JP6826824B2 - Flame-retardant resin composition and molded products using it, insulated wires and cables - Google Patents

Description

The present invention is a resin composition having excellent mechanical properties, acid resistance, chemical resistance, heat resistance, no foaming during molding, and excellent acid resistance, a molded product using the composition, and a resin composition thereof. It relates to electric wires / cables, optical fiber cables and other molded parts used as a coating material.

More specifically, the present invention relates to an insulated electric wire, an insulated electric wire, an electric cord automobile cable, a communication electric wire / cable, an electric wire / cable, and an optical fiber cord / cable used for internal or external wiring of an electric / electronic device. , Mainly related to flame-retardant resin materials used in electric wires / cables for automobiles, automobile vehicles, railway vehicles, ships, aircraft, industrial equipment, electronic equipment, electronic parts, etc.

Conventionally, insulated wires / cables / cords, optical fiber core wires, optical fiber cords for automobile wires / cables, automobile vehicles, railroad vehicles, ships, aircraft, industrial equipment, electronic devices, electronic parts, etc. have been flame-retardant and heat-resistant. Various properties such as properties and mechanical properties (for example, tensile properties and abrasion resistance) are required.

For this reason, polyvinyl chloride (PVC) compounds and polyolefin compounds containing halogen-based flame retardants containing bromine or chlorine atoms in their molecules are mainly used as the coating materials used for these wiring materials. It was.

However, when these are burned, corrosive gas may be generated from the halogen compound contained in the coating material, and this problem has been discussed in recent years, and there is no risk of generation of halogen-based gas, etc. A flame-retardant resin coated with a fuel material is being studied.

The non-halogen flame retardant material exhibits flame retardancy by blending a halogen-free flame retardant into the resin, and for various resins, for example, a polyolefin resin, a nylon resin, and a polyester resin. As a material, a material containing a metal hydrate such as aluminum hydroxide or magnesium hydroxide is used. In order to exhibit high flame retardancy, such a metal hydrate needs to be blended in a large amount as compared with a halogen-based flame retardant.

Among these metal hydrates, magnesium hydroxide has a relatively high flame retardant effect among such metal hydrates, and has been widely used as a non-halogen flame retardant mainly composed of polyolefin resins.

The resin composition containing magnesium hydroxide is weak against acid, and its physical properties are significantly deteriorated by various acidic chemicals such as acid rain and nitrogen oxides contained in exhaust gas. Therefore, a method of surface-treating the surface of magnesium hydroxide with a phosphoric acid ester or the like has been proposed.

However, when magnesium hydroxide treated with a phosphoric acid ester was used, the mechanical strength of the resin composition was significantly reduced, and its acid resistance was also insufficient.

On the other hand, aluminum hydroxide has excellent acid resistance and is stable, for example, less susceptible to nitrogen oxides contained in exhaust gas. However, since the decomposition temperature is low, it is decomposed at the time of compound molding or extrusion, and a stable molded body or electric wire cannot be obtained.

To solve this problem, a method has been proposed in which boehmite, which is more stable and does not easily decompose to high temperatures, is used as a flame retardant. However, since the amount of dehydration is low and the decomposition temperature is too high, a great effect as a flame-retardant material cannot be obtained.

Further, heat-resistant aluminum hydroxide as disclosed in Japanese Patent No. 4614354 (Patent Document 2) has been proposed. However, even if such heat-resistant aluminum hydroxide is used, there is a problem that decomposition occurs during molding and the electric wire and the molded body foam.

As a result of diligent studies, the inventors have conducted a flame-retardant resin composition having excellent acid resistance without foaming during molding by using a specific resin for a part or all of the base material, and a flame-retardant resin composition thereof. We were able to obtain the molded product, electric wire / cable material used.

Further, according to International Publication No. 2004/08897 (Patent Document 1) and Patent No. 4614354 (Patent Document 2), heat-resistant aluminum hydroxide is a flame retardant because it has a high dehydration temperature and a sufficient dehydration amount. It can be used for either a thermoplastic resin or a thermosetting resin. Synthetic resins can be used regardless of flame retardancy or flame retardancy. For example, methylmethacrylic resin, acrylic-styrene copolymer resin, ABS resin, polystyrene, polyethylene, polypropylene, polycarbonate, phenol resin, urea resin, melamine resin. , Epoxy resin, unsaturated polyester, diallyl phthalate and the like.

Here, most of the thermoplastic resins have a molding temperature around the temperature range in which aluminum hydroxide is dehydrated, and the dehydration of aluminum hydroxide causes foaming in the synthetic resin molded product, and lumps appear on the surface of the molded product. In some cases, the yield was reduced. In addition, thermosetting resins are often molded at a lower temperature than thermoplastic resins, but due to the characteristics of this synthetic resin, they may be used at high temperatures, for example, they are used for electrical and electronic equipment parts. In many cases, aluminum hydroxide was dehydrated depending on the ambient temperature used, which could reduce the yield and physical properties of the molded product. For example, when a thermosetting resin is used for an electronic substrate, the environmental temperature when soldering onto the electronic substrate is about 230 ° C., so that aluminum hydroxide is dehydrated and the yield of the electronic substrate is lowered. was there. Specifically, heat-resistant aluminum hydroxide is kneaded into polypropylene (PP) as a flame retardant, and heat-resistant aluminum hydroxide is cast in a film shape on an epoxy resin for evaluation.

However, this publication is clearly different from the technical fields and problems of electric wires / cables, optical fiber cables and other molded parts in soft thermoplastic resins as in the present invention.

International Publication No. 2004/080897 Japanese Patent No. 4614354

An object of the present invention is a resin composition having excellent mechanical properties, acid resistance, chemical resistance, and heat resistance, which does not foam during molding, and has excellent acid resistance, a molded product using the composition, and a resin thereof. It is an object of the present invention to provide electric wires / cables, optical fiber cables and other molded parts as a coating material using a composition.

According to the first invention, the present invention
Component (a) 100 parts by mass of a thermoplastic resin (A) containing a thermoplastic resin having a JIS shore hardness of A20 or more and a shore hardness of D54 or less.
Component (b) 15 to 250 parts by mass of an aluminum hydroxide composite having a 1% dehydration temperature of 240 ° C. or higher and a total dehydration amount of 25% or higher.
Flame-retardant resin composition (X), which is characterized by containing
Is provided.

According to the second invention
The above component (a) thermoplastic resin
Ethylene-vinyl acetate copolymer, ethylene- (meth) acrylic acid ester copolymer, ethylene- (meth) acrylic acid copolymer, polypropylene resin, polyethylene resin, ethylene-α-olefin copolymer, ethylene- α-Olefin-diene copolymer (rubber), (hydrogenated) aromatic vinyl compound-conjugated diene block copolymer, and (hydrogenated) aromatic vinyl compound-conjugated diene random copolymer, (hydrogenated) ) The flame retardant according to the first invention, which is at least one selected from the group consisting of a conjugated diene copolymer, chlorinated polyethylene, chloroprene rubber, acrylic rubber, polyurethane, polyester elastomer, and polyamide elastomer. A resin composition is provided.

According to the third invention
Provided is the flame-retardant resin composition according to the first or second invention, wherein the thermoplastic resin of the component (a) is 60% by mass or more among the resin components of the thermoplastic resin (A). Will be done.

According to the fourth invention
The flame-retardant resin composition according to any one of the first to third inventions is provided, wherein all the resin components of the thermoplastic resin (A) are composed of the thermoplastic resin of the component (a). ..

