JP2002226641A - Flexible flame-retardant resin composition of non- halogen type and its application product - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a flexible flame-retardant resin composition of a non- halogen type having a superior flame retardance and heat stability, excellent terminal workability and cutting resistance, good mechanical strengths and processability, intended for covering of a power source cord, an insulated cable and for electric insulation parts. SOLUTION: In this flexible flame-retardant resin composition of a non- halogen type, a metal hydrate in an amount of 50-250 pts.wt. is blended with 100 pts.wt. of a resin component comprizing (1) 15-75 wt.% of at least one polymer selected from an ethylene-vinyl acetate copolymer, an ethylene-ethyl acrylate copolymer and an ethylene-methyl methacrylate copolymer, (2) 10-30 wt.% of an ethylene-α-olefin copolymer, (3) 5-40 wt.% of a hydrogenated block copolymer obtained by hydrogenating a block copolymer having at least one polymer block A composed mainly of an aromatic vinyl compound and at least one polymer block B composed mainly of a conjugated diene compound, (4) 5-10 wt.% of polypropylene, and (5) 0.5-10 wt.% of a polyolefin resin modified with an unsaturated carboxylic acid.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION The present invention relates to a method for producing a high flame-retardant, heat-resistant material which does not generate halogen-based gas or smoke during combustion.
It relates to a flexible non-halogen flame-retardant resin composition having scratch resistance, end workability, good mechanical strength, and good moldability, and a power cord, an insulated wire and an electric insulation part using the resin composition. is there.

[0002]

2. Description of the Related Art In recent years, dioxins, lead, and other pollutants do not occur, and they are easier to recycle in order to reduce the burden on the environment and reduce the burden on the environment. Non-halogen flame-retardant resin compositions are used for insulating coatings or sheath materials for electric wires and cables.

[0003] These resin compositions generally use a polyolefin resin as a base polymer and generally use metal hydroxides such as magnesium hydroxide and aluminum hydroxide as flame retardants. However, these resin compositions have the following problems. (1) Polyolefin resins, particularly high-pressure low-density polyethylene, ethylene-α-olefin copolymer, ethylene-vinyl acetate copolymer (EVA), ethylene-ethyl acrylate copolymer (EEA), ethylene-methyl methacrylate copolymer Polymers (EMMA) and the like have crystal parts in a normal temperature range, though having a certain degree of difference, and have relatively high rigidity. In addition, the flame retardant effect of metal hydrate itself is not so large as compared with halogenated flame retardants, and it is necessary to increase the filling amount to provide sufficient flame retardancy. Increasing the hardness increases the hardness and flexural modulus of the resin composition. For this reason, electric wires and cables using a non-halogen resin composition containing a polyolefin-based resin as a base polymer as an insulating coating or a sheath material give a more rigid feel than those using vinyl chloride or the like. (2) When the filling amount of the metal hydrate is increased, the compatibility between the metal hydrate and the polymer molecule is reduced, and the shear viscosity of the resin composition is increased, so that the torque during extrusion molding is increased. However, the surface of the molded article loses smoothness, and it is necessary to reduce the molding linear velocity during extrusion molding. (3) To lower the rigidity, it is necessary to lower the crystallinity of the polyolefin resin as the base polymer. However, there is a limit to the reduction in crystallinity in the high-pressure polyethylene due to the production method. In the case of ethylene copolymer, increasing the comonomer content reduces crystallinity and improves flexibility.However, since the crystal part that has contributed to maintaining strength decreases, the mechanical strength and resistance of the resin composition are reduced. Heat deformability decreases. (4) On the other hand, when the filling amount of the metal hydrate is reduced in order to enhance the extrudability and flexibility, the flame retardancy of the resin composition is reduced. (5) In the case of a crystalline polymer, necking occurs when it is deformed beyond the yield point, and it is stretched. The material is unlikely to break due to stretching, but since the stretching state is irreversible, it does not return to its original state once it has expanded beyond the yield point. When processing the wire coating end, lightly insert a knife into the insulator and pull it out, especially when using a resin composition based on highly crystalline polyolefin resin for the insulator, the resin composition of the insulator The material is stretched, and a whisker-like residue is likely to be generated on the end, resulting in poor end processability. (6) In the case of a crystalline polymer, it is stretched when it undergoes deformation above the yield point, and since this stretched state is irreversible, it does not return to its original state once it has expanded beyond the yield point, and the material whitens (stress whitening). ). For this reason, a resin composition based on a polyolefin-based resin having a particularly high crystallinity has poor scratch resistance, and turns white when scratched.

In order to solve such a problem, a non-halogen flame-retardant resin composition using a styrene-based thermoplastic elastomer as a base polymer has been disclosed in Japanese Patent Application No. 11-148974.
Issue. However, since the resin composition has a high styrene-based thermoplastic elastomer ratio in the base polymer, the torque at the time of extrusion is high, and it is necessary to add a petroleum compound oil such as a process oil for the purpose of improving processability. There is a problem that the bleed and mechanical strength of the petroleum compound oil after molding are low.

