine compound and a triazine ring-containing amine compound, ammonia, or a pulse. Base urea. In this case, the flame retardancy of the flame retarded resin composition can be effectively improved.

The amine compound is preferably a mixture of a piperazine ring-containing amine compound and a triazine ring-containing amine compound. In this case, the flame retardancy of the flame-retardant resin composition can be further improved compared to when the amine compound is not composed of the above-mentioned mixture. In this case, the content ratio of the piperazine ring-containing amine compound in the mixture is preferably 20 to 55 mass%. At this time, the flame-retardant resin composition can have more excellent flame retardancy than when the content ratio of the piperazine ring-containing amine compound in the mixture exceeds the above range.

The addition ratio of the phosphate compound (B) with respect to 100 parts by mass of the polyolefin resin (A) is preferably more than 0 parts by mass and 120 parts by mass or less. At this time, when the addition ratio of the phosphate compound to 100 parts by mass of the polyolefin resin (A) is 0 parts by mass, the flame-retardant resin composition can have more excellent flame retardancy. When the addition ratio of the phosphate compound to 100 parts by mass of the polyolefin resin (A) exceeds 120 parts by mass, the processability can be further improved.

The addition ratio of the phosphate compound (B) is preferably 5 parts by mass or more, more preferably 15 parts by mass or more, and particularly preferably 20 parts by mass or more.

The addition ratio of the phosphate compound (B) to 100 parts by mass of the polyolefin resin (A) is more preferably 90 parts by mass or less. At this time, when the addition ratio of the phosphate compound (B) to 100 parts by mass of the polyolefin resin (A) exceeds 90 parts by mass, the processability of the flame-retardant resin composition can be further improved. In order to ensure excellent flame retardancy and improve processability, the addition ratio of the phosphate compound (B) to 100 parts by mass of the polyolefin resin (A) is more preferably 70 parts by mass or less. In order to make the specific gravity of the flame-retardant resin composition particularly small, the addition ratio of the phosphate compound (B) to 100 parts by mass of the polyolefin resin (A) is preferably 50 parts by mass or less, and more preferably 40 parts by mass. the following.

(C) Organic phosphorus compound The organic phosphorus compound (C) is represented by the general formula (2) as described above.

X ¹ and X ² in the general formula (2) are represented by the general formula (3). X ¹ and X ² may be the same or different from each other.

The AL in the above general formula (3) is a branched or linear aliphatic hydrocarbon group having 1 to 5 carbon atoms, but the carbon number of the aliphatic hydrocarbon group is preferably 1 or 2. In addition, Ar in the general formula (3) is a phenyl group, a naphthyl group, or an anthryl group which may have a substituent, and is bonded to an arbitrary carbon atom in AL. Among them, Ar is preferably phenyl. In the above general formula (3), n is an integer of 1 to 3, but 1 or 2 is preferable.

X ¹ and X ² in the general formula (2) are particularly preferably benzyl (phenylmethyl). At this time, the flame-retardant resin composition can have better processability than when X ¹ and X ² in the general formula (2) are not benzyl.

The organic phosphorus compound (C) is preferably added in an amount of 0 parts by mass or more and 50 parts by mass or less with respect to 100 parts by mass of the polyolefin resin (A). At this time, when the addition ratio of the organic phosphorus compound (C) to 100 parts by mass of the polyolefin resin (A) is 0 parts by mass, or 50 parts by mass or more, the processing of the flame-retardant resin composition can be further improved. And flame retardant.

The addition ratio of the organic phosphorus compound (C) to 100 parts by mass of the polyolefin resin (A) is preferably 1 part by mass or more. At this time, when the addition ratio of the organic phosphorus compound (C) to 100 parts by mass of the polyolefin resin (A) is less than 1 part by mass, the flame-retardant resin composition can obtain more excellent processability and flame retardancy. . From the viewpoint of further improving the processability and flame retardancy of the flame retardant resin composition, the addition ratio of the organic phosphorus compound (C) to the polyolefin resin (A) 100 parts by mass is more preferably 2.5 parts by mass or more. It is more preferably 5 parts by mass or more, and particularly preferably 10 parts by mass or more.