According to the fifth invention, the melt mass flow rate (JIS K7210 (1999), temperature 190 ° C., load 10 kg) of the flame-retardant resin composition (X) is 10 g / 10 minutes or less. The flame-retardant resin composition according to any one of the fourth inventions is provided.

According to the sixth invention
The component (b) contains 15 to 80 parts by mass of an aluminum hydroxide composite having a 1% dehydration temperature of 240 ° C. or higher and a total dehydration amount of 25% or higher with respect to 100 parts by mass of the thermoplastic resin (A). The flame-retardant resin composition (X) according to any one of the first to fifth inventions.
Is provided.

According to the seventh invention
The flame-retardant resin composition according to any one of the first to sixth inventions, wherein the average particle size of the component (b) aluminum hydroxide composite is 2.0 to 4.5 μm. Will be done.

According to the eighth invention
The insulated wire and cable according to any one of the first to seventh inventions, characterized in that the resin composition is formed around a conductor, are provided.

According to the ninth invention
The insulated wire according to any one of the first to eighth inventions is provided, wherein the resin composition is crosslinked.

According to the tenth invention
The molded part according to any one of the first to ninth inventions, characterized in that the resin composition is used, is provided.

By using a specific amount of a specific elastomer or rubber-based material for the base resin and adding an aluminum hydroxide composite having a 1% dehydration temperature of 240 ° C. or higher and a total dehydration amount of 25% or higher, the acid resistance is extremely high. It is possible to obtain a resin composition that is excellent and does not easily foam during compound preparation and molding.

Although the cause of this is not well understood, such highly heat-resistant aluminum hydroxide also generates several percent of water before the temperature rises to 240 ° C. Such moisture causes foaming in the compound or the molded product during compound molding or molding, causing poor appearance. On the other hand, by adding a specific amount, that is, 25% or more of a specific elastomer material or rubber material, the water generation is suppressed to 1% or less, so that the water content is retained in these resins and then diffused, which causes foaming. It is difficult and stable to mold the compound and the molded product, and it is possible to obtain a good resin composition and the molded product.

Further, when the average particle size of the heat-resistant aluminum hydroxide is 2.0 to 4.5 μm, foaming is significantly suppressed, and it is possible to obtain a resin composition and a molded product having good strength, acid resistance and appearance. It becomes. The cause of this is not well understood, but when the particle size is 2.0 μm or less, decomposition occurs rapidly during kneading or extrusion, and a large amount of water is generated, causing foaming. When the particle size is larger than 4.5 μm, the molded product The strength and elongation of the product will drop sharply.

Hereinafter, the constituent components of the flame-retardant resin composition of the present invention, the production of the flame-retardant resin composition, and the use of the flame-retardant resin composition will be described in detail.

1. 1. Constituent component (a) of flame-retardant resin composition: (essential component) (JIS standard) The thermoplastic resin component (a) having a shore hardness of A20 or more and a shore hardness of D54 or less is (JIS standard) a shore hardness of A20 or more. It is a thermoplastic resin having a shore hardness of D54 or less.

In particular,
Ethylene-vinyl acetate copolymer, ethylene- (meth) acrylic acid ester copolymer, ethylene- (meth) acrylic acid copolymer, polypropylene-based resin, polyethylene-based resin, ethylene-α-olefin copolymer, ethylene- α-Olefin-diene copolymer (rubber), (hydrogenated) aromatic vinyl compound-conjugated diene block copolymer, and (hydrogenated) aromatic vinyl compound-conjugated diene random copolymer, (hydrogenated) ) Conjugate diene copolymer, chlorinated polyethylene, chloroprene rubber, acrylic rubber, polyurethane, polyester elastomer, polyamide elastomer and the like can be mentioned.

Ingredient (a) is
(JIS standard) A thermoplastic resin having a shore hardness of A20 or more and a shore hardness of D54 or less. The above-mentioned ethylene-vinyl acetate copolymer, ethylene- (meth) acrylic acid ester copolymer, ethylene- (meth) acrylic acid. Copolymers, polypropylene-based resins, polyethylene-based resins, ethylene-α-olefin copolymers, ethylene-α-olefin-diene copolymers (rubber), (hydrogenated) aromatic vinyl compounds-conjugated diene-based block copolymers Combined and selected from (hydrous) aromatic vinyl compound-conjugated diene-based random copolymer, (hydrogenated) conjugated diene-based copolymer, chlorinated polyethylene, chloroprene rubber, acrylic rubber polyurethane, polyester elastomer, polyamide elastomer It is necessary that there is at least one species.

In the above ethylene-vinyl acetate copolymer, ethylene- (meth) acrylic acid copolymer, and ethylene- (meth) acrylic acid ester copolymer, all of them have melt mass flow rate (JIS K7210 (1999), temperature 190 ° C.). , Load 2.16 kg) is preferably 50 g / 10 minutes or less, more preferably 0.05 to 30 g / 10 minutes, still more preferably 0.1 to 10 g / 10 minutes. If the MFR is too high, the mechanical properties will deteriorate, and if it is too low, the moldability will deteriorate.

Here, examples of the (meth) acrylic acid ester in the ethylene- (meth) acrylic acid ester copolymer include an alcohol having 1 to 8 carbon atoms and an ester of (meth) acrylic acid, and specifically, ( Examples thereof include methyl acrylate (meth), ethyl (meth) acrylate, -n-butyl (meth) acrylate, -t-butyl (meth) acrylate, and -2-ethylhexyl (meth) acrylate.

In the ethylene-vinyl acetate copolymer, the ethylene- (meth) acrylic acid copolymer, and the ethylene- (meth) acrylic acid ester copolymer, the COOR-type functional groups contained therein are decarboxylated during (1) thermal decomposition. It causes a carbonation reaction and becomes CO ₂ as it is. In other words, it generates nonflammable gas without radiating combustion energy. (2) Since it is hydrophilic, the interface strength of the inorganic flame retardant with the metal hydrate is high, and the degree of deterioration of physical properties even if a large amount of inorganic flame retardant is added. (3) Since the comonomer that copolymerizes with ethylene is bulky, the acceptability of the inorganic flame retardant is high, and even if a large amount of the inorganic flame retardant is added, the degree of deterioration of the physical properties is small. It is a resin that is advantageous as a base material for a flammable resin composition. Further, the present invention is characterized in that a crosslinked resin composition is produced by melt-kneading at a low temperature, and there is a drawback that the use of these resins causes a decrease in manufacturability due to the development of adhesive ability during composition production. It can be suppressed.

Examples of the polypropylene-based resin include atactic polypropylene having low stereoregularity, a reactor TPO, and a random copolymer with an α-olefin.

As the atactic polypropylene having low stereoregularity, an atactic polypropylene having a flexural modulus of 800 MPa or less is preferable because it does not need to suppress foaming during kneading or raise the temperature during extrusion, and it is easy to retain water inside. The melt mass flow rate (JIS K7210 (1999), temperature 190 ° C., load 2.16 kg) is preferably 25 g / 10 minutes or less, more preferably 0.05 to 30 g / 10 minutes, still more preferably 0.1 to 10 g /. It is 10 minutes. If the MFR is too high, the strength, impact resistance and heat resistance are lowered, and if it is too low, the moldability is deteriorated.

The reactor TPO is a mixture of a crystalline polypropylene resin and an ethylene-α-olefin copolymer rubber, and is generally a trivial block copolymer having a large amount of rubber components.

