JP5306764B2 - Resin composition and resin molded body - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a resin composition that has high flame resistance and superior mechanical properties required for insulated wires, can be colored in arbitrary colors, holds electrical characteristics, and has no problems such as: elution of a heavy metal compound and a phosphorus compound by a reclamation upon disposal; and development of a lot of smoke and a corrosive gas by burning. <P>SOLUTION: This resin composition includes 100 pts.mass of a resin component (C) and 150-300 pts.mass of a metal hydrate, wherein the resin component (C) comprises: 100-20 mass% of a resin composition (A) obtained by grafting 0.5-15 mass% of (meth)acrylate monoester to at least one selected from the group consisting of a polyolefin, an ethylenic copolymer and an acrylic rubber; and 0-80 mass% of at least one component (B) selected from the group consisting of the polyolefin resin, the ethylenic copolymer and the acrylic rubber. <P>COPYRIGHT: (C)2010,JPO&amp;INPIT

Description

  The present invention relates to a resin composition that does not cause elution of heavy metal compounds, generation of a large amount of smoke or corrosive gas at the time of disposal such as landfill and incineration, and insulated wires used for internal and external wiring of electrical and electronic equipment It relates to a resin molded body.

  Various properties such as flame retardancy, tensile properties, and heat resistance are required for coating materials for insulated wires used for internal and external wiring of electric / electronic devices. For this reason, as a covering material for these insulated wires, a halogen-based flame retardant containing a bromine atom or a chlorine atom in the molecule is blended with a base resin mainly composed of polyvinyl chloride (PVC) compound or ethylene copolymer. It is well known to use a resin composition.

In recent years, various problems have been raised when an insulated wire using such a coating material is discarded without appropriate treatment. For example, when discarded by landfill, elution of plasticizers and heavy metal stabilizers blended in the coating material, and when incinerated, problems such as generation of a large amount of corrosive gas and generation of dioxins occur.
For this reason, studies are being actively conducted on techniques for coating electric wires with non-halogen flame retardant materials that do not generate harmful heavy metals or halogen-based gases.

  Conventional non-halogen flame retardant materials are those in which flame retardancy is expressed by blending a flame retardant containing no halogen with a resin. Examples of flame retardants for such coating materials include magnesium hydroxide, water Metal hydrates such as aluminum oxide, and as resins, polyethylene, ethylene-1-butene copolymer, ethylene-propylene copolymer, ethylene-vinyl acetate copolymer, ethylene-ethyl acrylate copolymer An ethylene-propylene-diene terpolymer is used.

  By the way, an electronic wire harness used in an electronic device is required to have high flame resistance from the viewpoint of safety, and has extremely strict flame resistance standards UL1581 (Reference Standard for Electrical Wires, Cables, and Flexible Cords). The VW-1 standard of the vertical flame test (Vertical Flame Test), the horizontal flame retardant standard, and the 60 degree inclined flame retardant characteristic defined in JIS C3005 must be cleared. Furthermore, with respect to properties other than flame retardancy, high mechanical properties such as elongation at break of 100% or higher and tensile strength at break of 10 MPa or higher are required according to UL and electrical appliance regulations.

In order to realize such high flame retardancy and mechanical characteristics in an insulated wire using a non-halogen flame retardant material, the following techniques have been studied.
First, an insulating composition using both red phosphorus and magnesium hydroxide has been studied. However, the red phosphorus cannot be colored in any color, including white, due to the coloration of red phosphorus. May run into the ground and enrich the lake.
In addition, an insulating composition in which a large amount of magnesium hydroxide is added has been studied, but it may burn depending on the thickness of the insulating layer, and the flame retardancy may be insufficient or the mechanical strength may be reduced. There is a problem that it drops significantly.

  Patent Document 1 discloses an example in which an inorganic flame retardant and a melamine cyanurate compound are used in combination with a polyolefin or an ethylene-based copolymer. However, the insulated wire using this composition is incompatible with the above-mentioned VW-1 standard, and when magnesium hydroxide surface-treated with a commonly used higher fatty acid is added to about 200 parts by mass, the mechanical strength is significantly reduced. To do.

Furthermore, the insulated wire is required to have high insulated electrical characteristics. However, in order to adapt the above-mentioned flame retardancy, for example, an ethylene vinyl acetate copolymer having a high VA content has to be used as a base material, and it has been difficult to maintain the insulating electrical characteristics.
Further, such a highly flame-retardant non-halogen insulated wire has a low dielectric breakdown voltage, and it has been difficult to reduce the thickness when used as a power line.
Japanese Patent Laid-Open No. 2-75642

  The present invention solves these problems, has high flame retardancy required for insulated wires and excellent mechanical properties, can be colored in any color, retains electrical properties, and is disposed by landfill at the time of disposal. To provide a resin composition free from problems such as elution of heavy metal compounds and phosphorus compounds, a large amount of smoke due to incineration, and generation of corrosive gas, and a resin molded body such as an insulated wire using this composition as an insulation coating material. Objective.