[0005]

SUMMARY OF THE INVENTION An object of the present invention is to eliminate the problems of the above-mentioned conventional non-halogen flame-retardant resin composition, to have a high degree of flame retardancy and heat resistance, to obtain a terminal workability, It is intended to provide a flexible non-halogen flame-retardant resin composition for a power cord having excellent scratch resistance, good mechanical strength and good moldability, coating of an insulated wire, and an electrically insulating part.

[0006]

SUMMARY OF THE INVENTION The present invention is directed to an ethylene-vinyl acetate copolymer (EVA), an ethylene-ethyl acrylate copolymer (EEA), and an ethylene-methyl methacrylate copolymer (EMMA). 15 to 75% by weight of at least one type of polymer, 10 to 30% by weight of an ethylene-α-olefin copolymer, at least one or more polymer blocks A mainly composed of a vinyl aromatic compound, and a conjugated diene compound. A hydrogenated block copolymer obtained by hydrogenating a block copolymer consisting of at least one or more polymer blocks B as a main component has a molecular weight of 5 to 5.
40% by weight, 5 to 10% by weight of polypropylene, 0.5 to 0.5% of polyolefin resin modified with unsaturated carboxylic acid.
A flexible non-halogen flame-retardant resin composition characterized in that 50 to 250 parts by weight of a metal hydrate is mixed with 100 parts by weight of a resin component consisting of 10% by weight.

Preferably, 0.1 to 10 parts by weight of a surfactant having an HLB of 10 or less and a kinematic viscosity (25 ° C.) in JIS Z 8803 of 100,000 cs or more based on the flexible non-halogen flame-retardant resin composition. 0.1 ~ of silicon
10 parts by weight, at least one selected from ethylene-vinyl acetate copolymer (EVA), ethylene-ethyl acrylate copolymer (EEA), and ethylene-methyl methacrylate copolymer (EMMA) Has a melt index of 0.2 to 3 g / 10 min at 190 ° C. and a load of 2.16 kg;
Vicat softening temperature in SK 6730 of 45-7
5 ° C., and the ethylene-α-olefin copolymer
The melt index at 0 ° C and a load of 2.16 kg is 0.3 to 10 g / 10 min, and the density is 0.860 to 0.
924 g / cm ³ , and a block copolymer comprising at least one polymer block A mainly composed of a vinyl aromatic compound and at least one polymer block B mainly composed of a conjugated diene compound is hydrogenated. The hydrogenated block copolymer obtained by the addition has a vinyl aromatic compound content in the range of 5 to 50% by weight, 70% or more of the conjugated diene compound portion is hydrogenated, and has a number average molecular weight. Is a hydrogenated block copolymer of 100,000 to 200,000, and polypropylene has a melt index of 0.3 to 10 g / 10 mi at 230 ° C. under a load of 2.16 kg.
n, the polyolefin resin modified with an unsaturated carboxylic acid is ethylene-α modified with an unsaturated carboxylic acid.
An olefin copolymer, wherein the metal hydrate has a weight mixing ratio of magnesium hydroxide surface-treated with a fatty acid or a fatty acid salt to magnesium hydroxide not surface-treated;
The surfactant is a flexible non-halogen flame-retardant resin composition in which the surfactant having an HLB of 0: 0 to 5: 5 and an HLB of 10 or less is a nonionic glycerin fatty acid ester or sorbitan fatty acid ester. Further, the present invention is a power cord, an insulated wire and an electrically insulated component using the above resin composition.

[0008]

DESCRIPTION OF THE PREFERRED EMBODIMENTS The present invention will be described below in detail.
The ethylene-vinyl acetate copolymer of the present invention (EV
A), ethylene-ethyl acrylate copolymer (EE
A), ethylene-methyl methacrylate copolymer (EM
At least one polymer selected from MA) has a polar group and improves the flame retardancy of the resin composition more than other polyolefin-based resins.

At least one selected from the group consisting of ethylene-vinyl acetate copolymer (EVA), ethylene-ethyl acrylate copolymer (EEA) and ethylene-methyl methacrylate copolymer (EMMA) used in the present invention. The melt index of the polymer at 190 ° C. under a load of 2.16 kg is 0.2 to 3 g / 10 min.
Vicat softening temperature in SK 6730 is 45-7
5 ° C. Their melt index is 0.2 g /
When it is less than 10 min, the torque at the time of extrusion of the resin composition is increased, and when it exceeds 3 g / 10 min, the mechanical strength of the resin composition is reduced. When the Vicat softening temperature is less than 45 ° C., the mechanical strength and The heat deformation resistance is reduced, and
When the temperature exceeds 5 ° C., the flexibility of the resin composition is impaired. These addition amounts are 15 to 75 parts per 100 parts by weight of the resin component.
% By weight. When the amount is less than 15% by weight, the flame retardancy of the resin composition is reduced. When the amount is more than 75%, the flexibility, end workability and scratch resistance of the resin composition are impaired.