The ratio of the crystalline polypropylene resin to the ethylene-α olefin copolymer rubber is preferably 20 to 70% by mass of the crystalline polypropylene resin and 30 to 80% by mass of the ethylene-α olefin copolymer rubber.

Examples of the crystalline polypropylene-based resin include a polypropylene homopolymer and a random copolymer with an α-olefin mainly composed of propylene.

Examples of the ethylene-α-olefin copolymer rubber include ethylene-propylene copolymer rubber, ethylene-butene copolymer rubber, ethylene-hexene copolymer rubber, and ethylene-octene copolymer rubber.

The melt mass flow rate (JIS K7210 (1999), temperature 190 ° C., load 2.16 kg) is preferably 25 g / 10 minutes or less, more preferably 0.05 to 30 g / 10 minutes, still more preferably 0.1 to 10 g /. It is 10 minutes. If the MFR is too high, the strength, impact resistance and heat resistance are lowered, and if it is too low, the moldability is deteriorated.

As the random copolymer of propylene and α-olefin, one having a flexural modulus of 800 MPa or less is preferable because it is not necessary to suppress foaming during kneading or raise the temperature during extrusion.

Ethylene is mainly mentioned as the α-olefin.

The melt mass flow rate (JIS K7210 (1999), temperature 190 ° C., load 2.16 kg) is preferably 50 g / 10 minutes or less, more preferably 0.05 to 30 g / 10 minutes, still more preferably 0.1 to 10 g /. It is 10 minutes. If the MFR is too high, the strength, impact resistance, and heat resistance characteristics are lowered, and if it is too low, the moldability is deteriorated.

Examples of the polyethylene-based resin, ethylene-α-olefin copolymer, and ethylene-α-olefin-diene copolymer (rubber) include ultra-low density polyethylene, low density polyethylene, linear low density polyethylene, and the like. However, linear low-density polyethylene polymerized by a single-site catalyst is preferable because of its high strength and the fact that a large amount of filler such as aluminum hydroxide can be added. The preferred density is 0.965 to 0.925.

The melt mass flow rate of the polyethylene resin (JIS K7210 (1999), temperature 190 ° C., load 2.16 kg) is preferably 25 g / 10 minutes or less, more preferably 0.05 to 30 g / 10 minutes, still more preferably. 0.1 to 10 g / 10 minutes. If the MFR is too high, the mechanical properties will deteriorate, and if it is too low, the moldability will deteriorate.

The ethylene / α-olefin copolymer and the ethylene-α-olefin-diene copolymer (rubber) include an ethylene / propylene copolymer, an ethylene / 1-butene copolymer, and an ethylene / propylene / unconjugated diene. Examples thereof include a copolymer, an ethylene / 1-hexene copolymer, and an ethylene / 1-octene copolymer.

The above (hydrogenated) aromatic vinyl compound-conjugated diene-based block copolymer, (hydrogenated) aromatic vinyl compound-conjugated diene-based random copolymer, and (hydrogenated) conjugated diene-based copolymer will be described.

The (hydrogenated) aromatic vinyl compound-conjugated diene block copolymer includes at least one polymer block A mainly composed of an aromatic vinyl compound and a polymer block B mainly composed of a conjugated diene compound. It is a block copolymer composed of at least one or a hydrogenated product thereof. For example, an aromatic vinyl compound-conjugated diene compound block copolymer having a structure such as AB, ABA, BABA, ABABAA, or hydrogenation thereof. You can list things.

The polymer block A mainly composed of an aromatic vinyl compound is preferably composed of only the aromatic vinyl compound, or 50% by weight or more, preferably 70% by weight or more of the aromatic vinyl compound, and any component, for example, a conjugated diene compound. It is a copolymer block with.

Further, the polymer block B mainly composed of the conjugated diene compound is preferably composed of only the conjugated diene compound, or has an optional component, for example, 50% by weight or more of the conjugated diene compound, preferably 70% by weight or more, and the aromatic vinyl compound. It is a copolymer block of.

The block copolymer contains, for example, 5 to 60% by weight, preferably 20 to 50% by weight, of an aromatic vinyl compound.

Further, in the polymer block A mainly composed of these aromatic vinyl compounds and the polymer block B mainly composed of the conjugated diene compound, the distribution of the units derived from the conjugated diene compound or the aromatic vinyl compound in the molecular chain is random. It may be tapered (monomer component increases or decreases along the molecular chain), partially blocked, or any combination thereof. When there are two or more polymer blocks A mainly composed of an aromatic vinyl compound or two or more polymer blocks B mainly composed of a conjugated diene compound, each polymer block has a different structure even if each has the same structure. There may be.

As the aromatic vinyl compound constituting the block copolymer, for example, one or more can be selected from styrene, α-methylstyrene, vinyltoluene, p-third butylstyrene and the like, and styrene is among them. preferable. As the conjugated diene compound, for example, one or more of butadiene, isoprene, 1,3-pentadiene, 2,3-dimethyl-1,3-butadiene and the like are selected, and among them, butadiene, isoprene and A combination of these is preferred.

Specific examples of the (hydrogenated) block copolymer include a styrene-butadiene-styrene copolymer (SBS), a styrene-isoprene-styrene copolymer (SIS), and a styrene-ethylene / butadiene-styrene copolymer (SIS). SEBS), styrene-ethylene / propylene-styrene copolymer (SEPS), styrene-ethylene / ethylene / propylene-styrene copolymer (SEEPS), partially hydrogenated styrene-butadiene-styrene copolymer (SBBS), styrene- Ethylene-butylene-ethylene copolymer (SEBC) and the like can be mentioned.

The (hydrogenated) block copolymer is a block copolymer composed of a polymer block A containing an aromatic vinyl compound as a main component and a polymer block B containing a conjugated diene compound as a main component. The hydrogenated block copolymer obtained by hydrogenating the polymer may have a molar ratio of 2 or less between the number of ethylene unit structures generated by hydrogenation and the number of linear α-olefin unit structures. In this case, the content of the aromatic vinyl compound is 50% by weight or less, preferably 5 to 35% by weight. If it exceeds 50% by weight, the hardness becomes higher, the hardness becomes higher than the hardness 54D, foaming is likely to occur during molding, and the moldability is easily impaired.

The (hydrogenated) aromatic vinyl compound-conjugated diene compound random copolymer is a random copolymer of a conjugated diene compound and an aromatic vinyl compound, preferably having a number average molecular weight of 5,000 to 1, It is 1,000,000, more preferably 10,000 to 350,000, the value of the degree of polydispersity (Mw / Mn) is 10 or less, and 1,2 bonds or 3,4 of the conjugated diene portion thereof. The vinyl bond content of the bond or the like is 5% or more, preferably 20 to 90%. If it is less than 5%, the feel of the obtained molded product becomes hard, which does not meet the object of the present invention. Here, the content of the aromatic vinyl compound is 40% by weight or less, preferably 5 to 35% by weight.

Examples of the aromatic vinyl compound include styrene, t-butyl styrene, α-methyl styrene, p-methyl styrene, divinyl benzene, 1,1-diphenyl styrene, N, N-diethyl-p-aminoethyl styrene, and vinyl toluene. , P-3rd butyl styrene and the like can be selected from one or more, and styrene is preferable.

As the conjugated diene compound, for example, one or more of butadiene, isoprene, 1,3-pentadiene, 2,3-dimethyl-1,3-butadiene and the like are selected, among which butadiene, isoprene and A combination of these is preferred.