The addition ratio of the organic phosphorus compound (C) to 100 parts by mass of the polyolefin resin (A) is preferably 45 parts by mass or less. At this time, when the addition ratio of the organic phosphorus compound (C) to 100 parts by mass of the polyolefin resin (A) exceeds 45 parts by mass, the processability and flame retardancy of the flame-retardant resin composition can be further improved. In order to reduce the specific gravity of the flame-retardant resin composition, the addition ratio of the organic phosphorus compound (C) to 100 parts by mass of the polyolefin resin (A) is preferably 40 parts by mass or less, and more preferably 30 parts by mass or less. Particularly preferred is 20 parts by mass or less.

The flame-retardant resin composition of the present invention may contain a fluorine-based anti-drip agent (D) in addition to the polyolefin resin (A), the phosphate compound (B), and the organic phosphorus compound (C). The fluorine-based anti-dripping agent (D) will be described in detail below.

(D) Fluorine-based anti-dripping agent (D) Fluorine-based anti-dripping agent (D) may contain a fluorine-containing fluorinated compound, which can prevent resin dripping (drip) during combustion. Such fluorine-containing compounds include, for example, fluorine-based resins such as polytetrafluoroethylene (hereinafter referred to as "PTFE"), polyvinylidene fluoride, and polyhexafluoropropylene. Further, the fluorine-containing compound may be an unmodified fluorine-containing compound or a modified fluorine-containing compound, but is preferably a modified one. At this time, compared with the case where the fluorine-containing compound is not modified, the fluorine-containing compound can be fibrillated efficiently, and the dispersibility of the flame-retardant resin composition can be further improved. As a result, the anti-dripping function of the anti-dripping agent (D) can be further improved. In addition, since the melt tension of the flame-retardant resin composition can be further increased, the processability and moldability of the flame-retardant resin composition can be further improved. Modified fluorine-containing compounds such as acid modified polytetrafluoroethylene.

The fluorine-based anti-drip agent (D) is added in a proportion of more than 0 parts by mass and 5 parts by mass or less with respect to 100 parts by mass of the polyolefin resin (A). At this time, when the addition ratio of the fluorine-based anti-dripping agent (D) to 100 parts by mass of the polyolefin resin (A) is 0 parts by mass, the anti-dripping performance can be found and compared with the polyolefin resin (A). When the addition ratio of 100 parts by mass of the fluorine-based anti-dripping agent (D) exceeds 5 parts by mass, the melt viscosity of the flame-retardant resin composition can be more sufficiently suppressed, and the processability of the flame-retardant resin composition can be further improved.

The addition ratio of the fluorine-based anti-drip agent (D) to 100 parts by mass of the polyolefin resin (A) is more preferably 0.2 parts by mass or more. At this time, the flame-retardant resin composition can have more excellent flame retardancy than the fluorine-based anti-drip agent (D) added ratio of less than 0.2 parts by mass relative to 100 parts by mass of the polyolefin resin (A). The addition ratio of the fluorine-based anti-drip agent (D) to 100 parts by mass of the polyolefin resin (A) is preferably 2 parts by mass or more.

The flame retardant resin composition may be provided with an antioxidant, a thermal deterioration inhibitor, an ultraviolet absorber, an ultraviolet deterioration inhibitor, an antifog agent, a cross-linking agent, and Foaming agent, conductive filler, heat dissipating agent, color pigment, etc.

The flame-retardant resin composition can be obtained by kneading a polyolefin resin (A), a phosphate compound (B), an organic phosphorus compound (C), and a fluorine-based anti-drip agent (D) as necessary. During the kneading, the heat necessary for imparting the molten polyolefin resin (A) with the shearing force necessary for dispersing the phosphate compound (B), the organic phosphorus compound (C), and the anti-dripping agent (D) when necessary can be used. Processing is performed by a kneading machine. As the kneading machine, for example, an open roll, a biaxial extruder, a Banbury mixer, a pressure kneader, and the like can be used.

<Molded Article> 次 Next, a molded article of the present invention will be described.

The molded article of the present invention contains the above-mentioned flame-retardant resin composition. Since this molded article contains a flame retardant resin composition that improves the processability while ensuring excellent flame retardancy, it is suitable for various applications where it is necessary to establish both excellent flame retardance and excellent processability. Such applications are, for example, TV back panels, capacitor boxes, insulation films inside keyboards, panels inside heaters, flame-resistant sheets for buildings, instrument panels for automobiles, packaging materials, and housings for home appliances.