[0010] The ethylene-α-olefin copolymer of the present invention improves the mechanical strength of the resin composition. The ethylene-α olefin copolymer used in the present invention has a temperature of 190 ° C.
2. Melt index at a load of 16 kg is 0.3
-10 g / 10 min, density 0.860-0.924
g / cm ³ . Single-site catalysts represented by metallocene catalysts, so-called Ziegler catalysts (titanium-based, chromium-based, etc.) as ethylene-α-olefin copolymers
And multi-site catalysts typified by any of the above. The α-olefin of the ethylene-α-olefin copolymer is C3-C12 such as propylene, butene-1, pentene-1, octene-1, 4-.
Methylpentene-1,4-methylhexene-1,4,4
-Dimethylpentene-1, nonene-1, decene-1, undecene-1, dodecene-1, and the like.

When the melt index of the ethylene-α-olefin copolymer used in the present invention at 190 ° C. and a load of 2.16 kg is less than 0.3 g / 10 min, the torque at the time of extrusion of the resin composition becomes high, and 10 g / 10 mi.
Above the n decreases the mechanical strength of the resin composition, density decreases the mechanical strength of the resin composition falls below 0.860g / cm ^3, the resin composition exceeds the 0.924g / cm ³ Flexibility is impaired.

The amount of the ethylene-α-olefin copolymer used in the present invention is based on 100 parts by weight of the resin component.
It is 10 to 30% by weight. When the amount is less than 10% by weight, the mechanical strength of the resin composition decreases, and when the amount exceeds 30% by weight, the terminal processability and the scratch resistance of the resin composition decrease.

The block copolymer comprising at least one polymer block A mainly comprising a vinyl aromatic compound of the present invention and at least one polymer block B mainly comprising a conjugated diene compound is hydrogenated. The hydrogenated block copolymer obtained by the above improves the flexibility, terminal workability, scratch resistance and heat resistance of the resin composition.

The vinyl aromatic compound in the hydrogenated block copolymer used in the present invention includes styrene, α-
Methylstyrene, o, m and p-methylstyrene,
Examples thereof include 1,3-dimethylstyrene, vinylnaphthalene, and vinylanthracene, and the polymer block A is a polymer composed of a homopolymer or a mixture thereof. Also,
Conjugated diene compounds include 1,3-butadiene, isopropylene, 2,3-dimethyl-1,3-butadiene, 1,3-
Examples thereof include pentadiene and 1,3-hexadiene, and the polymer block B is a polymer composed of a homopolymer or a mixture thereof.

The content of the vinyl aromatic compound in the hydrogenated block copolymer used in the present invention is 5 to 50% by weight.
It is. When the content of the vinyl aromatic compound is less than 5% by weight, the mechanical strength of the resin composition decreases, and when it exceeds 50% by weight, the rigidity of the resin composition increases and the flexibility cannot be maintained. In the hydrogenated block copolymer used in the present invention, 70% or more of the conjugated diene compound portion is hydrogenated. The hydrogenation rate of the conjugated diene compound part is 7
If it is less than 0%, the weather resistance is extremely poor and a great restriction is imposed on use, which is not preferable.

The number average molecular weight (Mn) of the hydrogenated block copolymer used in the present invention is at least 100,000, preferably in the range of 130,000 to 200,000, and the molecular weight distribution Mw / Mn is 10%. (Mw: weight average molecular weight), preferably 5 or less, more preferably 2 or less. When the number average molecular weight is less than 100,000, the mechanical strength of the resin composition decreases. On the other hand, when the number average molecular weight exceeds 200,000, the fluidity of the resin molded product decreases, and the torque during extrusion increases.

The structure of the hydrogenated block polymer used in the present invention may be linear or branched, and may be further modified, that is, it may be present at the molecular terminal or in the molecular chain. It may have a polar group such as a hydroxyl group, a carboxyl group and an epoxy group. The addition amount of the hydrogenated block copolymer used in the present invention is 100 parts of the resin component.
It is 5 to 40% by weight based on parts by weight. If the amount is less than 5% by weight, the flexibility, end workability, and scratch resistance of the resin composition are reduced. If the amount is more than 40% by weight, the torque at the time of extrusion of the resin composition is increased.

The polypropylene of the present invention improves the appearance of the resin composition. The type of propylene used in the present invention is not particularly limited, and may be a homopolypropylene, a random polypropylene, or a block polypropylene. Among them, homopolypropylene is excellent in heat resistance of the resin composition. The melt index of the polypropylene used in the present invention at 230 ° C. and a load of 2.16 kg is 0.3 to 10 g / 10 min. If it is less than 0.3 g / 10 min, the torque at the time of extrusion of the resin composition will be high. If it exceeds 10 g / 10 min, the hydrogenated block copolymer will be poorly dispersed, and the molded article of the resin composition will have bumps and impair the appearance. .

The amount of propylene used in the present invention is 5 to 10% by weight based on 100 parts by weight of the resin component.
If the amount is less than 5% by weight, the hydrogenated block copolymer becomes poorly dispersed, and the molded article of the resin composition suffers from bumps and impairs the appearance.
If it exceeds 10% by weight, the flexibility of the resin composition is impaired.