The aromatic vinyl compound and the conjugated diene compound are randomly bonded to each other, and Corsov [I. M. Kolthoff, J. et al. Polymer Sci. , Vol. 1 p. 429 (1946)], the block-shaped aromatic vinyl compound content is preferably 10% by weight or less, preferably 5% by weight or less, based on the fully bound aromatic vinyl compound. Further, the copolymer is preferably one in which at least 90% of the aliphatic double bonds based on the conjugated diene compound are hydrogenated.

Specific examples of the above (hydrogenated) styrene-butadiene random copolymer include hydrogenated SBR (Dynaron 1820P, JSR Co., Ltd.) and the like.

Examples of the (hydrogenated) conjugated diene-based copolymer include hydrogenated compounds of conjugated diene compound block copolymers, for example, crystalline ethylene blocks obtained by hydrogenating a block copolymer of butadiene and non-crystalline ethylene blocks. Examples thereof include block copolymers (CEBC) having a crystalline ethylene-butylene block. In the present invention, the hydrogenated additive of the conjugated diene compound block copolymer may be used alone or in combination of two or more.

Specific examples of the hydrogenated product of the conjugated diene compound block copolymer include Dynalon 6100P (trademark; manufactured by JSR Co., Ltd.) and the like.

As the chlorinated polyethylene, chlorinated polyethylene having a chlorine content of 20 to 45% by mass is preferable. By selecting these chlorinated polyethylenes, it is possible to set the JIS hardness to 20 A or more and 54 D or less, and it is possible to have a material having excellent moldability. The degree of chlorination indicating the hardness is, for example, a degree of chlorination of 20 to 45%.

The melt mass flow rate (JIS K7210 (1999), temperature 190 ° C., load 21.6 kg) is preferably 25 g / 10 minutes or less, more preferably 0.05 to 20 g / 10 minutes, still more preferably 0.1 to 10 g /. It is 10 minutes. If the MFR is too high, the strength, low temperature and impact resistance will decrease, and if it is too low, the moldability will deteriorate.

Examples of the chloroprene rubber include ordinary chloroprene rubber and copolymers with fluororubber. As the chloroprene rubber, the Mooney viscosity ML (1 + 4) at 100 ° C. is preferably 20 to 110, more preferably 40 to 100. Examples of commercially available products include Skype Ren (Tosoh), Denka Chloroprene (Denka), and Shoprene (Showa Denko). It is preferable that the crystallinity is low, but there is no problem even if the crystallinity is particularly high.

The acrylic rubber is a rubber elastic body obtained by copolymerizing a small amount of a monomer having various functional groups with an alkyl acrylate such as methyl acrylate, ethyl acrylate, butyl acrylate or the like as a monomer component. As the monomer to be copolymerized, 2-chloroethyl vinyl ether, methyl vinyl ketone, acrylic acid, acrylonitrile, butadiene and the like can be appropriately used. Specifically, Nipol AR (trade name, manufactured by Zeon Corporation), JSR AR (trade name, manufactured by JSR Corporation) and the like can be used. The acrylic rubber is not particularly limited in Mooney viscosity and the like.

In particular, it is preferable to use methyl acrylate as the monomer component, and in that case, a binary copolymer with ethylene or an unsaturated hydrocarbon having a carboxyl group in the side chain is used as the monomer. A polymerized ternary copolymer can be particularly preferably used. Specifically, in the case of a binary copolymer, Baymac DP can be used, and in the case of a ternary copolymer, Baymac G, Baymac HG, and Baymac GLS (trade names, all manufactured by DuPont) can be used. it can.

By blending these acrylic rubbers, the oxygen index can be increased and the flame retardancy can be significantly increased.

In the present invention, the component (a) is preferably 60% by mass or more, more preferably 80% by mass or more, and more preferably all the resin components are the thermoplastic resin of the above (a).

When the resin component of the above (a) is present in an amount of 60% by mass or more, a good molded product can be obtained without molding, but when the molding speed is increased, it is preferable that the resin component of the component (a) is large. ..

Further, a mineral oil or a plasticizer may be added as a partial replacement of the resin component (a). Examples of the mineral oil include paraffin-based oil, naphthen-based oil, and aroma-based oil. Among them, paraffin-based oil and naphthen-based oil are preferable, and paraffin-based oil is more preferable.

Examples of the plasticizer include a phthalate ester plasticizer, a trimellitic acid ester plasticizer, a polyester plasticizer, an adipic acid plasticizer, a pyromellitic acid ester plasticizer, and the like. This amount is preferably 2 times or less, preferably 1.5 times or less, and more preferably the same amount or less of the resin of the resin component (a).

Among the resin components of component (a),
(A) Ethylene-vinyl acetate copolymer and acrylic rubber having a melt mass flow rate (JIS K7210 (1999), temperature 190 ° C., load 2.16 kg) of 2 g / 10 minutes or less.
(I) Ethylene-α-olefin copolymer rubber, ethylene-α-olefin-diene copolymer rubber,
(C) (Hydrogenated) It is preferable that an aromatic vinyl compound-conjugated diene block copolymer is contained.

By containing these (a) to (c) thermoplastic resins, even if the temperature of the compound or the molding temperature rises, the compound or the molded product will hardly foam and cause an appearance defect. In addition, it becomes possible to obtain a molded product having both flexibility and chemical resistance.

The mechanism that makes it difficult to cause this poor appearance is not well understood, but the moisture generated by the decomposition of heat-resistant aluminum hydroxide dissolves in the non-crystalline parts of the resin components (a) to (c) at high temperatures, and the outside It is thought that this is because the occurrence of shavings can be suppressed. The components (a) to (c) are preferably contained in the resin (a) component in an amount of 10% by mass or more, preferably 20% by mass or more, and more preferably 35% by mass or more.

Component (c) (JIS standard) Polyolefin resin exceeding shore hardness D55 (optional component)
The component (c) is an optional component, and when the component (a) is 60% by mass or more and less than 100% by mass of the thermoplastic resin (A), it exceeds 0% by mass and is less than 40% by mass. Can include. (Here, component (a) + component (c) = 100% by mass.)
It is used for the purpose of imparting heat resistance and improving the strength of the flame-retardant resin composition.

Ingredient (c) is
(JIS standard) A polyolefin resin having a shore hardness of more than D55.
For example
(JIS standard) Polypropylene resin exceeding shore hardness D55 and (JIS standard) Polyethylene resin exceeding shore hardness D55.

(JIS standard) A polypropylene resin having a shore hardness of more than D55 is used for the purpose of improving the heat resistance, adjusting the hardness, and improving the moldability of the flame-retardant resin composition.

Polypropylene resins having a shore hardness of more than D55 (JIS standard) used as component (c) include, for example, a propylene homopolymer; propylene and a small amount of other α-olefins such as ethylene, 1-butene, 1-hexene, 1 -Copolymers with octene, 4-methyl-1-pentene, etc. (block copolymers, random copolymers); and the like can be mentioned. Among these, those having a melt mass flow rate (JIS K7210 (1999), temperature 210 ° C., load 10 kg) of 0.1 to 10 g / 10 minutes are preferable.

(JIS standard) A polyethylene-based resin having a shore hardness of more than D55 is used for the purpose of improving the strength, adjusting the hardness, and improving the moldability of the flame-retardant resin composition.

(JIS standard) Examples of the polyethylene-based resin having a shore hardness of more than D55 include high-density polyethylene obtained by the low-pressure method and low-density polyethylene obtained by the high-pressure method.

The melt mass flow rate (JIS K7210 (1999), temperature 190 ° C., load 2.16 kg) is preferably 50 g / 10 minutes or less, more preferably 0.05 to 30 g / 10 minutes, still more preferably 0.1 to 10 g /. It is 10 minutes. If the MFR is too high, the mechanical properties will deteriorate, and if it is too low, the moldability will deteriorate.

Component (b): (Indispensable component) Aluminum hydroxide composite having a 1% dehydration temperature of 240 ° C. or higher and a total dehydration amount of 25% or higher The 1% dehydration temperature of the present invention is 240 ° C. or higher and the total dehydration amount is As described in Japanese Patent No. 4614354, the heat-resistant aluminum hydroxide having a content of 25% or more is hydrothermally treated using a mixture of aluminum hydroxide and a reaction retarder as a raw material, or pressurized under a steam atmosphere. , Can be manufactured by heating. Here, the heat-resistant aluminum hydroxide is suppressed from boehmite formation even by hydrothermal treatment in a high temperature region, or by pressurization and heating in a steam atmosphere, and the dehydration temperature is raised while maintaining a sufficient amount of dehydration. It refers to aluminum hydroxide.

Further, hydrothermal treatment is to add water having a saturated water vapor content or more to a mixture of aluminum hydroxide and a reaction retarder and perform heat treatment using a pressure vessel such as an autoclave (hereinafter, this is referred to as "wet treatment"). (Sometimes). The treatment by pressurizing and heating in a steam atmosphere means using a pressure vessel such as an autoclave without adding water to the mixture of aluminum hydroxide and the reaction retarder, or by adding water less than the saturated steam amount. Pressurization and treatment (hereinafter, may be referred to as "dry treatment"). The heat-resistant aluminum hydroxide of the present invention can be produced by heating in a pressure vessel without adding water to a raw material in which aluminum hydroxide and a reaction retarder that delays boehmite formation are mixed. Heating in a pressure vessel without adding water to the raw material means that the heat treatment is performed without adding water to the raw material and without generating steam other than a part of the aluminum hydroxide of the raw material being dehydrated and steamed by heating. (Hereinafter, it may be called dry treatment). Further, in addition to the vapor pressure due to the water vapor described above, compressed air may be sent from the outside into the pressure vessel to pressurize.

The reaction retarder delays the boehmite formation of aluminum hydroxide in the case of wet treatment or dry treatment, and under a high thermal history (high treatment temperature and long treatment time such that aluminum hydroxide becomes 100% boehmite). However, it is a substance that enables the production of aluminum hydroxide having a low boehmite formation rate or not boehmite formation. Generally, when aluminum hydroxide is wet-treated or dry-treated, it has a relatively low thermal history (usually 160 ° C./3 hours for dry-type treatment, 170 ° C./10 hours for wet treatment (water / aluminum hydroxide weight ratio = 3), and further. Similarly, when sodium hydroxide is added by wet treatment (water / aluminum hydroxide weight ratio = 3) (170 ° C./3 hours in the case of sodium hydroxide / aluminum hydroxide molar ratio = 1/12)), it is almost 100%. It becomes boehmite. However, when the reaction retarder in the present invention is used, the boehmite formation rate of aluminum hydroxide can be sufficiently suppressed even if it is wet-treated at 215 ° C. for 10 hours or dry-treated. , The dehydration temperature can be significantly increased.

Regarding the mechanism of raising the dehydration temperature, (1) the crystals of aluminum hydroxide are rearranged due to the high thermal history and the Al—O bond is strengthened, and (2) the trace amount of aluminum hydroxide is very small due to the high thermal history. It dissolves and precipitates, the surface of aluminum hydroxide becomes smooth, and the number of places where dehydration starts decreases (the mechanism of dehydration starts from cracks (defects) on the surface of aluminum hydroxide, and dehydration further enlarges the cracks. Subsequent dehydration occurs in a chain).

The treatment temperature in the wet treatment or the dry treatment can be 170 ° C. or higher and 300 ° C. or lower, preferably 200 ° C. or higher and 250 ° C. or lower. This is because if the treatment temperature is low, the dehydration temperature cannot be raised sufficiently, and the higher the treatment temperature, the higher the thermal history, which is preferable. In addition to having to increase the amount, the pressure during processing becomes so high that the autoclave device becomes impractical. The treatment time in the wet treatment or the dry treatment can be 1 hour or more and 24 hours or less, preferably 5 hours or more and 10 hours or less. This is because if the treatment time is short, the dehydration temperature cannot be raised sufficiently, and the longer the treatment time, the higher the thermal history, which is preferable. This is because it becomes necessary to increase.

The reaction retarder is not particularly limited as long as it meets the above definition, but is sulfate, nitrate, phosphoric acid, tetrafluoroboric acid, diammonium hydrogen phosphate, sodium dihydrogen dihydrogen monohydrate, phosphorus. Inorganic acids such as sodium dihydrogen acid and potassium metaphosphate or salts thereof, organic acids such as acetic acid, succinic acid, lactic acid, fumaric acid and tartrate acid or salts thereof, silica, silane coupling agent, white carbon, hexafluorosilicic acid, Examples thereof include silicon compounds such as sodium hexafluorosilicate, potassium silicate, aluminum fluoride, fly ash, diatomaceous earth, and siloxane, and fluorine compounds. The fluorine compound means a compound containing a fluorine element widely, and the tetrafluoroboric acid is not only an inorganic acid but also a fluorine compound, and is hexafluorosilicate, sodium hexafluorosilicate, and fluorinated silicate. Potassium is both a silicon compound and a fluorine compound. Among these reaction retardants, silicon compounds and fluorine compounds are preferable, and amorphous silica, white carbon, hexafluorosilicate, sodium hexafluorosilicate, potassium silicate, aluminum fluoride, and tetrafluorosilicate are preferable. More preferred. Even under the same treatment conditions, the silicon compound and the fluorine compound have a higher dehydration temperature than other acids and show favorable results because these compounds not only have a reaction delay effect but also have a vitrified layer on the surface of aluminum hydroxide. It is presumed that the dehydration temperature rises because it has the effect of promoting formation or forming a coating layer on the surface of aluminum hydroxide, and it is necessary to break these layers to dehydrate during heat dehydration. In addition, two or more reaction retarders can be used in combination.

The amount of the reaction retarder to be mixed with aluminum hydroxide is preferably 0.05 to 10 parts by weight, more preferably 0.1 to 5 parts by weight, and 0.3 to 3 parts by weight with respect to 100 parts by weight of aluminum hydroxide. Is the most preferable. If it is less than 0.05 parts by weight, boehmite formation of aluminum hydroxide cannot be sufficiently suppressed, and if it is more than 10 parts by weight, a reaction retarder may be mixed in aluminum hydroxide as an impurity. This is because the amount of dehydration is relatively reduced when the amount exceeds 10 parts by weight even if there is no actual harm as an impurity. In the field of flame retardants, it is common practice to mix phosphorus-based, nitrogen-based, and other inorganic flame retardants with aluminum hydroxide flame retardants to produce synergistic effects, and when additives are added for this purpose. Can exceed this range.

The present inventors have previously proposed a flame-retardant filler made of aluminum hydroxide compounded with boehmite produced by hydrothermal treatment using aluminum hydroxide as a raw material (Japanese Patent Application No. 2002-103146). In the present invention, the higher the boehmite conversion rate, the higher the dehydration temperature of aluminum hydroxide, while the total dehydration amount decreases, and the lower the boehmite conversion rate, the lower the dehydration temperature of aluminum hydroxide. There is a contradictory relationship that the amount of dehydration increases, and there is a problem that it is difficult to maintain a sufficient amount of dehydration at the same time as raising the dehydration temperature. However, the heat-resistant aluminum hydroxide of the present invention can raise the dehydration temperature by suppressing boehmite formation of aluminum hydroxide with a high thermal history, and can maintain a sufficient amount of dehydration. It greatly improves the contradictory relationship of the amount of dehydration. More specifically, the 1% dehydration temperature, that is, the temperature at which 1% is dehydrated with respect to the total weight of the flame retardant, which is within the permissible range of the amount of water to be dehydrated by the flame retardant in the synthetic resin, is not hydrothermally treated. The temperature of aluminum hydroxide is about 210 to 230 ° C., whereas the temperature of heat-resistant aluminum hydroxide of the present invention is 245 ° C. or higher, most of which is 250 ° C. or higher, and a sufficient amount of dehydration is maintained.

The heat-resistant aluminum hydroxide of the present invention includes those in which aluminum hydroxide and boehmite are mixed due to partial boehmite formation, but the total dehydration amount is preferably 15% or more, more preferably 20% or more, and further. It is preferably 25% or more.

On the other hand, in order to suppress foaming, it is preferable that the total dehydration amount is 32% or less.

Further, the heat-resistant aluminum of the present invention preferably has a 1% dehydration temperature of 255 ° C. or higher and a total dehydration amount of 30% or higher. In this case, the average particle size of the raw material aluminum hydroxide is 2.5 μm or less. Is preferable.

1% dehydration temperature 0.8 g of a sample was thermogravimetrically measured at 10 ° C./min, and the rate of change in weight from 100 ° C. to 580 ° C. was taken as the total dehydration amount based on the weight at 100 ° C. Further, the measurement was started from 120 ° C., and the temperature at which 1% of the total dehydration amount was reduced was defined as the 1% dehydration temperature.

The average particle size is measured as follows. Using a modified alcohol (trade name: Solmix) as the dispersion medium, take 50 ml of the dispersion medium in a 200 ml beaker and add 0.2 g of heat-resistant aluminum hydroxide. Next, after dispersing for 3 minutes with an ultrasonic disperser (Nippon Seiki Seisakusho US-300T), measurement is performed using an HRA type microtrack particle size distribution meter (manufactured by Nikkiso Co., Ltd.).

The present flame-retardant resin composition may be crosslinked and used. Examples of the cross-linking method include a normal chemical cross-linking method, an electron beam cross-linking method, and a silane cross-linking method.

Examples of the chemical cross-linking method include phenol cross-linking, diamine cross-linking, and peroxide cross-linking.

Examples of the organic peroxide arbitrarily used in the present invention include dicumyl peroxide, di-tert-butyl peroxide, 2,5-dimethyl-2,5-di- (tert-butylperoxy) hexane, and 2 , 5-Dimethyl-2,5-di (tert-butylperoxy) hexin-3, 1,3-bis (tert-butylperoxyisopropyl) benzene, 1,1-bis (tert-butylperoxy) -3, 3,5-trimethylcyclohexane, n-butyl-4,4-bis (tert-butylperoxy) valerate, benzoyl peroxide, p-chlorobenzoyl peroxide, 2,4-dichlorobenzoyl peroxide, tert-butylperoxy Known examples include benzoate, tert-butyl peroxyisopropyl carbonate, diacetyl peroxide, lauroyl peroxide, tert-butyl cumyl peroxide and the like.

Examples of the cross-linking aid that may be used as needed include vinyl compounds and (meth) acrylate compounds.

These cross-linking aids are also used during electron beam cross-linking. When used for electron beam cross-linking, a methacrylate-based compound such as trimethylolpropane triacrylate, an allyl-based compound such as triallyl cyanurate, a maleimide-based compound, and a polyfunctional compound such as a divinyl-based compound are blended as a cross-linking aid. You may.

Further, as the silane coupling agent used as a silane bridge, a silane coupling agent having a high hydrolysis rate is preferably used, and more preferably R _b11 is Y ¹³ , and Y ¹¹ , Y ¹² and Y ¹³ are the same as each other. There is a silane coupling agent. More preferably, at least one of Y ¹¹ , Y ¹² and Y ¹³ is particularly preferably all methoxy groups.

Specific examples of the silane coupling agent having a vinyl group, a (meth) acryloyloxy group, and a (meth) acryloyloxyalkylene group at the ends include vinyltrimethoxysilane, vinyltriethoxysilane, vinyltributoxysilane, and vinyldimethoxy. Organosilanes such as ethoxysilane, vinyldimethoxybutoxysilane, vinyldiethoxybutoxysilane, allyltrimethoxysilane, allyltriethoxysilane, vinyltriacetoxysilane, methacryloxypropyltrimethoxysilane, methacryloxypropyltriethoxysilane, methacryloxypropyl Methyldimethoxysilane and the like can be mentioned. These silane coupling agents may be used alone or in combination of two or more. Among such crosslinkable silane coupling agents, a silane coupling agent having a vinyl group and an alkoxy group at the ends is more preferable, and vinyltrimethoxysilane and vinyltriethoxysilane are particularly preferable.

Those having a glycidyl group at the end are 3-glycidoxypropyltriethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, Examples thereof include 2- (3,4-epylcyclohexyl) ethyltrimethoxysilane. Of these, vinyltrimethoxysilane and vinyltriethoxysilane are preferable.

(Other ingredients)
In the present invention, if necessary, at least one fatty acid metal salt selected from zinc, magnesium and calcium can be blended in order to improve the dispersibility of the above metal hydrate. Examples of the fatty acid of the fatty acid metal salt include oleic acid, lauric acid, myristic acid, palmitic acid, stearic acid and the like, and stearic acid is preferable.

The insulating resin composition of the present invention includes various additives generally used in electric wires and cables, such as antioxidants, metal deactivators, flame retardant (auxiliary) agents, fillers, and the like. Lubricants and the like can be appropriately blended as long as the object of the present invention is not impaired.

Antioxidants include amine-based antioxidants such as 4,4'-dioctyl-diphenylamine, N, N'-diphenyl-p-phenylenediamine, and polymers of 2,2,4-trimethyl-1,2-dihydroquinolin. Agents, pentaerythrityl-tetrakis (3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate), octadecyl-3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate , 1,3,5-trimethyl-2,4,6-tris (3,5-di-t-butyl-4-hydroxybenzyl) Phenolic antioxidants such as benzene, bis (2-methyl-4- (2-methyl-4-) Sulfur-based antioxidants such as 3-n-alkylthiopropionyloxy) -5-t-butylphenyl) sulfide, 2-mercaptobenzoimidazole and zinc salts thereof, pentaerythritol-tetrakis (3-lauryl-thiopropionate), And so on.

Examples of the metal deactivator include N, N'-bis (3- (3,5-di-t-butyl-4-hydroxyphenyl) propionyl) hydrazine and 3- (N-salicyloyl) amino-1,2,4. -Triazole, 2,2'-oxamidbis- (ethyl 3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate) and the like can be mentioned.

Flame-retardant (auxiliary) agents and fillers include carbon, clay, zinc oxide, tin oxide, titanium oxide, magnesium oxide, molybdenum oxide, antimony trioxide, silicone compounds, quartz, talc, calcium carbonate, magnesium carbonate, and white carbon. And so on.