As a result of intensive studies in view of the above problems, the present inventors have used an ethylene copolymer, polyolefin, acrylic rubber as the base resin of the coating material, and a specific amount of monoester in all or part of the base resin. By grafting (meth) acrylate and using this resin, it is possible to obtain a resin composition and a resin molded article which are excellent in mechanical properties and electrical characteristics and have no flame retardant and do not generate harmful substances such as dioxin. I found out that I can.
The present invention is based on this finding.

That is, the present invention
(1) 0.5-15 mass of only monoester (meth) acrylate with respect to at least 1 sort (s) chosen from the group which contains an ethylene- vinyl acetate copolymer at least and consists of polyolefin, an ethylene-type copolymer, and an acrylic rubber. % And grafted resin composition (A) 100 to 20% by mass, and at least one selected from the group consisting of polyolefin, ethylene copolymer and acrylic rubber (B) 0 to 80% by mass A resin composition comprising 150 to 300 parts by mass of a metal hydrate with respect to 100 parts by mass of the resin component (C) to be obtained,
(2) Melting the metal hydrate and the resin to be grafted while grafting a monoester (meth) acrylate to at least one selected from the group consisting of polyolefins, ethylene copolymers, and acrylic rubbers and wherein the obtained by kneading at a temperature above (1) resin composition according to item,
(3) said resin having a polypropylene skeleton in the resin component (C), characterized in that it contains 5 to 50 mass% (1) or (2) the resin composition according to item,
(4) The resin composition according to any one of (1) to (3), wherein the metal hydrate is surface-treated with a reactive silane coupling agent.
(5) The resin composition according to any one of (1) to (4), wherein the acid content of the ethylene copolymer is 15 to 65% by mass in the resin component (C). ,
(6) Content of the said monoester (meth) acrylate is 0.5-10 mass% in the resin component (C), It is any one of (1)-(5) characterized by the above-mentioned. Resin composition,
(7) The insulating composition according to any one of (1) to (6), wherein the monoester (meth) acrylate is a compound represented by the following formula:

(Wherein n represents an integer of 1 to 25, R ¹ represents a hydrogen atom or a methyl group, and R ² represents a saturated aliphatic hydrocarbon group or an aromatic hydrocarbon group).
(8) The method for producing a resin composition according to (1), wherein the resin composition includes at least an ethylene-vinyl acetate copolymer and is selected from the group consisting of a polyolefin resin, an ethylene copolymer, and an acrylic rubber. A method for producing a resin composition, characterized by kneading at least the melting temperature of the grafted resin with a metal hydrate while grafting only a monoester (meth) acrylate on at least one kind,
(9) the (1) to the resin molded body, wherein the resin composition described coated on the outside of the conductor and / or optical fiber in any one of (7), and (10) the resin composition is intended to provide a resin molded article according to characteristics to (9) claim that it is crosslinked.

  The resin composition of the present invention uses a polyolefin resin and / or an ethylene copolymer and / or a resin obtained by grafting a monoester (meth) acrylate on an acrylic rubber as a part or all of a base resin, and a metal hydrate , Preferably a metal hydrate surface-treated with a reactive silane coupling agent is contained in the resin, and it has excellent mechanical properties, flame retardancy (such as vertical flame retardancy), insulated electrical properties, and dielectric breakdown voltage properties It can be set as a resin composition. Furthermore, by using this resin composition, it is possible to obtain a resin molded body such as an electric wire / cable excellent in mechanical characteristics, flame retardancy, and electrical characteristics.

The resin composition of the present invention, at least an ethylene - containing vinyl acetate copolymer and a polyolefin, ethylene copolymer, and only monoesters (meth) acrylate to at least one selected from the group consisting of acrylic rubber 0 0.5 to 15% by mass of the resin composition (A) 100 to 20% by mass and at least one selected from the group consisting of polyolefin resin, ethylene copolymer and acrylic rubber (B) 0 It contains 150 to 300 parts by mass of a metal hydrate with respect to 100 parts by mass of the resin component (C) consisting of ˜80% by mass.

  Usually, a non-halogen resin composition and an electric wire using the same have a low volume resistivity and insulation resistance, and further, when immersed for a long period of time, the volume resistivity and insulation resistance further decrease. However, in the resin composition of the present invention, by grafting monoester (meth) acrylate onto the base material, not only the volume resistivity and insulation resistance are improved, but also the volume resistivity and insulation resistance after long-term water immersion. Greatly improved. Furthermore, it was found that the dielectric breakdown voltage was improved, and particularly the dielectric breakdown voltage after water immersion was greatly improved. The reason for the improvement of the insulation resistance and breakdown voltage is not clear, but the grafted ester part surrounds the metal hydrate, which relaxes the interface between the resin and the metal hydrate, resulting in a volume resistivity. It is estimated that the breakdown voltage has improved. Further, by surrounding the metal hydrate, it is considered that the metal hydrate is less affected by water and changes due to water immersion are reduced.