The polyolefin resin modified with the unsaturated carboxylic acid of the present invention improves the appearance of the resin composition. The amount of the polyolefin resin modified with the unsaturated carboxylic acid used in the present invention is based on 100 parts by weight of the resin component.
0.5 to 10% by weight. If the amount is less than 0.5% by weight, the metal hydrate will have poor dispersibility, and the molded article of the resin composition will have bumps and impair the appearance. descend. Examples of unsaturated carboxylic acids include acrylic acid, methacrylic acid, maleic acid, monobasic acids and dibasic acids such as fumaric acid and the above-mentioned metal salts of unsaturated carboxylic acids, amides, imides, esters and anhydrides, Most preferred is maleic anhydride, and its modification rate is suitably from 0.05 to 5 parts by weight.

The polyolefin resin modified with an unsaturated carboxylic acid used in the present invention is an ethylene-α-olefin copolymer modified with an unsaturated carboxylic acid. As the ethylene-α-olefin copolymer, those polymerized by any of single-site catalysts typified by metallocene catalysts, multi-site catalysts typified by so-called Ziegler catalysts (titanium-based, chromium-based, etc.) can be used. The α-olefin of the ethylene-α-olefin copolymer is C3-C12, for example, propylene, butene-1, pentene-1, octene-1, 4-methylpentene-1, 4-
Methylhexene-1,4,4-dimethylpentene-1,
Nonene-1, decene-1, undecene-1, dodecene
1, etc.

The metal hydrate of the present invention imparts the flame retardancy of the resin composition. The metal hydrate used in the present invention includes magnesium hydroxide and aluminum hydroxide. Preferably, by using magnesium hydroxide as the metal hydrate, a resin composition having stable processability can be obtained. Since the extrusion temperature of the resin composition using the hydrogenated block copolymer needs to be set to a relatively high temperature (170 to 220 ° C.), the temperature at which the adsorbed water is released is high (about 350 ° C.).
The use of magnesium hydroxide is very effective in stabilizing workability. As magnesium hydroxide, both those using natural brucite ore as a raw material and synthetic products using seawater or the like as a raw material can be used in the same manner. Since synthetic products are superior in purity, a resin composition having higher flame retardancy and good processability tends to be obtained. The average particle size of the metal hydrate is preferably 5 μm or less, more preferably 2 μm or less. When the average particle size exceeds 5 μm, the flame retardancy of the resin composition decreases, and the appearance of the molded product is impaired. Here, the average particle diameter (D5
0) indicates the particle diameter when the relative particle amount is 50% using a laser diffraction type particle size distribution apparatus.

The metal hydrate used in the present invention has a weight mixing ratio of magnesium hydroxide surface-treated with a fatty acid or a fatty acid salt to magnesium hydroxide not subjected to a surface treatment, from 10: 0 to 5: 5. Examples of fatty acids or fatty acid salts to be surface-treated on magnesium hydroxide include oleic acid and stearic acid. When the weight mixing ratio of magnesium hydroxide surface-treated with a fatty acid or a fatty acid salt to magnesium hydroxide not surface-treated is out of the above range, the torque at the time of extrusion of the resin composition increases.

The amount of the metal hydrate used in the present invention is 50 to 250 parts by weight based on 100 parts by weight of the resin component. If the amount is less than 50 parts by weight, the flame retardancy of the resin composition becomes insufficient, and if it exceeds 250 parts by weight, the mechanical strength and the scratch resistance are reduced.

The surfactant of the present invention having an HLB of 10 or less reduces the torque at the time of extrusion of the resin composition, improves the moldability and improves the mechanical strength of the resin composition. The surfactant used in the present invention is preferably a nonionic surfactant, for example, glycerin fatty acid ester, sorbitan fatty acid ester, sorbite fatty acid ester, pentaerythritol fatty acid ester, ethylene glycol fatty acid ester, propylene glycol fatty acid ester, polyglycerin And higher fatty acid esters of sucrose, higher alcohols of polyethylene glycol or adducts of higher fatty acids (those having a shorter polyethylene glycol chain), alkyl glucosides, alkyl maltosides, and the like, and silicone-based HLB of 10 or less. Examples of the nonionic surfactant include polyether-modified dimethylpolysiloxanes, polyether-modified methylphenylpolysiloxanes, and polyether-modified methylhydrogen polysiloxanes. Hexane include dimethyl polysiloxane polyalkylene glycol copolymers, methyl phenyl polysiloxane polyalkylene glycol copolymers, methyl hydrogen polysiloxane polyalkylene glycol copolymer and the like. In the present invention, one or more of these nonionic surfactants can be used.

The HLB used here is a value calculated by the following equation. HLB = 20 × Mn / MM M: molecular weight of surfactant Mn: molecular weight of hydrophilic group portion The surfactant used in the present invention has an HLB of 10 or less, preferably 7 or less, more preferably 5 or less, and most preferably 3 or less. It is as follows. If the HLB exceeds 10, the metal hydrate cannot be sufficiently dispersed, so that the moldability and mechanical strength of the resin composition cannot be sufficiently improved. In the surfactant used in the present invention, it is preferable that the polyoxyethylene chain or the like of the hydrophilic group be as short as possible or not included. If there is a long polyoxyethylene chain, HLB becomes large and metal hydrate cannot be dispersed, so that the moldability and mechanical strength of the resin composition cannot be improved.