Examples of lubricants include hydrocarbon-based, fatty acid-based, fatty acid amide-based, ester-based, alcohol-based, and metal soap-based lubricants. Among them, wax E and wax OP (trade names, manufactured by Hoechst) are used inside. Examples include ester-based, alcohol-based, and metal soap-based, which simultaneously exhibit slipperiness and external slipperiness. Among them, zinc stearate, magnesium stearate, and calcium stearate have the effect of improving insulation resistance, and zinc stearate and magnesium stearate have the effect of preventing rheumatism. Furthermore, by using a fatty acid amide together as a lubricant, it becomes possible to easily control the adhesion to the conductor.

2. 2. Production of Flame Retardant Resin Composition The flame retardant resin composition of the present invention is obtained by melt-kneading each of the above components with a commonly used kneading device such as a twin-screw kneading extruder, a Banbury mixer, a kneader, or a roll. be able to.

3. 3. Manufacture of Molded Body Next, the resin molded body of the present invention will be described.
The resin molded body of the present invention can be molded into various shapes such as an insulated electric wire / cable provided with a conductor / optical fiber inside, a hollow tube, and a sheet.

In the case of an optical fiber, there are no restrictions on the wire diameter and the number of wires, and in the case of an insulated wire, the conductor diameter and the material of the conductor are not particularly limited, and are appropriately determined according to the application. The wall thickness of the coating layer of the insulating resin composition formed around the conductor is also not particularly limited, but is preferably 0.15 to 1 mm. Further, the insulating layer may have a multilayer structure, and may have an intermediate layer or the like in addition to the coating layer formed of the insulating resin composition of the present invention.

In the case of a cable, the resin composition may be used to bundle several outerly coated conductors, optical fibers, etc., twisted, and then coated on the outer side, or other resins. The resin composition may be coated on the outside after bundling several pieces coated on the outside such as a conductor and an optical fiber using the composition and then twisting the conductor, or the conductor using the resin composition. After bundling several pieces coated on the outside such as an optical fiber, the resin composition may be coated on the outside after twisting.

The resin molded product of the present invention may be crosslinked with the above-mentioned insulating resin composition of the present invention. In that case, the insulating resin composition of the present invention can be produced by extrusion-coating around the conductor using an ordinary extrusion molding machine for electric wire production, and then cross-linking the coating layer. By using a crosslinked body as the coating layer, not only the heat resistance but also the flame retardancy is improved.

The method of cross-linking is not particularly limited, and can be carried out by an electron beam cross-linking method or a chemical cross-linking method. When the electron beam cross-linking method is used, the dose of the electron beam is appropriately 1 to 30 Mrad.

In the case of the chemical cross-linking method, an organic peroxide such as hydroperoxide, dialkyl peroxide, diacyl peroxide, peroxy ester, ketone peroxy ester, or ketone peroxide is blended as a cross-linking agent in the resin composition, and cross-linked by heat treatment after extrusion molding coating. To do.

Hereinafter, the present invention will be described with reference to Examples, but the present invention is not limited thereto.

1. 1. Evaluation method ・ Appearance test (1) Immediately after taking out the Banbury Mixer Immediately after taking out the Banbury mixer, it was confirmed whether there was foaming.
○ 5 cm square with no observation of foaming
5 cm square with 1 to 5 or less foams
5 cm square with 5 or more foams ×
And said.
○ and △ were accepted.
-Appearance test (2) Immediately after the extruder The extruder head was set to 180 ° C., and the screw rotation speed was 20 r. p. m. Foaming was confirmed with the head open.
○ for which foaming was not observed
Those with only small foam with a diameter of 1 mm or less are △
Those in which foaming larger than 1 mm in diameter was observed ×
And said.
It does not necessarily have to be ○ or △.
-Appearance test (3) Immediately after the extruder The extruder head was set to 200 ° C., and the screw rotation speed was 40 r. p. m. Foaming was confirmed with the head open.
○ for which foaming was not observed
Those with only small foam with a diameter of 1 mm or less are △
Those in which foaming larger than 1 mm in diameter was observed ×
And said.
It does not necessarily have to be ○ or △.
-Appearance test (4) The electric wire extruder head was set to 180 ° C., and the screw rotation speed was 20 r. p. m. The electric wire was manufactured in Japan and foaming was confirmed.
○ for which foaming was not observed
Those with less than 1 foam per 1 m
Those in which more than one foaming was observed per 1 m ×
And said.
○ and △ were passed. ・ Appearance test (5) The electric wire extruder head was set to 180 ° C., and the screw rotation speed was 30 r. p. m. The electric wire was manufactured in Japan and foaming was confirmed.
○ for which foaming was not observed
Those with less than 1 foam per 1 m
Those in which more than one foaming was observed per 1 m ×
And said.
It does not necessarily have to be ○ or △.
-Acetic acid resistance test A 10 wt% acetic acid aqueous solution was placed in a desiccator, the electric wire was held on the desiccator so as not to come into contact with the liquid, and the electric wire was left at 25 ° C. for 48 hours.
After that, the electric wire was taken out and the appearance was confirmed.
Those with water droplets on the wire surface ×
○ If there are no water droplets on the wire surface
And said.
・ 60 degree tilt flame retardant test A 60 degree tilt flame retardant test was conducted in accordance with JIS C 3005. Three tests were conducted, and the case where even one passed was marked as ◯.

2. 2. Raw materials used The following materials were used as the raw materials for each component.
Thermoplastic resin (A)
(A) JIS standard shore hardness A20 or more, shore hardness D54 or less Thermoplastic resin EPDM ethylene / propylene / non-conjugated diene copolymer rubber 3720P (Dow Chemical) Shore hardness A72 Mooney viscosity 20 Ethylene content 70%
EPM Ethylene Propylene Random Copolymer Rubber Mitsui 0045 (Mitsui Chemicals) Shore Hardness A60
Elastomer-based material Styrene-based elastomer Septon 4077 (Kuraray) SEEPS Shore hardness A78
Acrylic rubber Baymac DP (DuPont) Shore hardness A61
EVA
EV180 (Mitsui Duupon Polychemical) Shore Hardness A77
EEA
NUC6510 (NUC) Shore hardness A88
Maleic Acid Modified Styrene Elastomer Clayton 1901FG Shore Hardness A75
Chlorinated polyethylene Eraslen 402NA (Showa Denko) Shore hardness A58
Ethylene-α-olefin rubber Engage 7256 (Dow Chemical) Shore hardness A82
Component (c) Thermoplastic resin exceeding JIS shore hardness D54 (optional component)
PP
SunAllomer PB222A (SunAllomer) Shore Hardness D75
LLDPE
CU5003 (Sumitomo Chemical) Shore hardness D58
NCC7540 (Nippon Unicar) Shore hardness D58
LDPE
UBE C 180 (Ube Maruzen Petrochemical) Shore hardness D57
(X) Others PW-90 Idemitsu Kosan Co., Ltd. Paraffin oil Trimerit N-08 Kao Co., Ltd. (X-1) Glidant Polyethylene wax Product name: PE-WAX (manufactured by Honeywell)
(X-2) Copper damage inhibitor Product name: CDA-1 (manufactured by ADECA)
(X-3) Hindert Phenolic Antioxidant Ilganox 1010 (manufactured by BASF)
Component (b) Aluminum hydroxide composite having a 1% dehydration temperature of 240 ° C. or higher and a total dehydration amount of 25% or higher.