When such a monoester (meth) acrylate is added, the strength, elongation and flame retardancy of the resin composition are significantly reduced. However, it has been found that by adding such a monoester (meth) acrylate to the base material after grafting, the mechanical properties are improved and the flame retardancy is greatly improved. Furthermore, the moldability of the resin is better than when it is not grafted, and the productivity is also excellent.
Although the reason why the flame retardancy is improved is not clear, it is presumed that the oxygen coefficient of the resin itself is improved by grafting the oxygen-containing portion.

  Hereinafter, each component contained in the resin composition of the present invention, specifically the insulating resin composition, will be described.

(Resin component (C))
<1> Ethylene copolymer In the resin composition of the present invention, an ethylene copolymer can be used as one component of the resin. Specific examples of the ethylene copolymer that can be used in the present invention include ethylene-vinyl acetate copolymer (EVA), ethylene- (meth) acrylic acid copolymer, ethylene- (meth) alkyl acrylate copolymer. Examples include coalescence. These may be used alone or in combination of two or more.

From the viewpoint of flame retardancy and improvement of mechanical properties, an ethylene-vinyl acetate copolymer is preferable as the ethylene polymer used in the present invention. Further, in order to improve flame retardancy, the content of copolymerized components copolymerized with ethylene (for example, EVA is vinyl acetate (VA) content, EEA is ethyl acrylate (EA) content) is 23-80. % By mass is preferable, and more preferably 25 to 80% by mass. Further, MFR (melt flow rate) (ASTM-D-1238) of an ethylene copolymer is 0.2 to 20, more preferably 0.5 from the viewpoint of strength and kneadability of the resin composition. About 10 to 10 is preferable.
In general, when EVA having a high VA content is used, flame retardancy is improved, but volume specific resistance, insulation electric resistance, and dielectric breakdown voltage are remarkably lowered. By grafting the monoester (meth) acrylate of the present invention, a decrease in insulation resistance and a decrease in dielectric breakdown voltage can be suppressed. Furthermore, since the same level of flame retardancy can be maintained even when the VA content is lowered, the volume resistivity and dielectric breakdown voltage can be further improved.

  In this invention, an ethylene-type copolymer can be used in both the part (resin composition) (A) which grafts monoester (meth) acrylate, and the part (B) which does not. The total acid content of the ethylene-based copolymer in the resin component (C) is preferably 15% by mass to 65% by mass, and more preferably 18% by mass to 55% by mass. This is because if the content is too large, the effects of electrical properties and flame retardancy produced by grafting the monoester (meth) acrylate are almost lost. On the other hand, if the content is too low, the flame retardancy is lowered or the mechanical strength is significantly lowered.

<2> Acrylic rubber An acrylic rubber can be used in the present invention.
Acrylic rubber is a rubber elastic body obtained by copolymerizing a small amount of monomers having various functional groups with alkyl acrylates such as methyl acrylate, ethyl acrylate and butyl acrylate as monomer components. As a monomer to be used, 2-chloroethyl vinyl ether, methyl vinyl ketone, acrylic acid, acrylonitrile, butadiene, or the like can be appropriately used. Specifically, Nipol AR (trade name, manufactured by Nippon Zeon Co., Ltd.), JSR AR (trade name, manufactured by JSR Corp.) or the like can be used.

In particular, it is preferable to use methyl acrylate as the monomer component. In this case, a binary copolymer with ethylene and an unsaturated hydrocarbon having a carboxyl group in the side chain are further used as monomers. A polymerized ternary copolymer can be particularly preferably used. Specifically, in the case of a binary copolymer, Baymac D or Baymac DLS, and in the case of a ternary copolymer, Baymac G, Baymac HG, Baymac LS, Baymac GLS (trade names, both of which are Mitsui and DuPont) Polychemical Co., Ltd.) can be used.
By blending these acrylic rubbers, the peelability is improved without extending the covering material like a whisker when peeling. In addition, flame retardancy is remarkably improved by blending acrylic rubber. By using acrylic rubber in combination with the ethylene-based copolymer, it becomes possible to have relatively high insulating properties while maintaining flame retardancy.

  In the present invention, the acrylic rubber can be used in both the part (A) grafted with the monoester (meth) acrylate and the part (B) not grafted, preferably 0 to 60% by mass in the resin component (C), More preferably, it is used at a ratio of 0 to 45% by mass. This is because when the amount of acrylic rubber is too large, not only the extrudability of the electric wires is remarkably lowered, but also the adhesion between the electric wires at the time of uncrosslinking is remarkably increased and the productivity is greatly reduced.