The surfactant used in the present invention is a nonionic surfactant. It is not preferable to use a surfactant other than the nonionic surfactant because, when a reactive substance such as another surface treating agent or a cross-linking agent is present, there is a high possibility of acting as a reaction inhibitor thereof. For example, a metal salt of a higher fatty acid such as calcium stearate, which is an anionic surfactant, has a strong hydrophilicity, so that the mechanical strength of the resin composition can be improved even when integral blending is performed at the time of kneading the metal hydrate and the resin. In addition, it reduces the scratch resistance of the resin composition, and furthermore, when used in combination with a coupling agent such as aminosilane, the metal salt of a higher fatty acid such as calcium stearate is ionic. Because it acts as a reaction inhibitor, the coupling agent cannot improve the mechanical strength of the resin composition, and
In the case of a fatty acid such as stearic acid, since the acid is an acid, when used in combination with a reactant such as a coupling agent, the coupling agent cannot improve the mechanical strength of the resin composition.

If the surfactant itself has water absorbency, the surfactant used in the present invention absorbs water after molding the resin composition, which may deteriorate mechanical strength and impact resistance. It is preferable to use a surfactant having low or no activity.

The molecular weight of the surfactant used in the present invention is preferably from 300 to 10,000, more preferably from 500 to 5,000, and most preferably from 700 to 5,000.
2,000. If the molecular weight of the surfactant is less than 300, it is not preferable because bleeding may occur after molding of the resin composition or volatilization may occur due to heat during molding. On the other hand, if the molecular weight exceeds 10,000, it cannot be arranged sufficiently at the interface between the resin and the metal hydrate during integral blending, and the mechanical strength of the resin composition cannot be improved or the mechanical strength is improved. In addition, the amount of the surfactant added must be extremely increased, which is not preferable.

As described above, the surfactant used in the present invention is preferably a nonionic surfactant having a certain molecular weight and a low HLB, such as fatty acid esters such as glycerin fatty acid esters, sorbitan fatty acid esters, and saccharides. Preferably glycerin, sorbitan, higher fatty acid esters such as sugars, most preferably glycerol monostearate, sorbitan trioleate,
Sorbitan tristearate.

The amount of the surfactant used in the present invention is 0.1 to 10 parts by weight, preferably 0.3 to 5 parts by weight, based on 100 parts by weight of the resin component.
More preferably, the amount is 0.5 part by weight to 1 part by weight. When the amount of the surfactant is less than 0.1 part by weight, the effect of the surfactant is not sufficiently exhibited, and the moldability and mechanical strength of the resin composition are not sufficiently improved. On the other hand, when the amount exceeds 10 parts by weight, problems such as bleeding of the surfactant after molding of the resin composition and deterioration of flame retardancy of the resin composition occur.

As a method of adding the surfactant used in the present invention, a method of kneading the resin and the metal hydrate and simultaneously integrating the surfactant is preferable. This is because, if the surfactant mentioned in the present invention is used, the surface treatment of the metal hydrate with the surfactant in advance is not required, and the surfactant is added at the same time as the kneading of the resin and the metal hydrate. Then, the moldability and mechanical strength of the resin composition can be improved. This can reduce the production cost of the resin composition. The surface treatment of the metal hydrate with a surfactant before use does not adversely affect the physical properties of the resin composition, but in this case, a surface treatment step of the metal hydrate is required, and Manufacturing costs cannot be reduced. HLB is 10
Although the detailed mechanism of the following surfactant addition effect is not clear, while improving the affinity between the resin and the metal hydrate, the steric hindrance effect of the surfactant, etc. It is presumed that they are sufficiently dispersed by preventing local agglomeration from each other, and improve the moldability and mechanical strength of the resin composition.

The silicone oil of the present invention improves the flame retardancy and moldability of the resin composition. Regarding the type of silicone oil used in the present invention, dimethyl silicone oil is good in terms of molding and processing of the resin composition, and JIS
The kinematic viscosity (25 ° C.) of Z8803 needs to be 100,000 cs or more, and preferably 100,000 to 500,000 cs. If it is less than 100,000 cs, it will undesirably bleed to the molding surface of the resin composition due to the change over time, and
If it exceeds s, the viscosity will suddenly increase, and the workability of charging during production will be deteriorated, which is not preferable. The kinematic viscosity (25 ° C.) used here is determined by a single cylinder rotary viscometer according to JIS Z 8803.

The addition amount of the silicone oil is 0.1 to 10 parts by weight. If the amount is less than 0.1 part by weight, the flame retardancy and molding processability of the resin composition are not improved. Bleeding or the like is generated on the molding surface of the resin composition due to a specific change, which is not preferable.