(1) Adjustment of heat-resistant aluminum hydroxide Using commercially available aluminum hydroxide and silica (manufactured by Nippon Silica Industry Co., Ltd.) as a reaction retardant, aluminum hydroxide and silica were stirred with a mixer for 30 seconds. The mixture was placed in a stainless steel vat and cured in an autoclave at 215 ° C. for 8 hours. After completion of the reaction, the obtained reaction product was dried to obtain heat-resistant aluminum hydroxide.
The following aluminum hydroxide was used. C-301N Average particle size 1.5 μm
C-303 Average particle size 2.5 μm
CL-303 Average particle size 4.0 μm
Heidilite H43M Average particle size 0.75 μm

1% dehydration temperature 0.8 g of a sample was thermogravimetrically measured at 10 ° C./min, and the rate of change in weight from 100 ° C. to 580 ° C. was taken as the total dehydration amount based on the weight at 100 ° C. Further, the measurement was started from 120 ° C., and the temperature at which 1% of the total dehydration amount was reduced was defined as the 1% dehydration temperature.
The average particle size is measured as follows. Using a modified alcohol (trade name: Solmix) as the dispersion medium, take 50 ml of the dispersion medium in a 200 ml beaker and add 0.2 g of heat-resistant aluminum hydroxide. Next, after dispersing for 3 minutes with an ultrasonic disperser (Nippon Seiki Seisakusho US-300T), measurement is performed using an HRA type microtrack particle size distribution meter (manufactured by Nikkiso Co., Ltd.).
Comparative component Heidilite H43M (Showa Denko) 1% Dehydration temperature 221 ° C, total dehydration 35%
C-301N (Sumitomo Chemical) 1% dehydration temperature 223 ° C, total dehydration 35%
C-303 (Sumitomo Chemical) 1% dehydration temperature 231 ° C, total dehydration 35%
CL-303 (Sumitomo Chemical) 1% dehydration temperature 233 ° C, total dehydration 35%
Magnesium hydroxide Magnesium hydroxide surface-treated with a silane coupling agent Brand name: Kisuma 5L (manufactured by Kyowa Chemical Industry Co., Ltd.)
1% dehydration temperature 300 ° C or higher Optional additive component Lubricants Calcium stearate (NOF)
Anti-aging agent Hindert phenolic antioxidant Irganox 1010 (manufactured by BASF)

Examples 1-17, Comparative Examples 1-6
Table 1 shows the content of each component of the resin compositions of Examples and Comparative Examples (the numerical values in the table are parts by mass). Each component shown in the table was dry-blended at room temperature and melt-kneaded at 195 to 205 ° C. using a Banbury mixer to prepare each flame-retardant resin composition.
The appearance of the obtained resin composition was confirmed, and the presence or absence of foaming was investigated.

Next, the flame-retardant resin compositions of the above Examples and Comparative Examples, which were previously melt-kneaded, were extruded onto a conductor (tin-plated annealed copper wire having a conductor diameter of 0.8 mmφ) using an extrusion coating device for manufacturing electric wires. Each was coated by the method to produce an insulated wire. The outer diameter was 1.3 mm and the wall thickness of the insulating layer was 0.25 mm.
The following evaluations were performed for each of the obtained insulated wires, and the obtained results are shown in the table.

As is clear from Table 1, the flame-retardant resin composition of the present invention had good properties (Examples 1 to 17).
On the other hand, as shown in Table 1, the comparative example had a problem in either the foaming test or the acid resistance test (Comparative Examples 1 to 6).

The flame-retardant resin composition of the present invention is excellent in mechanical properties, acid resistance, chemical resistance, and heat resistance, and is excellent in acid resistance without foaming during molding. Therefore, the resin composition and the composition were used. It can be suitably used as a material for a molded product, an electric wire / cable as a coating material using the resin composition thereof, an optical fiber cable, and other molded parts.

Claims (12)

100 parts by mass of a thermoplastic resin composition (A) containing a thermoplastic resin having a JIS shore hardness of A 58 or more and a shore hardness of A 88 or less.
25 to 240 parts by mass of aluminum hydroxide composite having a 1% dehydration temperature of 240 ° C. or higher and a total dehydration amount of 25% or higher.
Contains,
The thermoplastic resin
Ethylene-vinyl acetate copolymer, ethylene-acrylic acid ester copolymer, ethylene-methacrylic acid ester copolymer, ethylene-α-olefin copolymer, and ethylene-α-olefin-diene copolymer, and , Styrene-conjugated diene-based random copolymer, styrene-conjugated diene-based block copolymer, hydrogenated styrene-conjugated diene-based random copolymer, hydrogenated styrene-conjugated diene-based block copolymer, and maleic acid modification A flame-retardant resin composition (X) for an insulated electric wire and a cable, which comprises at least one selected from a styrene-based elastomer which is one of styrene-based elastomers and chlorinated polyethylene . The flame-retardant resin composition (X) for insulated wires and cables according to claim 1 , wherein the thermoplastic resin is 60 to 100% by mass in the components of the thermoplastic resin composition (A). .. Among the components of the thermoplastic resin composition (A), the total amount of the ethylene-vinyl acetate copolymer and the ethylene-α-olefin copolymer as the thermoplastic resin is 70 to 80 % by mass, and the styrene. The total amount of the styrene-based elastomer and the ethylene-acrylic acid ester copolymer, the total amount of the styrene-based elastomer and the ethylene-methacrylic acid ester copolymer, and any one of the styrene-based elastomers in the previous term are 10 to 30 % by mass. The flame-retardant resin composition (X) for an insulated electric wire and a cable according to claim 2 , wherein the composition is characterized by the above. Among the components of the thermoplastic resin composition (A), the ethylene-vinyl acetate copolymer is 20 to 50% by mass, and the ethylene-α-olefin copolymer is 20 to 60 % by mass. The flame-retardant resin composition (X) for an insulated electric wire and a cable according to claim 3 . In component of the thermoplastic resin composition (A), as the thermoplastic resin, insulated wire and flame cable retardant resin composition according to claim 2, wherein the chlorinated polyethylene is 90 mass% (X). 20% by mass of the styrene-based elastomer is contained as the thermoplastic resin in the components of the thermoplastic resin composition (A), and the ethylene-α-olefin-diene copolymer or the ethylene-α-olefin copolymer weight. The flame-retardant resin composition (X) for an insulated electric wire and a cable according to claim 2, wherein the mixture contains 40% by mass. The flame retardant for insulated electric wires and cables according to any one of claims 1 to 6 , wherein the component of the thermoplastic resin composition (A) contains 0 to 15 % by mass of paraffin oil. Resin composition (X). Melt mass flow rate (JIS)
The flame-retardant resin composition for insulated wires and cables according to any one of claims 1 to 7 , wherein K7210 (1999), temperature 190 ° C., load 10 kg) is 10 g / 10 minutes or less. X). The insulated wire according to any one of claims 1 to 8 , wherein 25 to 100 parts by mass of the aluminum hydroxide composite is contained with respect to 100 parts by mass of the thermoplastic resin composition (A). And flame-retardant resin composition (X) for cables. The flame-retardant resin composition for an insulated electric wire and a cable according to any one of claims 1 to 9 , wherein the average particle size of the aluminum hydroxide composite is 2.0 to 4.5 μm. ). An insulated electric wire and a cable, wherein the conductor is coated with the flame-retardant resin composition (X) according to any one of claims 1 to 10 . The insulated wire and cable according to claim 11 , wherein the flame-retardant resin composition (X) is crosslinked.