<3> Polyolefin Examples of polyolefin include polyethylene, polypropylene, polybutene, polymethylpentene and derivatives thereof, ethylene α-olefin copolymer, ethylene-propylene rubber, ethylene-butadiene rubber, and reactor-TPO. Polyolefins can be used both in the component (A) grafted with monoester (meth) acrylate and in the part (B) not. The polyolefin content is preferably 5 to 80% by mass, more preferably 5 to 40% by mass, and more preferably 10 to 40% by mass in the resin component (C). By containing polyolefin, the heat deformation characteristics, heat resistance, strength, etc. can be improved.

The polyolefin is preferably a polyethylene resin such as low density polyethylene, linear low density polyethylene, or metallocene polyethylene, or a resin having a polypropylene skeleton such as homopolypropylene, random polypropylene, block polypropylene, or reactor TPO.
The resin having a polypropylene skeleton is contained in 100% by mass of the resin component (C), preferably 5 to 50% by mass, and more preferably 8 to 40% by mass. This is because by introducing a resin having a polypropylene skeleton, it can be used up to a relatively high temperature without crosslinking.

<4> Polyolefin / ethylene copolymer modified with unsaturated carboxylic acid The polyolefin or ethylene copolymer modified with unsaturated carboxylic acid is <3> polyolefin or <1> ethylene copolymer, respectively. Can be used in whole or in part.
Polyolefins modified with unsaturated carboxylic acids are linear polyethylene, ultra-low density polyethylene, high density polyethylene, polypropylene, ethylene-vinyl acetate (VA) copolymer, ethylene-acrylic acid copolymer, ethylene-ethyl. An acrylate (EA) copolymer, an ethylene copolymer such as an ethylene-methacrylate copolymer, a resin modified with an unsaturated carboxylic acid or a derivative thereof, and as an unsaturated carboxylic acid used for modification, For example, maleic acid, itaconic acid, fumaric acid and the like can be mentioned, and examples of unsaturated carboxylic acid derivatives include maleic acid monoester, maleic acid diester, maleic anhydride, itaconic acid monoester, itaconic acid diester, itaconic anhydride, Fumaric acid monoester, fumaric acid diester, fumaric anhydride, etc. A. The modification of the polyolefin can be performed, for example, by melting and kneading the polyolefin and the unsaturated carboxylic acid in the presence of the organic peroxide. The modification amount of maleic acid is usually about 0.5 to 7% by mass.

Polyolefins modified with unsaturated carboxylic acids are effective as a compatibilizer for resins and fillers, ethylene copolymers and styrene elastomers, polyolefins with styrene resins in the side chain, and ethylene propylene rubber. It has the effect of improving the characteristics, suppressing the decrease in insulation resistance when immersed, and increasing the strength of the compound.
The blending amount of the <4> component is preferably 2 to 30% by mass and more preferably 5 to 20% by mass in the resin component (C).

<5> Monoester methacrylate A monoester (meth) acrylate grafted on part or all of the base material used in the present invention is used.
Monoester (meth) acrylates can be grafted to the resin by heating with peroxide during or after blending.
The monoester (meth) acrylate used is preferably

(In the formula, n represents an integer of 1 to 25, R ¹ represents a hydrogen atom or a methyl group, and R ² represents a saturated aliphatic hydrocarbon group or an aromatic hydrocarbon group.)
It is a monoester (meth) acrylate shown by.
In the above formula, R ² is preferably a saturated aliphatic hydrocarbon group or aromatic hydrocarbon group having 1 to 6 carbon atoms, more preferably a methyl group or a phenyl group.
n is preferably 1-15, more preferably 1-6.

This monoester (meth) acrylate is preferably grafted by adding an organic peroxide and heating after mixing with the resin to be grafted or during mixing.
The heating temperature is preferably higher than the melting temperature of the resin to be grafted.

Examples of the organic peroxide 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) hexyne-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, diacetyl peroxide, lauroyl peroxide , Tert-butyl cumyl peroxide, etc. It can gel.
Of these, in terms of odor, 2,5-dimethyl-2,5-di- (tert-butylperoxy) hexane, 2,5-dimethyl-2,5-di- (tert-butylperoxy) hexyne -3 is most preferred.
The amount of the organic peroxide is 0.1 to 1.5 parts by mass, and more preferably 0.15 to 1.0 part by mass with respect to 100 parts by mass of the resin to be grafted.

  This monoester (meth) acrylate is required to be 0.5% by mass to 15% by mass with respect to the resin of the resin composition (A) to be grafted, preferably 0.8% by mass to 3% by mass. . If the amount is less than 0.5% by mass, the effect is substantially lost. If the amount is more than 15% by mass, the graft resin is gelled and appears as a scum in the resin composition or the covering portion of the electric wire / cable. Getting worse. The content of the monoester (meth) acrylate in the resin component (C) is preferably 0.2% by mass to 10% by mass, and more preferably 0.5% by mass to 8% by mass.

The resin component (C) in the present invention is a <5> monoester (meth) acrylate for at least one selected from the above <1> ethylene copolymers, <2> acrylic rubbers, and <3> polyolefins. 0.5 to 15% by mass of a grafted resin composition (A), <1> at least one component selected from an ethylene copolymer, <2> acrylic rubber, and <3> polyolefin ( And B).
Content of the resin composition (A) in a resin component (C) is 100-20 mass%, Preferably it is 100-30 mass%, More preferably, it is 100-50 mass%.
Moreover, content of the component (B) in a resin component (C) is 0-80 mass%, Preferably it is 0-70 mass%, More preferably, it is 0-50 mass%.
The polyolefin, ethylene copolymer, or acrylic rubber used in the resin composition (A) and the polyolefin, ethylene copolymer, or acrylic rubber of the component (B) may be the same or different.

(Metal hydrate)
The type of metal hydrate that can be used in the present invention is not particularly limited. For example, aluminum hydroxide, magnesium hydroxide, hydrated aluminum silicate, hydrated magnesium silicate, basic magnesium carbonate, orthosilicate aluminum, hydro Examples thereof include metal compounds having a hydroxyl group or crystal water such as tarside, and these may be used alone or in combination of two or more. Of these metal hydrates, aluminum hydroxide and magnesium hydroxide are preferred. Of these, magnesium hydroxide is preferred.

Examples of the metal hydrate include untreated, treated with fatty acid, treated with phosphate ester, and treated with silane coupling agent. Of these, those treated with a silane coupling agent are preferred.
Examples of the silane coupling agent used for the surface treatment of the metal hydrate include those having an alkyl group, an alkoxy group, an amino group, a vinyl group, and an epoxy group at the terminal. These silane coupling agents may be used alone or in combination of two or more. Among them, it is preferable to use a reactive silane coupling agent such as an amino group, a vinyl group, or an epoxy group at the terminal, and among them, it is preferable to use one having a vinyl group or an epoxy group as one component, for example, Vinyltrimethoxysilane, vinyltriethoxysilane, glycidoxypropyltrimethoxysilane, glycidoxypropyltriethoxysilane, glycidoxypropylmethyldimethoxysilane, methacryloxypropyltrimethoxysilane, methacryloxypropyltriethoxysilane, methacryloxy Examples include propylmethyldimethoxysilane. These silane coupling agents having reactivity at the ends may be used singly or in combination of two or more. These silane coupling agents are at least 20% by mass or more, preferably 40% by mass or more, more preferably 60% by mass or more, based on the total silane coupling agent.

  As the surface-treated aluminum hydroxide for the silane coupling agent that can be used in the present invention, surface-untreated aluminum hydroxide (such as Hydrite H42M (trade name, manufactured by Showa Denko KK)) has reactivity at the above-mentioned ends. Examples thereof include those that have been surface-treated with a silane coupling agent.

  Further, as the surface-treated magnesium hydroxide for the silane coupling agent that can be used in the present invention, a surface-untreated one (as a commercially available product, Kisuma 5 (trade name, manufactured by Kyowa Chemical Co., Ltd.), stearic acid, olein, etc. Surface-treated with fatty acids such as acids (Kisuma 5A (trade name, manufactured by Kyowa Chemical Co., Ltd.), etc., and those treated with phosphate ester were surface-treated with a silane coupling agent having reactivity at the terminal. Or commercially available products of magnesium hydroxide (Kisuma 5L, Kisuma 5P (both trade names, manufactured by Kyowa Chemical Co., Ltd.)) already surface-treated with a silane coupling agent having reactivity at the terminal.

  In addition to the above, a metal that has been surface-treated using a silane coupling agent that has a terminal reactivity in addition to magnesium hydroxide or aluminum hydroxide that has been partially surface-treated with a fatty acid or a phosphate ester in advance. Hydrates can also be used.

  When performing the surface treatment of the metal hydrate, the silane coupling agent can be blended with the untreated or partially surface-treated metal hydrate in advance or at the time of kneading. The silane coupling agent at this time is appropriately added in an amount sufficient for the surface treatment. Specifically, it is 0.1 to 3.0% by mass, preferably 0.15 to 2%, based on the metal hydrate. 5 mass%, More preferably, it is 0.2-1.5 mass%.

  In this invention, the compounding quantity of this metal hydrate is 150 mass parts-300 mass parts with respect to 100 mass parts of resin components (C), Preferably it is 170-280 mass parts. If the blended amount of the metal hydrate is too small, the required flame retardancy cannot be ensured, and if it is too large, the mechanical strength is significantly lowered.

  In addition, although not particularly limited, the metal hydrate surface-treated with a silane coupling agent having a vinyl group or an epoxy group at the terminal, and the metal hydrate surface-treated with a non-reactive silane coupling agent at the terminal Or a non-treated metal hydrate can be used, but a metal whose surface is treated with a silane coupling agent having a terminal reactivity at 50% by mass or more, more preferably 70% by mass or more of the total metal hydrate. It is preferable to be a hydrate.

(Other ingredients)
In this invention, in order to improve the dispersibility of said metal hydrate, at least 1 sort (s) of fatty acid metal salt chosen from zinc, magnesium, and calcium can be mix | blended as needed. Examples of the fatty acid of the fatty acid metal salt include oleic acid, lauric acid, myristic acid, palmitic acid, and stearic acid, and stearic acid is preferable.

In order to further improve the flame retardancy in the present invention, a melamine cyanurate compound may be added. The melamine cyanurate compound is preferably a fine particle size. The average particle size of the melamine cyanurate compound used in the present invention is preferably 10 μm or less, more preferably 7 μm or less, and even more preferably 5 μm or less. Moreover, the melamine cyanurate compound surface-treated from the dispersible surface is used preferably.
Examples of the melamine cyanurate compound that can be used in the present invention include those commercially available from MCA-6000 (trade name, manufactured by Nissan Chemical Co., Ltd.) and Merpur 15 (trade name: Ciba Japan Co., Ltd.).

  In this invention, the compounding quantity of a melamine cyanurate compound is 0-70 mass parts with respect to a total of 100 mass parts of an ethylene-type copolymer and acrylic rubber, Preferably it is 0-60 mass parts. When there are too many melamine cyanurate compounds, mechanical strength, especially elongation will fall and the appearance when it is set as an electric wire will deteriorate remarkably. The melamine cyanurate compound has an effect of greatly improving the flame retardancy due to the synergistic effect with the acrylic rubber, so it is desirable to add it when high flame retardancy is required.

The insulating resin composition of the present invention can be blended with at least one selected from zinc stannate, zinc hydroxystannate and zinc borate as necessary, and can further improve flame retardancy. By using these compounds, the speed of shell formation during combustion is increased and the shell formation becomes stronger. Accordingly, the flame retardancy can be dramatically improved together with the melamine cyanurate compound that generates gas from the inside during combustion.
The average particle size of zinc borate, hydroxy hydroxystannate, and zinc stannate used in the present invention is preferably 5 μm or less, and more preferably 3 μm or less.
Specific examples of zinc borate that can be used in the present invention include Alkanex FRC-500 (2ZnO / 3B ₂ O ₃ .3.5H ₂ O) and FRC-600 (both trade names, Mizusawa Chemical Co., Ltd.). Etc.). Examples of zinc stannate (ZnSnO ₃ ) and hydroxy hydroxy stannate (ZnSn (OH) ₆ ) include Alkanex ZS and Alkanex ZHS (both trade names, manufactured by Mizusawa Chemical Co., Ltd.).

  In the insulating resin composition of the present invention, various additives commonly used in electric wires and cables, such as antioxidants, metal deactivators, flame retardants (auxiliaries), fillers, A lubricant and the like can be appropriately blended within a range not impairing the object of the present invention.

  Antioxidants include amine-based antioxidants such as 4,4′-dioctyl diphenylamine, N, N′-diphenyl-p-phenylenediamine, and 2,2,4-trimethyl-1,2-dihydroquinoline polymer. Agent, 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) benzene and the like, bis (2-methyl-4- ( 3-n-alkylthiopropionyloxy) -5-tert-butylphenyl) sulfide, 2-mercaptobenzimidazole and its zinc salt, pentaerythritol Lithol - tetrakis (3-lauryl - thiopropionate) sulfur based antioxidants such as, and the like.

Examples of metal deactivators include N, N′-bis (3- (3,5-di-t-butyl-4-hydroxyphenyl) propionyl) hydrazine, 3- (N-salicyloyl) amino-1,2,4. -Triazole, 2,2'-oxamidobis- (ethyl 3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate) and the like.
Flame retardant (auxiliary) and filler include carbon, clay, zinc oxide, tin oxide, titanium oxide, magnesium oxide, molybdenum oxide, antimony trioxide, silicone compound, quartz, talc, calcium carbonate, magnesium carbonate, white carbon Etc.

  Examples of lubricants include hydrocarbons, fatty acids, fatty acid amides, esters, alcohols, metal soaps, among others, wax E, wax OP (both trade names, manufactured by Hoechst), etc. Examples include ester-based, alcohol-based, and metal soap-based materials that exhibit both lubricity and external lubricity. Among them, zinc stearate, magnesium stearate, and calcium stearate have an effect of improving insulation resistance, and zinc stearate and magnesium stearate have an effect of preventing the eyes. Furthermore, by using a fatty acid amide in combination as a lubricant, it becomes possible to easily control the adhesion to the conductor.

The insulating resin composition of the present invention can be obtained by melt-kneading each of the above components with a commonly used kneading apparatus such as a twin-screw kneading extruder, a Banbury mixer, a kneader, or a roll.
Preferably, melting of the resin to be grafted with the metal hydrate while grafting the monoester (meth) acrylate to at least one selected from the group consisting of the above polyolefin, ethylene copolymer, and acrylic rubber It is kneaded at a temperature or higher.
The monoester (meth) acrylate graft can be obtained by melt-kneading using a commonly used kneading apparatus such as a twin-screw kneading extruder, a Banbury mixer, a kneader, or a roll. This grafting step may be performed in advance or at the same time as kneading with a flame retardant or the like.

Next, the resin molded product 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 wire / cable provided with a conductor / optical fiber therein, a hollow tube, a sheet and the like.

  In the case of an optical fiber, the diameter and number of strands are not limited, and in the case of an insulated wire, the conductor diameter, the material of the conductor, etc. are not particularly limited, and are appropriately determined according to the application. The thickness of the coating layer of the insulating resin composition formed around the conductor is not particularly limited, but is preferably 0.15 to 1 mm. In addition, the insulating layer may have a multilayer structure, and may have an intermediate layer in addition to the coating layer formed of the insulating resin composition of the present invention.

  In the case of a cable, this resin composition may be used to bundle a number of conductors, optical fibers, and the like that are coated on the outside, and then twisted together to coat the resin composition on the outside. After bundling several conductors, optical fibers and the like coated on the outside using the composition, the resin composition may be coated on the outside after twisting, or using the resin composition, a conductor, After bundling several coated optical fibers and the like, and then twisting them, another resin composition may be coated on the outside.

  The resin molded body of the present invention may crosslink the 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 electric wire production extruder, and then crosslinking the coating layer. By making the coating layer a crosslinked body, not only the heat resistance is improved, but also the flame retardancy is improved.

The method for crosslinking is not particularly limited, and can be performed by an electron beam crosslinking method or a chemical crosslinking method.
When the electron beam crosslinking method is used, the electron beam dose is suitably 1 to 30 Mrad.
In the case of the chemical crosslinking method, organic peroxides such as hydroperoxides, dialkyl peroxides, diacyl peroxides, peroxy esters, ketone peroxy esters, and ketone peroxides are blended into the resin composition as a crosslinking agent, and crosslinked by heat treatment after extrusion coating. To do.

  EXAMPLES Hereinafter, although this invention is demonstrated further in detail based on an Example, this invention is not limited to this.

Examples and Comparative Examples First, each component (part by mass) shown in the first step shown in the following table was dry blended at room temperature, and melt-kneaded using a Banbury mixer to prepare a grafted resin composition. Furthermore, using this resin, each component (part by mass) shown in the second step was dry blended at room temperature and melt-kneaded using a Banbury mixer to produce each insulating resin composition.
Next, using an extrusion coating apparatus for producing electric wires, an insulating resin composition previously melt-kneaded on a conductor (conducting tin-plated annealed copper stranded wire with a conductor diameter of 0.76 mmφ: 17 / 0.16 mmφ) is extruded. Insulated wires were manufactured respectively. The outer diameter was 1.64 mm (the thickness of the coating layer was 0.42 mm). Some electric wires (Example 15) were cross-linked by coating with an electron beam at 5 Mrad after coating.
In addition, the following were used for each component shown in the following table.

(01) Ethylene-vinyl acetate copolymer
EV180 (trade name, manufactured by Mitsui DuPont Polychemical Co., Ltd.)
VA content 33% by mass
(02) Ethylene-vinyl acetate copolymer
YX-21 (trade name, manufactured by Tosoh Corporation)
VA content 41% by mass
(03) Ethylene-vinyl acetate copolymer
Revaprene 800HV (trade name, manufactured by LANXESS)
VA content 80% by mass
(04) Ethylene-vinyl acetate copolymer
Revaprene VPKA8784 (trade name, manufactured by LANXESS)
VA content 70% by mass
(05) Ethylene-ethyl acrylate copolymer
A-714 (trade name, manufactured by Mitsui DuPont Polychemical Co., Ltd.)
EA content 25% by mass
(06) Ternary copolymer acrylic rubber
Baymac DP (trade name, manufactured by Mitsui DuPont Polychemicals)
(07) Block polypropylene
BC3A (Product name: Made of Japan Polypropylene)
(08) Modified polypropylene
Polybond P1001 (trade name, manufactured by Chemtura)
(09) Maleic acid modified LLDPE
L-6100M (trade name, manufactured by Nippon Polyethylene)
(10) Monoester methacrylate
NK-ester M-40G (trade name, manufactured by Shin-Nakamura Chemical Co., Ltd.)
(11) Monoester methacrylate
NK-ester M-90G (trade name, manufactured by Shin-Nakamura Chemical Co., Ltd.)
(12) Monoester methacrylate
NK-ester M-230G (trade name, manufactured by Shin-Nakamura Chemical Co., Ltd.)
(13) Monoester methacrylate
NK-Ester PHE-6G (trade name, manufactured by Shin-Nakamura Chemical Co., Ltd.)
(14) Monoester acrylate
NK-Ester AM-30G (trade name, manufactured by Shin-Nakamura Chemical Co., Ltd.)
(15) Metallocene polyethylene
Kernel KF360 (trade name, manufactured by Nippon Polyethylene)
(16) Surface-treated magnesium hydroxide with a silane coupling agent having a vinyl group at the terminal
Kisuma 5L (trade name, manufactured by Kyowa Chemical)
(17) Organic peroxide
Perhexa 25B (trade name, manufactured by NOF Corporation)
(18) Hindered phenol anti-aging agent
Irganox 1010 (trade name, manufactured by Ciba Geigy)
(19) Lubricant
AC polyethylene NO. 6 (PE-WAX) (trade name, manufactured by Honeywell)

The following evaluation tests were performed on the obtained insulated wires. The results are shown in Table 1.
1) Elongation and Tensile Strength The elongation (%) of each insulated wire and the tensile strength (MPa) of the coating layer were measured based on JIS C 3005 under conditions of 25 mm between marked lines and a pulling speed of 500 mm / min. The required properties of elongation and tensile strength are each 100% or more and 10 MPa or more.
2) Flame Retardancy For each insulated wire, a Vertical Flame Test of UL1581 was performed and the number of passes was shown (passed number / N number).
3) Insulation resistance (IR)
About each insulated wire, the initial value (1h) of the insulation resistance prescribed | regulated to JISC3005 and the insulation resistance after 24 hours water immersion (24h) were measured.
The initial value is 100 MΩ · km or more, and after 24 hours, 20 MΩ · km or more is required 4) Dielectric breakdown voltage (BDV)
The wire was cut into 60 cm, the conductors at both ends were bound, and a ring-shaped sample was used to conduct an underwater pressure resistance test based on JIS C 3005. The breakdown voltage was determined at a pressure increase rate of 1 kV / sec.
Moreover, the same test was done after wiping off the moisture for the sample immersed in water at 20 ° C. for 24 hours.
The initial value is 20 kV or more, and 10 kV or more is required after being immersed in water. 5) Mass production of electric wires Mass production of electric wires has been confirmed that the wire can be extruded ○: Appearance is good and mass production is possible at an extrusion speed of 100 m / min or more There is no problem.
X: There is a problem in either the extrusion speed or the appearance.

  As shown in Table 1, in Comparative Examples 1 to 3, the breakdown voltage after being immersed in water for 24 hours did not reach the required value. In Comparative Examples 1 and 3, the required properties of tensile strength were not observed, and in addition, Cited Example 2 had difficulty in flame retardancy, and Cited Example 3 had difficulty in mass productivity. On the other hand, in Examples 1-15, in any evaluation test, it became a result without a problem.

Claims (10)

Add at least 15 to 15% by mass of monoester (meth) acrylate with respect to at least one selected from the group consisting of polyolefin, ethylene copolymer, and acrylic rubber, including at least ethylene-vinyl acetate copolymer Resin component comprising 100 to 20% by mass of a resin composition (A) obtained by grafting and at least one (B) of 0 to 80% by mass selected from the group consisting of polyolefin, ethylene copolymer, and acrylic rubber (C) The resin composition characterized by containing 150-300 mass parts of metal hydrates with respect to 100 mass parts. While grafting a monoester (meth) acrylate to at least one selected from the group consisting of polyolefin, ethylene-based copolymer, and acrylic rubber, a temperature not lower than the melting temperature of the metal hydrate and the grafted resin The resin composition according to claim 1 , wherein the resin composition is obtained by kneading. The resin composition according to claim 1 or 2 , wherein the resin component (C) contains 5 to 50% by mass of a resin having a polypropylene skeleton.   The resin composition according to claim 1, wherein the metal hydrate is surface-treated with a reactive silane coupling agent.   The resin composition according to any one of claims 1 to 4, wherein the acid content of the ethylene copolymer is 15 to 65 mass% in the resin component (C).   Content of the said monoester (meth) acrylate is 0.5-10 mass% in a resin component (C), The resin composition of any one of Claims 1-5 characterized by the above-mentioned. The resin composition according to any one of claims 1 to 6, wherein the monoester (meth) acrylate is a compound represented by the following formula.

(In the formula, n represents an integer of 1 to 25, R ¹ represents a hydrogen atom or a methyl group, and R ² represents a saturated aliphatic hydrocarbon group or an aromatic hydrocarbon group.) It is a manufacturing method of the resin composition of Claim 1, Comprising: With respect to at least 1 sort (s) chosen from the group which consists of a polyolefin resin, an ethylene-type copolymer, and an acrylic rubber at least including an ethylene-vinyl acetate copolymer. A method for producing a resin composition, characterized by kneading at a temperature equal to or higher than the melting temperature of the metal hydrate and the resin to be grafted while grafting only the monoester (meth) acrylate.   A resin molded article, wherein the resin composition according to any one of claims 1 to 7 is coated on the outside of a conductor and / or an optical fiber. The resin molded article according to claim 9 , wherein the resin composition is crosslinked.