In the resin composition of the present invention, a softening agent, paraffin oil, process oil or the like which is optionally used for a rubber material for the purpose of improving flexibility and processability does not impair the properties of the resin composition. You may use it in the range. Further, in the resin composition of the present invention, if necessary, red phosphorus, a flame retardant auxiliary for a phosphate, and further, oxidation of a hindered phenol type, a hindered amine type, a lactone type, a phosphorus type, a sulfur type, a vitamin E type or the like. Resin molding materials, such as inhibitors, metal deactivators such as hydrazines, light stabilizers such as hindered amines, ultraviolet absorbers such as benzotriazoles, ultraviolet hiding agents such as titanium oxide, carbon and other coloring pigments, etc. May be used in a range that does not impair the properties of the resin composition.

The compound of the resin molded product of the present invention is melt-mixed in a single-screw or twin-screw kneading extruder, a kneading kneader, a banbury, a kneading roll, etc., which are usually used for compound production, and formed into an appropriate shape if necessary. It can be manufactured by performing granulation or the like. Extrusion coating of insulators and sheaths for electric wires, plugs, etc.
Injection molding of an adapter or the like can be performed according to a general method using general equipment. The processing temperature at that time is set between 160 and 220 ° C. based on the blending system.

[0037]

The present invention will be described below by way of examples, which are merely examples and the present invention is not limited to these examples. Compounds of the respective formulations of Examples and Comparative Examples shown above Tables 1 to 4 were produced. Mixing was performed by a kneader mixer, the kneader temperature was set to 180 to 200 ° C., and the mixture was pelletized.

Various evaluations were performed based on the following. (1) Tensile properties: using the resin composition compounded of the present invention, the conductor cross-sectional area 2 mm ² was prepared by extrusion, cut parallel code line core number 2 to 10 cm, to prepare a test piece by far the conductor, A tensile test was performed. The test was conducted at a tensile speed of 200 mm / min using a tensile tester, and the distance between the marked lines was 5 cm. The cross-sectional area of the test piece was calculated by measuring the weight of the test piece and the specific gravity according to JIS K7112. And the tensile strength is 10 MPa or more and the elongation is 3
Those with 50% or more were evaluated as "O", and the others were evaluated as "X".

(2) Heat aging resistance: A test piece was prepared in the same manner as in the above (1), and after a heat treatment at 90 ° C. for 96 hours, a tensile test was carried out in the same manner as in the above (1). The residual ratio from the normal value before the heat treatment obtained in the above was determined. Then, those having a residual ratio of tensile strength of 80% or more and a residual ratio of elongation of 65% or more were evaluated as “○”, and the others were evaluated as “X”.

(3) Resistance to Heat Deformation: The heat deformation rate was measured in accordance with “Appendix 18 of Appended Table 1” of “Technical Standards and Handling Rules for Electrical Appliances”. Using the resin composition compound of the present invention, a parallel cord having a conductor cross-sectional area of 2 mm ² and a number of wire cores of 2 was manufactured by extrusion and used as a test sample. The test conditions were set temperature: 75 ° C., load: 5N, load time: 30 minutes, and those having a heating deformation rate of 10% or less were rated “○”, and the others were rated “x”.

(4) Flexibility: The resin composition of the present invention was sufficiently melt-mixed using an open roll or the like, and then a standard test piece was prepared from a press-formed 1 mm thick sheet. The flexural modulus was measured according to 7106. And the flexural modulus is 1300k
Those having gf / cm ² or less were rated “○”, and the others were rated “x”.

(5) Flame retardancy: A parallel cord having a conductor cross-sectional area of 2 mm ² and a number of wire cores of 2 was manufactured by extrusion using the resin composition of the present invention, and used as a test sample.
Tested in accordance with SC3005.28 Incline test, time from removal of flame gently to extinguishing naturally (seconds)
Was measured. Those that disappeared naturally within 60 seconds were marked with “○”, and those that did not disappear were marked with “x”.

(6) End workability: resin composition of the present invention
Using a compound, conductor cross-sectional area 2mm ^Two, 2 cores flat
Line code is manufactured by extrusion and used as a test sample.
Was. Set on a terminal processing machine for plug processing, flat terminal
Processing was performed. 10 terminals processed, all remaining
"○" indicates that processing was possible, and "
“×” was assigned.

(7) Scratch resistance: The resin composition of the present invention was sufficiently melt-mixed using an open roll or the like, and then a press-formed sheet having a thickness of 1 mm was prepared, and R = 2.5 mm The sapphire needle was placed upright on the sheet surface, and the sheet was slid at a speed of 2000 mm / min. The load (g) when the sheet was damaged and whitened at that time was taken as the point of damage. And when the load at the time of being damaged was 800 g or more, it was set as "O", and the others were set as "X".

(8) Extrudability: resin composition of the present invention
Using a compound, conductor cross-sectional area 2mm ^Two, 2 cores flat
Press the line code using a 75 mm extruder (L / D = 24)
Out processing, line speed of more than 60m / min, 120A
The following extrusion load current, and inorganic aggregates, irregularities,
Smooth extruded appearance with no code and bloom
Check that all items are satisfactory
"○", items that were not satisfied with "x"
did.