The shape of the formed body of the present invention is, for example, a sheet shape, a plate shape, etc., but the shape of the formed body is preferably a sheet shape.

In addition, the thickness of the formed body is not particularly limited, but even if the formed body of the present invention has a thickness of 5 mm or less, the workability can be improved while ensuring excellent flame retardancy.

The molded body can be obtained by, for example, forming a flame-retardant resin composition by using an extrusion molding method, an injection molding method, a vacuum molding method, a pressure molding method, or the like. The formed body may be composed of a flame retardant resin composition monomer, or a combination of a flame retardant resin composition and a reinforcing material such as glass fiber woven cloth and paper depending on the application.

<Cable> The cable of the present invention will be described next with reference to FIGS. 1 and 2. Fig. 1 is a partial side view showing a cable-embodiment of the present invention. FIG. 2 is a cross-sectional view taken along the line II-II of FIG. 1.

As shown in FIGS. 1 and 2, the cable 10 is a tubular covering layer 3 including an insulated wire 4 and a covered insulating wire 4. The insulated wire 4 is a tubular insulating layer 2 having a conductor 1 and a covered conductor 1.

In this case, the tubular insulating layer 2 and the coating layer 3 are composed of the above-mentioned flame-retardant resin composition, and the above-mentioned flame-retardant resin composition can improve processability while ensuring excellent flame-retardant properties. Therefore, the insulating layer 2 and the coating layer 3 composed of the flame-retardant resin composition can have excellent flame-retardant properties and good appearance. Therefore, the cable 10 can have excellent flame resistance and good appearance.

(Conductor) The conductor 1 may be constituted by only one prime line, or may be constituted by bundling a plurality of prime lines. The diameter of the conductor 1 and the material of the conductor are not particularly limited, and can be appropriately determined depending on the application. As the material of the conductor 1, for example, copper, aluminum, or an alloy containing these is preferable, but a conductive material such as a carbon material may also be used as appropriate.

(Covering Layer) The covering layer 3 is a so-called bushing that protects the insulating layer 2 from physical or chemical damage.

<Fiber Optic Cable> Next, the optical fiber cable of the present invention will be described with reference to FIG. 3. Fig. 3 is a sectional view showing an embodiment of an optical fiber cable according to the present invention.

As shown in FIG. 3, the optical fiber cable 20 includes two tension members 22 and 23, an optical fiber 24, and a covering portion 25 covering the optical fiber cable 20. At this time, the optical fiber 24 is provided so as to penetrate the coating portion 25. The covering portion 25 is composed of an insulator covering the optical fiber 24, and the insulating system is composed of the flame-retardant resin composition that constitutes the insulating layer 2 and the covering layer 3 of the insulated wire 4 in the embodiment described above. In addition, the insulation system constituting the covering portion 25 may be directly covered with the optical fiber 24 (see FIG. 3), or may be covered indirectly.

The coating portion 25 is composed of the flame-retardant resin composition, and the flame-retardant resin composition can improve the processability while ensuring excellent flame-retardant properties. Therefore, the coating portion 25 made of the flame-retardant resin composition can have excellent flame-retardant properties and good appearance. Therefore, the optical fiber cable 20 can have excellent flame resistance and good appearance.

This invention is not limited to the said embodiment. For example, the cable of the above embodiment uses the cable 10 having one insulated wire 4, but the cable of the present invention is not limited to the cable having one insulated wire 4, and may be a cable having two or more insulated wires 4 inside the coating layer 3. . A resin portion made of polypropylene or the like may be provided between the covering layer 3 and the insulated wire 4.

In the above embodiment, the insulating layer 2 and the covering layer 3 of the insulated wire 4 are composed of the above-mentioned flame-retardant resin composition, but the insulating layer 2 may be composed of a general insulating resin, and only the covering layer 3 is composed of It consists of the said flame-resistant resin composition.

The covering portion 25 in the optical fiber cable 20 is made of an insulator. However, the covering portion 25 may have a covering body covering the insulator. At this time, the covering body may be formed or not formed of the flame-resistant resin composition that constitutes the insulating layer 2 and the covering layer 3 of the insulated wire 4 in the above embodiment, but the insulating layer 2 and the covering that constitute the insulated wire 4 in the above embodiment The layer 3 is preferably composed of a flame-retardant resin composition.

In the above-mentioned embodiment, the optical fiber cable 20 includes the tension members 22 and 23, but the tension member in the optical fiber cable of the present invention is not necessary and can be omitted. Examples

Hereinafter, the content of the present invention will be described more specifically using examples, but the present invention is not limited to the following examples.

(Examples 1 to 112 and Comparative Examples 1 to 46) 聚烯烃 Add polyolefin resin (A), phosphate compound (B), organic phosphorus compound (C), and fluorine-based anti-drip agent in the amounts shown in Tables 1 to 22. After (D), kneading was performed at 180 ° C using an open roll to obtain a flame-retardant resin composition. In addition, the unit of the addition amount of each additional component in Table 1-Table 22 is a mass part.

Specifically, the polyolefin resin (A), the phosphate compound (B), the organic phosphorus compound (C), and the anti-drip agent (D) are used as described below. (A) Polyolefin resin (A1) block copolymer of ethylene and propylene (b-EP-1, manufactured by Prima AG, MFR = 3.5g / 10min) (A2) block copolymer of ethylene and propylene ( b-EP-2, made by Pleum Corporation, MFR = 30g / 10min) (A3) Homopolypropylene (h-PP, made by Pleme Corporation) (A4) High-density polyethylene (HDPE, Japanese polyethylene) Co., Ltd.) (A5) Linear low-density polyethylene (LLDPE, manufactured by Sumitomo Chemical Co., Ltd.) (A6) Modified polypropylene resin (PP elastomer, manufactured by Mitsui Chemicals Co., Ltd.) (A7) Hydrogenated styrene butadiene Ethylene rubber (hydrogenated SBR, manufactured by JSR Corporation) (A8) olefin crystal ethylene butene olefin block copolymer (CEBC, manufactured by JSR Corporation) (B) phosphate compound (B1) piperazine pyrophosphate and melamine pyrophosphate Flame retardant composed of (B2) Piperazine pyrophosphate and melamine pyrophosphate and zinc oxide (B3) Flame retardant composed of melamine pyrophosphate (B4) Flame retardant composed of melamine orthophosphate (B5) Flame retardant composed of melamine polyphosphate. Melamine polyphosphate is a salt of polyphosphoric acid and melamine. Polyphosphoric acid is m in general formula (1). On the phosphoric acid. (B6) The flame retardant composed of ammonium polyphosphate is a salt of polyphosphoric acid and ammonia, and polyphosphoric acid is a phosphoric acid in which m is 3 or more in general formula (1). (B7) The flame retardant composed of pulse base urea phosphate pulse base urea is a salt of phosphoric acid and pulse base urea, and phosphoric acid is a phosphoric acid in which m is 1 in general formula (1). (B8) The flame retardant composed of melamine polyphosphate-melamine and melamine is a salt of polyphosphoric acid, melamine, melamine and melamine (double salt) Polyphosphoric acid is a phosphoric acid in which m is 3 or more in the general formula (1). (C) Organophosphorus compound (C1) Phosphonic acid-pentaerythritol ester flame retardant (X ¹ and X ² in general formula (2) are flame retardants of benzyl (phenylmethyl)) (C2) Phosphonic acid- Pentaerythritol ester flame retardant (X ¹ and X ² in the general formula (2) are flame retardants of phenylethyl) (C3) Phosphonic acid-pentaerythritol ester flame retardant (X ¹ and X in the general formula (2) X ² is a phenylpropyl flame retardant) (C4) phosphonic acid-pentaerythritol ester flame retardant (X ¹ and X ² in the general formula (2) are phenyl butyl flame retardants) (C5) phosphine Acid-pentaerythritol ester flame retardant (X ¹ and X ² in general formula (2) are phenylpentyl flame retardants) (C6) Phosphonic acid-pentaerythritol ester flame retardant (X in general formula (2) ¹ and X ² are the flame-retardant isopropyl phenyl) (C7) acid - pentaerythritol-based flame-retardant (general formula (2) X ¹ and X ² are the fire retardant naphthylmethyl) ( C8) Phosphonic acid-pentaerythritol ester flame retardant (X ¹ and X ² in general formula (2) are anthracenyl methyl flame retardants) (C9) Phosphonic acid-pentaerythritol ester flame retardant (general formula (2 ) Where X ¹ is phenylmethyl and X ² is naphthylmethyl flame retardant) (D) Fluorine-based anti-drip agent (D1) Acid modified polytetrafluoroethylene particles (modified PTFE) (D2) Modified polytetrafluoroethylene particles (non- Quality PTFE)

The flame retardancy and processability of the flame retarded resin compositions of Examples 1 to 112 and Comparative Examples 1 to 46 obtained as described above were evaluated by the following methods.

<Flammability> 热 The flame-retardant resin compositions of Examples 1 to 112 and Comparative Examples 1 to 46 were hot-pressed at 180 ° C, and the obtained thicknesses were 0.2mm, 0.4mm, 0.8mm, 1.6mm, 3mm, and 4mm 5mm 7 kinds of sheets were subjected to UL94 vertical combustion test to evaluate flame resistance. Next, the number of the sheets having the highest flame retardance number among the 7 types of sheets is used as the evaluation result of the flame retardancy of this embodiment and the comparative example. The results are shown in Tables 1 to 22. The numerical values in parentheses in Tables 1 to 22 indicate the thickness of the smallest sheet among the thicknesses of the sheets having the same flame retardance level. In addition, in Tables 1 to 22, the criteria for passing or failing the flame retardance are as follows. Pass. ． ． ． V-0, V-1 or V-2 failed. ． ． Burn all

In addition, in order to investigate the inferiority of the flame retardance between these examples in the examples with the number of stages V-0 in Examples 1 to 112, UL94 5V test was performed. The 5V test of UL94 consists of a short book test and a flat plate test. The short book test uses a short book-like test piece (length 125mm × width 13mm × thickness 2mm), and the flat plate test system uses a flat test piece (150mm × 150mm × 2mm thick) ).

Secondly, the examples where both the short book test and the plate test are qualified are judged as "5VA", only the short book test is qualified, but the examples that fail the plate test are judged as "5VB", and the short book test and the plate test are not qualified "All burned". The results are shown in Tables 1 to 22. In the embodiment with the stage number of V-0, the embodiment judged as "5VA" has a higher flame retardance stage than the embodiment judged as "5VB", and the embodiment judged as "5VB" has a ratio judgement The embodiment of "full burn" has a higher flame resistance level. In addition, "-" in Tables 1-22 shows that the 5V test of UL94 was not performed.

<Processability> The MFR of the flame-retardant resin composition of Examples 1 to 112 and Comparative Examples 1 to 46 was measured under conditions of a temperature of 230 ° C and a load of 2.16 kgf in accordance with JIS K7210. In each of the examples and comparative examples, the increase in MFR of the MFR of the resin composition with respect to 100 parts by mass of the organic phosphorus compound (C) in the polyolefin resin (A) was calculated by the following formula. rate. The results are shown in Tables 1 to 22. The unit of MFR in Tables 1 to 22 is g / 10min.

<Specific gravity> 比 The specific gravity of the flame-retardant resin compositions of Examples 1 to 112 and Comparative Examples 1 to 46 was measured using an electronic hydrometer (manufactured by Alfamirage). The results are shown in Tables 1 to 22.

From the results shown in Tables 1 to 22, it is known that in Examples 1 to 112, the evaluation results of the flame retardancy were V-0, V-1, or V-2, and Examples 1 to 112 were based on the viewpoint of flame retardancy. Meet the eligibility criteria. On the other hand, it was found that the evaluation results of the flame retardancy in Comparative Examples 1 to 46 were total burn, and Comparative Examples 1 to 46 did not meet the acceptance criteria from the viewpoint of flame retardancy.

In addition, in Examples 1 to 112 and Comparative Examples 25 to 28, since the MFR increase rate based on the MFR of the resin composition in which only the organic phosphorus compound (C) was added in an amount of 0 parts by mass was positive, it was confirmed Increase MFR. On the other hand, in Comparative Examples 1 to 24 and 29 to 46, only the organic phosphorus compound (C) was added in an amount of 0 parts by mass of the resin composition. The MFR was based on the MFR increase rate of 0% or less. .

From the above, it is known that by using the above-mentioned phosphate compound and the above-mentioned organic phosphorus compound in combination with the flame-retardant resin composition of the present invention, it is confirmed that it is possible to improve processability while ensuring excellent flame retardancy compared with the use of the above-mentioned phosphate compound alone. .

1: conductor 2: insulating layer 3: covering layer 4: insulated wire 10: cable 20: optical fiber cable 24: optical fiber 25: covering portion (insulator)

Fig. 1 is a partial side view showing an embodiment of a cable according to the present invention. FIG. 2 is a cross-sectional view taken along the line II-II in FIG. 1. FIG. 3 is a cross-sectional view showing an embodiment of the optical fiber cable of the present invention.

Claims (15)

A flame-retardant resin composition containing a polyolefin resin (A), a phosphate compound (B), and an organic phosphorus compound (C), and the phosphate compound (B) is represented by the following general formula (1) A salt of phosphoric acid with an amine compound having at least one amine group in the molecule, and the organic phosphorus compound (C) is represented by the following general formula (2), (In the above general formula (1), m represents an integer from 1 to 100) (In the above general formula (2), X ¹ and X ² are the same or different, and are represented by the following general formula (3)) (In the above general formula (3), AL is a branched or linear aliphatic hydrocarbon group having 1 to 5 carbon atoms, and Ar is a phenyl group, a naphthyl group, or an anthryl group which may have a substituent, and is bonded to AL Any carbon atom, n represents an integer of 1 to 3). The flame-retardant resin composition according to claim 1, wherein the phosphate compound (B) is added in a proportion of more than 0 parts by mass and 120 parts by mass or less with respect to 100 parts by mass of the polyolefin resin (A). The flame-retardant resin composition according to claim 1 or 2, wherein the organic phosphorus compound (C) is added in a proportion of more than 0 parts by mass and 50 parts by mass or less with respect to 100 parts by mass of the polyolefin resin (A). The flame-retardant resin composition according to claim 3, wherein the organic phosphorus compound (C) is added in a proportion of 5 parts by mass or more and 40 parts by mass or less with respect to 100 parts by mass of the polyolefin resin (A). The flame-retardant resin composition according to claim 1 or 2, wherein X ¹ and X ² in the aforementioned general formula (2) are a benzyl group. For example, the flame retardant resin composition of claim 1 or 2, wherein m in the general formula (1) is 1 to 2, and the amine compound is an amine compound containing a triazine ring, an amine compound containing a piperazine ring, A mixture of triazine ring-containing amine compounds, ammonia, or Guanidine urea. The flame retardant resin composition according to claim 1 or 2, wherein the amine compound is a mixture of a piperazine ring-containing amine compound and a triazine ring-containing amine compound. The flame-retardant resin composition according to claim 1 or 2, wherein a fluorine-based anti-drip agent (D) is further added in a proportion of more than 0 parts by mass and 5 parts by mass or less with respect to 100 parts by mass of the polyolefin resin (A). The flame-retardant resin composition according to claim 1 or 2, wherein the polyolefin resin (A) contains a polypropylene resin. The flame-retardant resin composition according to claim 1 or 2, wherein the polyolefin resin (A) contains an elastomer. The flame-retardant resin composition according to claim 10, wherein the content of the elastomer in the polyolefin resin (A) is 60% by mass or less. A molded article containing the flame-retardant resin composition according to any one of claims 1 to 11. An insulated wire is provided with a conductor and an insulating layer covering the conductor. The insulating layer is made of a nonflammable resin composition according to any one of claims 1 to 11. A cable is provided with an insulated wire having a conductor and an insulating layer covering the conductor, and a covering layer covering the insulated wire, and at least one of the insulating layer and the covering layer is as in claim 1 to 11 It is composed of any of the flame-retardant resin compositions. An optical fiber cable is provided with an optical fiber and a covering portion covering the optical fiber, the covering portion is an insulator having the optical fiber covered, and the insulation system is made of a nonflammable resin composition according to any one of claims 1 to 11. Made up.