(9) Weather resistance: Using the resin composition of the present invention, a parallel cord having a conductor cross-sectional area of 2 mm ² and a number of wire cores of 2 was manufactured by extrusion to obtain a test sample. After the accelerated weathering test (sunshine weather, black panel temperature 63 ° C., rain for 60 minutes during 12 minutes × 500 hr), the surface state of the test sample was observed. X ".

[0047]

[Table 1]

[0048]

[Table 2]

[0049]

[Table 3]

[0050]

[Table 4]

* Raw materials used * (1) EVA: ethylene-vinyl acetate copolymer (MI; 2.0 g / 10 min, Vicat softening temperature: 50 ° C.) (2) EEA: ethylene-ethyl acrylate copolymer (MI; (3) EMMA: Ethylene-methyl methacrylate copolymer (MI; 0.3 g / 10 min, Vicat softening temperature; 70 ° C) (1) EVA: Ethylene-vinyl acetate copolymer Polymer (MI; 0.1 g / 10 min, Vicat softening temperature; 50 ° C.) (5) EMMA: ethylene-methyl methacrylate copolymer (MI; 3.5 g / 10 min, Vicat softening temperature; 60 ° C.) (6) EEA: ethylene -Ethyl acrylate copolymer (MI; 0.6 g / 10 min, Vicat softening temperature; 42 ° C) (7) EVA: ethylene-vinyl acetate copolymer (MI; 2.3 g / 10 min, Vicat softening temperature; 80 ° C) (8) ) Ethylene-octene copolymer: MI; 0.5 g / 10 mi
n, density: 0.865 g / cm ³ (9) Ethylene-butene copolymer: MI; 1.0 g / 10 min,
Density: 0.920 g / cm ³ (10) Ethylene-octene copolymer: MI; 0.2 g / 10 mi
n, density: 0.865 g / cm ³ (11) Ethylene-butene copolymer: MI; 12.0 g / 10 mi
n, density: 0.920 g / cm ³ (12) Ethylene-octene copolymer: MI; 0.5 g / 10 mi
n, density: 0.855 g / cm ³ (13) Ethylene-butene copolymer: MI; 1.0 g / 10 min,
Density: 0.930 g / cm ³ (14) SEPS: hydrogenated block copolymer having a structure of polystyrene-hydrogenated isoprene-polystyrene (styrene content: 30%, hydrogenation rate: 70% or more, number average molecular weight : 170,000) (15) SEPS: hydrogenated block copolymer having a structure of polystyrene-hydrogenated isoprene-polystyrene (styrene content: 30%, hydrogenation rate: 70% or more, number average molecular weight: 80,000) (16) SEBS: hydrogenated block copolymer having a structure of polystyrene-hydrogenated butadiene-polystyrene (styrene content: 30%, hydrogenation rate: 70% or more, number average molecular weight: 120,000) (17) ) SEBS: hydrogenated block copolymer having a polystyrene-hydrogenated butadiene-polystyrene structure (styrene content: 30%, hydrogenation rate: 70% or more, number average molecular weight: 60,000) (18) SEPS: hydrogenated block copolymer having a polystyrene-hydrogenated isoprene-polystyrene structure (styrene content: 3%, hydrogenation rate: 70% or more, number average molecular weight: 170,000) (19) SEBS: hydrogenated block copolymer having a structure of polystyrene-hydrogenated butadiene-polystyrene (styrene content: 55%, hydrogenation rate: 70% or more, number average molecular weight: 120,000) (20) SEPS: polystyrene A hydrogenated block copolymer having a structure of hydrogenated isoprene-polystyrene (styrene content: 30%, hydrogenation rate: less than 70%, number average molecular weight: 170,000) (21) SEBS: polystyrene-hydrogenated Hydrogenated block copolymer having a butadiene-polystyrene structure (styrene content: 30%, hydrogenation rate: 70% or more, number average molecular weight: 220,000) (22) PP: PO Lipropylene (homopolymer, MI;
5 g / 10 min, density: 0.900 g / cm ³ ) (23) PP: polypropylene (homopolymer, MI;
2g / 10min, density: 0.900g / cm ³ ) (24) PP: polypropylene (homopolymer, MI; 1)
2.0 g / 10min, ^{density; 0.900g / cm 3) (25} ) maleic anhydride-modified LLDPE: polar group modification ratio;
0.2wt% (26) Magnesium hydroxide with surface treatment: Synthetic product, D5
0; 1.8 μm (27) Magnesium hydroxide without surface treatment: Synthetic product, D5
0; 1.8 μm (28) Glycerin fatty acid ester (HLB = 3.0) (29) Sorbitan fatty acid ester (HLB = 4.3) (30) Anionic surfactant (HLB = 3.0) (31) Non-ionic surfactant Ionic surfactant (HLB = 16.7)

As is clear from the table, the materials shown in the examples show good mechanical strength, heat resistance, flexibility, flame retardancy, end workability, scratch resistance, molding workability, and weather resistance. ing. On the other hand, in all of the comparative examples, the above-mentioned characteristics are not balanced.

[0053]

According to the present invention, no halogen-based gas or smoke is generated at the time of combustion, and it has high flame retardancy, heat resistance, scratch resistance, end workability, mechanical strength and molding. A flexible non-halogen flame-retardant resin composition having good processability, and a power cord, an insulated wire and an electrically insulated component using the resin composition are obtained.

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat ゛ (Reference) C08L 23/12 C08L 23/12 23/26 23/26 53/02 53/02 83/04 83/04 H01B 3/00 H01B 3/00 A 3/44 3/44 MF KP 7/295 7/34 BF term (reference) 4F071 AA15 AA20 AA67 AA75 AA81 AA82 AA85 AA88 AB17 AE07 AE10 AF14 AF45 AF47 AH12 BA01 BB06 BC06 4J002 BB05X BB06W BB07W BB124 BB15X BB215 BP01Y CN025 CP035 CP185 DE076 DE146 EH047 FB236 FD020 FD030 FD090 FD130 FD136 FD317 GQ01 5G303 AA06 AA08 AB20 BA12 CA09 CA11 CD03 5G305 AA03 CA02 AB15 AB02 AB15 AB23 CA04 CB02 CC08 CD01 CD02 CD04 CD06 CD14

Claims (12)

[Claims] 1. A method according to claim 1, wherein at least one polymer selected from the group consisting of ethylene-vinyl acetate copolymer (EVA), ethylene-ethyl acrylate copolymer (EEA) and ethylene-methyl methacrylate copolymer (EMMA) is used. To 75% by weight, 10 to 30% by weight of an ethylene-α-olefin copolymer, at least one polymer block A mainly composed of a vinyl aromatic compound, and a polymer block B mainly composed of a conjugated diene compound. 5 to 40% by weight of a hydrogenated block copolymer, 5 to 10% by weight of polypropylene, and a polyolefin resin modified with an unsaturated carboxylic acid obtained by hydrogenating a block copolymer having at least one or more Metal hydrate is added in an amount of 50 to 25 with respect to 100 parts by weight of a resin component consisting of 0.5 to 10% by weight.
0 parts by weight of a flexible non-halogen flame-retardant resin composition. 2. The flexible non-halogen flame-retardant resin composition according to claim 1, wherein 0.1 to 10 parts by weight of a surfactant having an HLB of 10 or less and a kinematic viscosity (25 ° C.) of 10 according to JIS Z 8803. 0.1 ~
10 parts by weight of a flexible non-halogen flame retardant resin composition. 3. At least one polymer selected from ethylene-vinyl acetate copolymer (EVA), ethylene-ethyl acrylate copolymer (EEA), and ethylene-methyl methacrylate copolymer (EMMA), Melt index at 190 ° C. under a load of 2.16 kg is 0.2 to 3 g / 10 min, JIS K
The flexible non-halogen flame-retardant resin composition according to claim 1 or 2, wherein the Vicat softening temperature in 6730 is 45 to 75 ° C. 4. An ethylene-α-olefin copolymer comprising 1
Melt index at 90 ° C, 2.16 kg load is 0.3 to 10 g / 10 min, density is 0.860 to
The flexible non-halogen flame-retardant resin composition according to claim 1, wherein the composition is 0.924 g / cm ³ . 5. A hydrogenated block copolymer comprising at least one polymer block A mainly composed of a vinyl aromatic compound and at least one polymer block B mainly composed of a conjugated diene compound. The hydrogenated block copolymer obtained by the above method has a vinyl aromatic compound content in the range of 5 to 50% by weight and a conjugated diene compound portion of 7%.
0% or more is hydrogenated and has a number average molecular weight of 10
5. The flexible non-halogen flame-retardant resin composition according to claim 1, wherein the amount is from 10,000 to 200,000. 6. Polypropylene is 230 ° C., 2.16
Melt index in kg load is 0.3 to 10 g
The flexible non-halogen flame-retardant resin composition according to any one of claims 1 to 5, which is / 10 min. 7. The flexible non-halogen-free resin according to claim 1, wherein the polyolefin resin modified with an unsaturated carboxylic acid is an ethylene-α-olefin copolymer modified with an unsaturated carboxylic acid. Flammable resin composition. 8. The metal hydrate has a weight mixing ratio of magnesium hydroxide surface-treated with a fatty acid or a fatty acid salt and magnesium hydroxide not surface-treated with 10: 0 to 5:
The flexible non-halogen flame-retardant resin composition according to any one of claims 1 to 7, which is 5. 9. The flexible non-halogen flame-retardant resin composition according to any one of 2 to 8, wherein the surfactant having an HLB of 10 or less is a nonionic glycerin fatty acid ester or sorbitan fatty acid ester. 10. A power cord using the flexible non-halogen flame-retardant resin composition according to any one of claims 1 to 9. 11. An insulated wire using the flexible non-halogen flame-retardant resin composition according to any one of claims 1 to 9. 12. An electrically insulating part using the flexible non-halogen flame-retardant resin composition according to claim 1. Description: