JP3515501B2 - Flame-retardant resin composition and molded part using the same - Google Patents

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a flame-retardant resin composition excellent in mechanical properties, flexibility, heat resistance and flame retardancy without requiring a crosslinking facility during processing, and the composition. The present invention relates to a wiring material, a fiber optic cord, and other molded parts having a coating material of. More specifically, the present invention is used as a covering material for an insulated wire, an electric cable, an electric cord, an optical fiber core wire, an optical fiber cord, or the like used for internal or external wiring of an electric / electronic device, or a mold for a power cord or the like. Flame-retardant resin composition suitable for materials, tubes and sheets, and wiring materials and other molded parts using the same, heat resistance, flexibility, and external damage resistance without requiring special equipment such as crosslinking equipment after processing. It is an excellent flame retardant resin composition, especially when it is discarded such as landfill and combustion, there is no elution of heavy metal compounds, a large amount of smoke, no generation of harmful gas, and it is suitable for recycling after use, The present invention relates to a flame-retardant resin composition that addresses environmental problems, and wiring materials and other molded parts using the same.

[0002]

2. Description of the Related Art Insulated electric wires, cables, cords, optical fiber cores, optical fiber cords, etc. used for internal and external wiring of electric and electronic equipments have flame retardancy, heat resistance and mechanical properties (for example, tensile strength). Various characteristics such as characteristics and abrasion resistance are required. Therefore, as a coating material used for these wiring materials, a polyvinyl chloride (PVC) compound or a polyolefin compound containing a halogen-based flame retardant containing a bromine atom or a chlorine atom in the molecule is mainly used. It was However, if these materials are disposed of without proper treatment and landfilled, the plasticizer and heavy metal stabilizer contained in the coating material will elute, and if burned, they will be included in the coating material. Hazardous gas may be generated from the halogen compounds generated, and in recent years, this problem has been discussed. Therefore, wiring materials covered with non-halogen flame-retardant materials that are not likely to cause harmful plasticizers and heavy metals to elute, and halogen-based gases, which are feared to affect the environment, are being studied. . Non-halogen flame-retardant materials exhibit flame retardancy by blending a flame-retardant containing no halogen with the resin.
-Difficulty in ethylene-based copolymers such as butene copolymer, ethylene / propylene copolymer, ethylene / vinyl acetate copolymer, ethylene / ethyl acrylate copolymer, ethylene / propylene / diene terpolymer. A material in which a large amount of a metal hydrate such as aluminum hydroxide or magnesium hydroxide is mixed as a combustor is used for the wiring material.

Standards such as flame retardancy, heat resistance, mechanical properties (for example, tensile properties, wear resistance) required for wiring materials for electric and electronic devices are defined by UL, JIS and the like. In particular, regarding flame retardancy, the test method changes depending on the required level (use thereof) and the like. So in fact,
It should have flame retardancy at least according to the required level. For example, UL1581 (related standards for wires, cables and flexible cords (Reference St
and for for Electrical Wire
s, Cables and Flexible Cor
ds)) vertical combustion test (Vertical)
Frame Test) (VW-1) and JIS C
3005 (rubber / plastic insulated wire test method) specifies the flame resistance and the like that pass the horizontal test and the tilt test. Among these, in the case of imparting a high degree of flame retardancy to the non-halogen flame-retardant material so far as to pass the VW-1 or tilt test, an ethylene / 1-butene copolymer, an ethylene / propylene copolymer, To 100 parts by weight of the resin component of the ethylene-based copolymer such as ethylene / vinyl acetate copolymer, ethylene / ethyl acrylate copolymer, ethylene / propylene / diene terpolymer,
It is necessary to mix 150 to 200 parts by weight of a metal hydrate, which is a flame retardant, and as a result, there is a problem that mechanical properties such as tensile properties and abrasion resistance of the coating material are significantly reduced. In order to solve this problem, a method of reducing the compounding amount of the metal hydrate (for example, about 120 parts by weight of the metal hydrate which is a flame retardant with respect to 100 parts by weight of the resin) and adding red phosphorus. Has been taken. By the way,
Wiring materials that use polyvinyl chloride compounds or polyolefin compounds containing halogen-based flame retardants as coating materials, which are used in electronic devices, are wires, cables, and cords for the purpose of distinguishing the type of wiring material and the connection part. It is used by printing on the surface of, and coloring in several kinds of colors. However, a non-halogen coating material containing a metal hydrate and red phosphorus in order to achieve both high flame retardancy and mechanical properties can be printed on or colored in any color because of the red phosphorus coloring. However, there is a problem in that a wiring member whose type and connection portion can be easily distinguished cannot be obtained. Furthermore, regarding the phosphorus released from phosphorus-containing flame-retardant materials after disposal, environmental impact,
For example, pollution of water resources due to eutrophication has become a problem.

Further, wiring materials used in electric and electronic equipment may be required to have heat resistance of 80 ° C. to 105 ° C., and further 125 ° C. in a continuous use state. In such a case, a method of cross-linking the coating material by an electron beam cross-linking method, a chemical cross-linking method, or the like is used for the purpose of imparting high heat resistance to the wiring material. However, while the cross-linked wiring material has improved heat resistance of the coating material, it cannot be re-melted, which makes reuse difficult,
It has been pointed out that recyclability is poor. For example, when recovering the metal used for the conductor, it is often necessary to burn the coating material, etc., and avoid the above-mentioned environmental problems associated with conventional coating materials containing halogen or phosphorus. I can't. In addition, special equipment such as electron beam cross-linking equipment and chemical cross-linking equipment must be prepared, which increases the cost of equipment and the cost of electric wires and is a factor that reduces versatility.

On the other hand, as a method of realizing heat resistance of about 80 ° C. to 105 ° C. in a wiring material that does not crosslink, there is a method of using a resin having a high melting point such as polypropylene resin. However, although such a resin has good heat resistance, it is poor in flexibility, and when the wiring material covering it is bent, the phenomenon of whitening of the surface is observed.
This whitening phenomenon is not observed in the wiring material coated with polyvinyl chloride compound that is currently used in electric and electronic devices. On the other hand, in a wiring material coated with a non-halogen flame-retardant material containing a large amount of metal hydrate, this whitening phenomenon is severe regardless of the presence or absence of crosslinking. Therefore, as wiring material,
There is still a need for improvement in using the non-halogen flame-retardant material that is whitened by the current bending. Since the usage temperature of the wiring material coated with polyvinyl chloride compound is usually about 80 ° C or 105 ° C at the UL rated temperature, it is necessary that the non-halogen flame-retardant material replacing this wiring material also has this heat resistance. Become. Specifically, for heat resistance of UL80 ° C, heat deformation test and heat aging test in 121 ° C atmosphere, and for heat resistance of UL105 ° C, heat deformation test, heat aging test in 136 ° C atmosphere, etc. Therefore, an alternative non-halogen flame retardant material should be at least 121 ° C, preferably 136 ° C.
It is necessary not to melt at ℃. In addition, molded parts such as power plugs have the same problems as described above, and have heat resistance, flexibility and flame retardancy, and development of recyclable and remoldable molded parts is required.

In the wiring for electronic equipment used for electronic equipment, it is necessary to pass the particularly strict vertical flame-retardant standard (UL1581 VW-1) defined by the UL standard. However, it is difficult to significantly improve the flame retardancy even if a large amount of metal hydrate is blended using a resin having a high melting point such as the polypropylene resin described above, and the vertical flame retardancy standard is a strict flame retardancy standard. Does not fit. In addition, the electric wire coating material used for home electric appliances and the like is required to have mechanical characteristics defined by UL standard, for example, and the elongation of 100
%, A tensile strength of 10.3 MPa or more is required. Particularly in the case of a power cord, since it is bundled and shipped, further flexibility is required. On the other hand, similar heat deformation characteristics, flame retardancy characteristics, mechanical strength, and flexibility are required for molded parts such as power plugs, in addition to tubes and electric wire parts other than electric wires and sheets. In particular, sheets and tubes used for protection and connection of electric wires and construction materials are required to have surface flexibility and scratch resistance, but it has been difficult for conventional non-halogen materials to simultaneously satisfy these characteristics.

[0007]

DISCLOSURE OF THE INVENTION The present invention solves the above problems and is excellent in flame retardancy, heat resistance and mechanical properties, and elutes heavy metal compounds at the time of disposal such as landfill and combustion, It is an object of the present invention to provide a flame-retardant resin composition and a molded article that do not generate a large amount of smoke and harmful gas and that meet recent environmental problems. Further, the present invention, while satisfying these characteristics, can be reused because the coating material can be remelted, does not whiten even when bent, is not easily scratched, and has particularly high flame retardancy and flexibility. Another object of the present invention is to provide a flame-retardant resin composition, a wiring material using the same, an optical fiber core wire, an optical fiber cord, and other molded parts.

[0008]

The above-described problems have been solved by the following inventions. (1) (a) At least two polymer blocks A whose main constituent is a vinyl aromatic compound, and at least one polymer block B whose main constituent is a conjugated diene compound. Block copolymer, and / or hydrogenated block copolymer obtained by hydrogenating the block copolymer 3 to 55% by weight, (b) non-aromatic softening agent for rubber 0
To 40 wt%, (c) ethylene / α-olefin copolymer 0 to 80 wt%, (d1) ethylene-vinyl acetate copolymer, ethylene- (meth) acrylic acid copolymer, or ethylene- (meth) 5-80% by weight of at least one kind of acrylate copolymer, (e) 0-50% by weight of polypropylene resin, (f) 0-30% by weight of modified polyethylene resin modified with unsaturated carboxylic acid or its derivative,
And (p) 0.01 to 0.6 parts by weight of organic peroxide, and (h) (meth) acrylate to 100 parts by weight of the thermoplastic resin component (A) consisting of 0 to 45% by weight of acrylic rubber. -And / or allylic crosslinking aids 0.03 to 1.8 parts by weight, and metal hydrate (B) 50
~ 300 parts by weight of the metal hydrate (B)
(I) When the metal hydrate (B) is 50 parts by weight or more and less than 100 parts by weight, the thermoplastic resin component (A) 100
50 parts by weight or more of the metal hydrate pretreated with the silane coupling agent based on parts by weight; (ii) 100 parts by weight or more of the metal hydrate (B) 300
In the case of less than or equal to parts by weight, at least half of the metal hydrate (B) is a mixture having a composition in which the metal hydrate is pretreated with a silane coupling agent, and the thermoplastic resin component (A) A flame-retardant resin composition characterized by being heated and kneaded at a melting temperature or higher.

(2) (a) At least two polymer blocks A whose main constituent is a vinyl aromatic compound.
And a block copolymer comprising at least one polymer block B containing a conjugated diene compound as a main component, and / or a hydrogenated block copolymer obtained by hydrogenating the block copolymer in an amount of 3 to 30 wt. %, (B) 0 to 20% by weight of a non-aromatic softening agent for rubber, (c) 0 to 20% by weight of ethylene / α-olefin copolymer, (d1) ethylene-vinyl acetate copolymer, ethylene- ( 35-80% by weight of at least one kind of (meth) acrylic acid copolymer or ethylene- (meth) acrylic acid ester copolymer, (e) polypropylene resin 0-35% by weight, (f) unsaturated carboxylic acid or its Modified polyethylene resin modified with derivative 0
To 30% by weight, and (p) 0 to 45% by weight of the acrylic rubber, 100 g by weight of the thermoplastic resin component (A), 0.01 to 0.6 parts by weight of (g) organic peroxide, (h) ) (Meth) acrylate-based and / or allyl-based cross-linking aid 0.03 to 1.8 parts by weight, and the metal hydrate (B) in an amount of 50 to 300 parts by weight. (I) When the metal hydrate (B) is 50 parts by weight or more and less than 100 parts by weight, the thermoplastic resin component (A) 100
50 parts by weight or more of the metal hydrate pretreated with the silane coupling agent based on parts by weight; (ii) 100 parts by weight or more of the metal hydrate (B) 300
In the case of less than or equal to parts by weight, at least half of the metal hydrate (B) is a mixture having a composition in which the metal hydrate is pretreated with a silane coupling agent, and the thermoplastic resin component (A) A flame-retardant resin composition characterized by being heated and kneaded at a melting temperature or higher.

(3) (a) At least two polymer blocks A whose main constituent is a vinyl aromatic compound.
And a block copolymer comprising at least one polymer block B containing a conjugated diene compound as a main component, and / or a hydrogenated block copolymer obtained by hydrogenating the block copolymer 3 to 40 wt. %, (B) 0 to 40% by weight of a non-aromatic softening agent for rubber, (c) 0 to 80% by weight of ethylene / α-olefin copolymer, (d2) 5 to 50% by weight of ethylene / propylene copolymer rubber. %, (E) 0 to 50% by weight of polypropylene resin, and (f) 0 to 30% by weight of modified polyethylene resin modified with an unsaturated carboxylic acid or a derivative thereof (A) 100
(G) 0.01 to 100 parts by weight of organic peroxide
0.6 parts by weight, (h) (meth) acrylate-based and /
Or 0.03 to 1.8 parts by weight of an allylic crosslinking aid and 50 to 300 parts by weight of a metal hydrate (B), and the metal hydrate (B) is (i) the metal. When the hydrate (B) is 50 parts by weight or more and less than 100 parts by weight, the thermoplastic resin component (A) 100
25 parts by weight or more of the metal hydrate pretreated with the silane coupling agent based on parts by weight; (ii) 100 parts by weight or more of the metal hydrate (B) 300
In the case of less than or equal to parts by weight, at least 1 of the metal hydrate (B)
/ 4 amount is a mixture having a composition which is a metal hydrate pretreated with a silane coupling agent, and is obtained by heating and kneading at a melting temperature of the thermoplastic resin component (A) or higher. Flame-retardant resin composition.

(4) (a) At least two polymer blocks A whose main constituent is a vinyl aromatic compound.
And at least one polymer block B containing a conjugated diene compound as a main component, and / or a hydrogenated block copolymer obtained by hydrogenating the block copolymer in an amount of 3 to 55 parts by weight. %, (B) 0 to 40% by weight of a non-aromatic softening agent for rubber, (c) 0 to 80% by weight of ethylene / α-olefin copolymer, (d1) ethylene-vinyl acetate copolymer, ethylene- ( 5 to 80% by weight of at least one kind of (meth) acrylic acid copolymer or ethylene- (meth) acrylic acid ester copolymer, (d2) 5 to 50% by weight of ethylene / propylene copolymer rubber, (e)
Thermoplastic resin component (A) 100 comprising 0 to 50% by weight of polypropylene resin, 0 to 30% by weight of (f) modified polyethylene resin modified with unsaturated carboxylic acid or its derivative, and (p) 0 to 45% by weight of acrylic rubber. (G) 0.01 to 0.6 parts by weight of organic peroxide, (h) 0.03 to 1.8 parts by weight of (meth) acrylate-based and / or allyl-based crosslinking assistant, and metal The hydrate (B) is contained in a proportion of 50 to 300 parts by weight, and the metal hydrate (B) is (i) when the metal hydrate (B) is 50 parts by weight or more and less than 100 parts by weight. , The thermoplastic resin component (A) 100
50 parts by weight or more of the metal hydrate pretreated with the silane coupling agent based on parts by weight; (ii) 100 parts by weight or more of the metal hydrate (B) 300
In the case of less than or equal to parts by weight, at least half of the metal hydrate (B) is a mixture having a composition in which the metal hydrate is pretreated with a silane coupling agent, and the thermoplastic resin component (A) A flame-retardant resin composition characterized by being heated and kneaded at a melting temperature or higher.

(5) (a) At least two polymer blocks A whose main constituent is a vinyl aromatic compound.
And at least one polymer block B containing a conjugated diene compound as a main component, and / or a hydrogenated block copolymer obtained by hydrogenating the block copolymer in an amount of 3 to 55 parts by weight. %, (B) 0 to 40% by weight of a softening agent for non-aromatic rubber, (c) 0 to 80% by weight of ethylene / α-olefin copolymer, (d1) ethylene-vinyl acetate copolymer, ethylene- ( 5 to 80% by weight of at least one of (meth) acrylic acid copolymer or ethylene- (meth) acrylic acid ester copolymer, and (e) the melting point (Tm) of the polypropylene component measured by a differential scanning calorimeter is 163. ℃ or less, and the heat of crystal fusion (△
Hm) is not more than 55 J / g polypropylene resin 0-85 which is mainly composed of atactic polypropylene polymer
% By weight, (f) 0 to 30% by weight of a modified polyethylene resin modified with an unsaturated carboxylic acid or its derivative, and (p) 0 to 45% by weight of an acrylic rubber based on 100 parts by weight of a thermoplastic resin component (A). (G) 0.01 to 0.6 parts by weight of organic peroxide, (h) (meth) acrylate-based and / or allyl-based crosslinking aid 0.03 to
1.8 parts by weight and 50 to 300 parts by weight of the metal hydrate (B), and the metal hydrate (B) is (i) 50 parts by weight of the metal hydrate (B). Above 100 parts by weight, the thermoplastic resin component (A) 100
50 parts by weight or more of the metal hydrate pretreated with the silane coupling agent based on parts by weight; (ii) 100 parts by weight or more of the metal hydrate (B) 300
In the case of less than or equal to parts by weight, at least half of the metal hydrate (B) is a mixture having a composition in which the metal hydrate is pretreated with a silane coupling agent, and the thermoplastic resin component (A) A flame-retardant resin composition characterized by being heated and kneaded at a melting temperature or higher.

(6) (a) At least two polymer blocks A whose main constituent is a vinyl aromatic compound.
And a block copolymer comprising at least one polymer block B containing a conjugated diene compound as a main component, and / or a hydrogenated block copolymer obtained by hydrogenating the block copolymer in an amount of 3 to 30 wt. %, (B) 0 to 20% by weight of a non-aromatic softening agent for rubber, (c) 0 to 20% by weight of ethylene / α-olefin copolymer, (d1) ethylene-vinyl acetate copolymer, ethylene- ( 35 to 80% by weight of at least one of (meth) acrylic acid copolymer or ethylene- (meth) acrylic acid ester copolymer, and (e) the melting point (Tm) of the polypropylene component measured by a differential scanning calorimeter is 163. ℃ or less, and the heat of crystal fusion (△
Hm) is 55 J / g or less, and polypropylene resin 0 to 35 whose main component is an atactic polypropylene polymer
% By weight, (f) 0 to 30% by weight of a modified polyethylene resin modified with an unsaturated carboxylic acid or its derivative, and (p) 0 to 45% by weight of an acrylic rubber based on 100 parts by weight of a thermoplastic resin component (A). (G) 0.01 to 0.6 parts by weight of organic peroxide, (h) (meth) acrylate-based and / or allyl-based crosslinking aid 0.03 to
1.8 parts by weight and 50 to 300 parts by weight of the metal hydrate (B), and the metal hydrate (B) is (i) 50 parts by weight of the metal hydrate (B). Above 100 parts by weight, the thermoplastic resin component (A) 100
50 parts by weight or more of the metal hydrate pretreated with the silane coupling agent based on parts by weight; (ii) 100 parts by weight or more of the metal hydrate (B) 300
In the case of less than or equal to parts by weight, at least half of the metal hydrate (B) is a mixture having a composition in which the metal hydrate is pretreated with a silane coupling agent, and the thermoplastic resin component (A) A flame-retardant resin composition characterized by being heated and kneaded at a melting temperature or higher.

(7) (a) At least two polymer blocks A whose main constituent is a vinyl aromatic compound.
And a block copolymer comprising at least one polymer block B containing a conjugated diene compound as a main component, and / or a hydrogenated block copolymer obtained by hydrogenating the block copolymer 3 to 40 wt. %, (B) 0 to 40% by weight of a non-aromatic softening agent for rubber, (c) 0 to 80% by weight of ethylene / α-olefin copolymer, (d2) 5 to 50% by weight of ethylene / propylene copolymer rubber. %, (E) Melting point of polypropylene component measured by differential scanning calorimeter (T
m) is 163 ° C. or less, and the heat of fusion of crystal (ΔH
m) from 0 to 85% by weight of a polypropylene resin whose main component is an atactic polypropylene polymer having 55 J / g or less, and (f) from 0 to 30% by weight of a modified polyethylene resin modified with an unsaturated carboxylic acid or a derivative thereof. To 100 parts by weight of the thermoplastic resin component (A)
(G) 0.01 to 0.6 parts by weight of organic peroxide,
(H) 0.03 to 1.8 parts by weight of a (meth) acrylate-based and / or allyl-based cross-linking aid, and 50 to 300 parts by weight of a metal hydrate (B). (B) includes (i) when the metal hydrate (B) is 50 parts by weight or more and less than 100 parts by weight, the thermoplastic resin component (A) 100
25 parts by weight or more of the metal hydrate pretreated with the silane coupling agent based on parts by weight; (ii) 100 parts by weight or more of the metal hydrate (B) 300
In the case of less than or equal to parts by weight, at least 1 of the metal hydrate (B)
/ 4 amount is a mixture having a composition which is a metal hydrate pretreated with a silane coupling agent, and is obtained by heating and kneading at a melting temperature of the thermoplastic resin component (A) or higher. Flame-retardant resin composition.

(8) (a) At least two polymer blocks A whose main constituent is a vinyl aromatic compound.
And at least one polymer block B containing a conjugated diene compound as a main component, and / or a hydrogenated block copolymer obtained by hydrogenating the block copolymer in an amount of 3 to 55 parts by weight. %, (B) 0 to 40% by weight of a non-aromatic softening agent for rubber, (c) 0 to 80% by weight of ethylene / α-olefin copolymer, (d1) ethylene-vinyl acetate copolymer, ethylene- ( 5 to 80% by weight of at least one kind of (meth) acrylic acid copolymer or ethylene- (meth) acrylic acid ester copolymer, (d2) 5 to 50% by weight of ethylene / propylene copolymer rubber, (e)
Polypropylene resin containing an atactic polypropylene polymer as a main component, which has a melting point (Tm) of the polypropylene component measured by a differential scanning calorimeter of 163 ° C. or less and a heat of crystal fusion (ΔHm) of 55 J / g or less ~
With respect to 100 parts by weight of a thermoplastic resin component (A) consisting of 85% by weight, (f) 0 to 30% by weight of a modified polyethylene resin modified with an unsaturated carboxylic acid or a derivative thereof, and (p) 0 to 45% by weight of an acrylic rubber. (G) 0.01 to 0.6 parts by weight of organic peroxide, (h) (meth) acrylate-based and / or allyl-based crosslinking aid 0.03 to
1.8 parts by weight and 50 to 300 parts by weight of the metal hydrate (B), and the metal hydrate (B) is (i) 50 parts by weight of the metal hydrate (B). Above 100 parts by weight, the thermoplastic resin component (A) 100
50 parts by weight or more of the metal hydrate pretreated with the silane coupling agent based on parts by weight; (ii) 100 parts by weight or more of the metal hydrate (B) 300
In the case of less than or equal to parts by weight, at least half of the metal hydrate (B) is a mixture having a composition in which the metal hydrate is pretreated with a silane coupling agent, and the thermoplastic resin component (A) A flame-retardant resin composition characterized by being heated and kneaded at a melting temperature or higher. (9) The crosslinking aid (h) has the general formula

[0016]

[Chemical 2]

(Where R is H or CH ₃ and n
Is an integer of 1-9. (1) to (8), which is a (meth) acrylate-based crosslinking assistant represented by
The flame-retardant resin composition according to any one of items. (10) The flame-retardant resin composition according to any one of items (1) to (9), wherein the metal hydrate (B) is magnesium hydroxide. (11) The flame-retardant resin composition according to any one of items (1) to (10), wherein the silane coupling agent is a silane compound having a vinyl group and / or an epoxy group at the terminal. . (12) Ethylene-vinyl acetate copolymer, ethylene-
At least one kind of (meth) acrylic acid copolymer or ethylene- (meth) acrylic acid ester copolymer (d
1) is an ethylene-vinyl acetate copolymer having a vinyl acetate component content of 25% by weight or more, (1), (2), (4), (5), (6) or (8) ) Item, the flame-retardant resin composition. (13) The melamine cyanurate is contained in an amount of 3 to 70 parts by weight based on 100 parts by weight of the thermoplastic resin component (A). Flammable resin composition.

(14) 0.5 to 2 of at least one selected from zinc borate, zinc stannate and zinc hydroxystannate is added to 100 parts by weight of the thermoplastic resin component (A).
0 weight part is contained, The flame-retardant resin composition of any one of (1)-(13) characterized by the above-mentioned. (15) A flame-retardant resin composition according to any one of (1) to (14), which is provided as a coating layer on the outside of a conductor or an optical fiber element wire or / and an optical fiber core wire Molded article. (16) A molded part formed by molding the flame-retardant resin composition according to any one of (1) to (14).

(17) Any one of (1) to (14)
In the flame-retardant resin composition according to the item (a), at least two polymer blocks A having (a) a vinyl aromatic compound as a main component thereof, and at least one polymer block A having a conjugated diene compound as a main component. Block copolymer consisting of individual polymer blocks B, and / or a hydrogenated block copolymer obtained by hydrogenating this, (b) a non-aromatic softening agent for rubber, (c) ethylene / α -Olefin copolymer, (d1) ethylene-vinyl acetate copolymer, ethylene- (meth) acrylic acid copolymer, or ethylene-
At least one kind of (meth) acrylic acid ester copolymer and / or (d2) ethylene / propylene copolymer rubber, (e) polypropylene resin, (f) modified polyethylene resin modified with unsaturated carboxylic acid or its derivative, (P) acrylic rubber, (g) organic peroxide,
(H) A (meth) acrylate-based and / or an allyl-based crosslinking aid and a metal hydrate (B) are simultaneously heated and kneaded at a melting temperature of the resin components (a) to (f) or higher to perform a crosslinking treatment. A method for producing a flame-retardant resin composition, comprising:

(18) Any one of (1) to (14)
In the flame-retardant resin composition according to the item 1, in the first step, (a) at least two polymer blocks A containing a vinyl aromatic compound as a main constituent, and a conjugated diene compound as a main constituent. A block copolymer composed of at least one polymer block B, and / or a hydrogenated block copolymer obtained by hydrogenating the same.
(B) Non-aromatic softening agent for rubber, (c) ethylene / α-
At least one type of olefin copolymer, (d1) ethylene-vinyl acetate copolymer, ethylene- (meth) acrylic acid copolymer, or ethylene- (meth) acrylic acid ester copolymer and / or (d2) ethylene -Propylene copolymer rubber, (e) polypropylene resin, (f)
A modified polyethylene resin modified with an unsaturated carboxylic acid or a derivative thereof and (p) acrylic rubber are heated and kneaded to obtain a thermoplastic resin component (A), and then the resin components (A) and (g ) Organic peroxide, (h)
A (meth) acrylate-based and / or allyl-based crosslinking aid and a metal hydrate (B) are heated and kneaded at a melting temperature of the thermoplastic resin component (A) or higher to perform a crosslinking treatment. A method for producing a flame-retardant resin composition.

In the present invention, the amount of the organic peroxide contained together with the resin component, the amount and the kind of the crosslinking aid can be appropriately set within the above range to obtain a loose crosslinking structure having a low crosslinking density, and By selecting a specific metal hydrate, a large amount of metal hydrate can be blended.

[0022]

BEST MODE FOR CARRYING OUT THE INVENTION The present invention will be described in detail below. First, each component of the flame-retardant resin composition of the present invention will be described. (A) Thermoplastic resin component The thermoplastic resin component (A) includes (a) at least two polymer blocks A containing a vinyl aromatic compound as a main component, and a conjugated diene compound as a component. A block copolymer mainly composed of at least one polymer block B, and / or a hydrogenated block copolymer obtained by hydrogenating the same, (b) a non-aromatic rubber softener, c) an ethylene / α-olefin copolymer,
(D1) ethylene-vinyl acetate copolymer, ethylene-
At least one type of (meth) acrylic acid copolymer or ethylene- (meth) acrylic acid ester copolymer and / or (d2) ethylene / propylene copolymer rubber, (e) polypropylene resin, (f) unsaturated Modified polyethylene resin modified with carboxylic acid or its derivative,
And (p) acrylic rubber.

Component (a) Block Copolymer The component (a) of the present invention comprises at least two polymer blocks A containing a vinyl aromatic compound as a main constituent.
And a block copolymer comprising at least one polymer block B containing a conjugated diene compound as a main component, or a block copolymer obtained by hydrogenating the same, or a mixture thereof, for example, A- B-A, B-A-B
Examples thereof include vinyl aromatic compound-conjugated diene compound block copolymers having a structure such as —A and ABABABA, and hydrogenated products thereof. The (hydrogenated) block copolymer (hereinafter, the (hydrogenated) block copolymer means a block copolymer and / or a hydrogenated block copolymer) is a vinyl aromatic compound in an amount of 5 to 60. %, Preferably 20 to 50% by weight. The polymer block A, whose main constituent is a vinyl aromatic compound, preferably consists only of the vinyl aromatic compound or is greater than 50% by weight, preferably 7%.
0% by weight or more of a vinyl aromatic compound and a (hydrogenated) conjugated diene compound (hereinafter, a (hydrogenated) conjugated diene compound means a conjugated diene compound and / or a hydrogenated conjugated diene compound. ) Is a copolymer block with. The polymer block B, whose main constituent is a (hydrogenated) conjugated diene compound, preferably consists only of a (hydrogenated) conjugated diene compound or is greater than 50% by weight, preferably 70% by weight. %
It is a copolymer block of the above (hydrogenated) conjugated diene compound and a vinyl aromatic compound. In each of the polymer block A containing the vinyl aromatic compound as the main constituent and the polymer block B containing the (hydrogenated) conjugated diene compound as the main constituent, the vinyl aromatic in the molecular chain is Distribution of repeating units from group compounds or (hydrogenated) conjugated diene compounds is random, tapered (increasing or decreasing monomer content along the molecular chain), partially blocky or any combination of these May be. In the case where there are two or more polymer blocks A containing a vinyl aromatic compound as a main constituent, or polymer blocks B containing a (hydrogenated) conjugated diene compound as a main constituent,
Each may have the same structure or different structures.

As the vinyl aromatic compound constituting the (hydrogenated) block copolymer, for example, one or more selected from styrene, α-methylstyrene, vinyltoluene, p-tert-butylstyrene and the like. Of these, styrene is preferred. As the conjugated diene compound, for example, one kind or two or more kinds are selected from butadiene, isoprene, 1,3-pentadiene, 2,3-dimethyl-1,3-butadiene, and the like. Among them, butadiene,
Isoprene and combinations thereof are preferred. Polymer block B mainly composed of conjugated diene compound
The microstructure in can be arbitrarily selected. For example, in the polybutadiene block, those having a 1,2-microstructure of 20 to 50%, particularly 25 to 45% are preferable, and those in which at least 90% of butadiene-based aliphatic double bonds are hydrogenated are preferable. In the polyisoprene block, 70 to 1 of the isoprene compound is used.
00% by weight has a 1,4-microstructure and at least 90% of the aliphatic double bonds based on the isoprene compound
Is preferably hydrogenated. The weight average molecular weight of the (hydrogenated) block copolymer used in the present invention having the above structure is preferably 5,000 to 1,500,000, more preferably 10,000 to 550,000, and further preferably 100,000. ˜550,000, particularly preferably 100,000 to 400,000. Molecular weight distribution (weight average molecular weight (Mw) and number average molecular weight (M
The ratio (Mw / Mn) of n) is preferably 10 or less, more preferably 5 or less, and more preferably 2 or less. The molecular structure of the (hydrogenated) block copolymer is linear, branched,
It may be radial or any combination thereof.

A number of methods have been proposed as a method for producing these (hydrogenated) block copolymers, and a typical method is, for example, the method described in Japanese Patent Publication No. 40-23798. It can be obtained by block polymerization in an inert solvent using a lithium catalyst or a Ziegler type catalyst. Further, for example, the hydrogenated block copolymer is obtained by hydrogenating the block copolymer obtained by the above method in the presence of a hydrogenation catalyst in an inert solvent. Specific examples of the (hydrogenated) block copolymer include SBS (styrene / butadiene block copolymer), SIS (styrene / isoprene block copolymer), SEBS (hydrogenated SBS), SEPS (hydrogenated SIS), and the like. You can In the present invention, a particularly preferred (hydrogenated) block copolymer is a polymer block A whose main component is styrene, and isoprene whose main component is 7
0-100% by weight has a 1,4-microstructure and at least 90% of the isoprene-based aliphatic double bonds
Is a hydrogenated block copolymer having a weight average molecular weight of 50,000 to 550,000 and a polymer block B which has been hydrogenated. More preferably, 90 to 100% by weight of isoprene is the hydrogenated block copolymer having a 1,4-microstructure. The amount of the component (a) used is 3 to 55% by weight in the thermoplastic resin component (A). When the content of the component (a) is less than 3% by weight, not only the strength and elongation are greatly lowered, but also the bleeding of the component (b) is caused, the heat deformation characteristics are greatly deteriorated, and the heat resistance characteristics are also deteriorated. On the other hand, when it is more than 55% by weight, not only the extrusion moldability is remarkably lowered, but also the flame retardancy, heat shock resistance and the like are remarkably lowered. When the ethylene-propylene copolymer rubber of the component (d2) is used, the compounding amount of the component (a) is 3 to 40% by weight in the thermoplastic resin component (A). When using an ethylene-propylene copolymer rubber, for the purpose of suppressing bleeding of the softening agent for a non-aromatic rubber added to reduce the extrusion load, (a)
The component is 3% by weight or more in the thermoplastic resin component (A). In order to maintain strength, heat deformation characteristics, extrusion characteristics and the like while maintaining high vertical flame retardancy in wiring materials, the range of component (a) is 3 in the resin component (A).
It is preferably ˜30% by weight.

Component (b) Softening Agent for Non-Aromatic Rubber As the component (b) of the present invention, a non-aromatic mineral oil or a liquid or low molecular weight synthetic softening agent can be used. The mineral oil softening agent used for rubber is a mixture of three aromatic ring, naphthene ring and paraffin chain, and paraffin chain carbon number occupies 50% or more of total carbon number. That is, those having a carbon number of naphthene ring of 30 to 40% are called naphthene type, and those having an aromatic carbon number of 30% or more are called aromatic type. The mineral oil type rubber softening agents used as the component (b) of the present invention are paraffin type and naphthene type softeners in the above categories. The aromatic softening agent is not preferable because the component (a) becomes soluble due to its use, the crosslinking reaction is inhibited, and the physical properties of the obtained composition cannot be improved. As the component (b), a paraffinic one is preferable, and a paraffinic one having a small amount of aromatic ring components is particularly preferable. The properties of these non-aromatic softeners for rubber are such that the dynamic viscosity at 37.8 ° C. is 20 to 500 cS.
t, pour point is −10 to −15 ° C., flash point (COC) is 1
Those exhibiting 70 to 300 ° C. are preferable. The blending amount of the component (b) is 0 to 40% by weight in the thermoplastic resin component (A). If the amount is more than 40% by weight, not only the mechanical strength is greatly lowered, but also the flame retardancy and the heat deformability are greatly lowered. When the ethylene-propylene copolymer rubber of the component (d2) is used, the extrudability is significantly reduced,
In this case, the component (b) is preferably 5% by weight or more, more preferably 10% by weight or more in order to improve the extrudability. Even in a system in which ethylene-propylene copolymer rubber is added, when the amount of polypropylene is large, polypropylene does not participate in cross-linking during kneading and cross-linking, and further causes a decrease in molecular weight, which serves as a fluidized bed. It becomes possible to process without impairing the extrudability even without the component (b). In order to maintain strength, heat deformation characteristics, extrusion characteristics, etc. while maintaining high vertical flame retardancy in wiring materials, the range of component (b) is 0 to 0 in the resin component (A). It is preferably 20% by weight. A part of the component (b) may be added after the heat treatment in the presence of organic peroxide, but it may cause bleeding out. The component (b) preferably has a weight average molecular weight of 100 to 2,000.

Component (c) Ethylene / α-olefin Copolymer As the component (c) of the present invention, an ethylene / α-olefin copolymer is used. The ethylene / α-olefin copolymer (c) is preferably a copolymer of ethylene and an α-olefin having 4 to 12 carbon atoms, and specific examples of the α-olefin include 1-butene and 1-butene. Hexene, 4-methyl-1-pentene, 1-octene, 1-decene, 1-dodecene and the like can be mentioned. As the ethylene / α-olefin copolymer, LLDPE (linear low-density polyethylene), LDPE (low-density polyethylene), VLDPE
(Ultra low density polyethylene), EBR (ethylene / butadiene rubber), and ethylene / α-olefin copolymer synthesized in the presence of a single site catalyst.
Among these, ethylene / α-olefin copolymers synthesized in the presence of a single site catalyst are preferable. The ethylene / α-olefin copolymer (c) has a density of 0.94.
It is preferably 0 g / cm ³ or less, more preferably 0.93.
0 g / cm ³ or less, more preferably 0.925 g / c
m ³ or less, particularly preferably 0.915 g / cm ³ or less. This is because if the density is high, it becomes difficult to highly fill the metal hydrate, and the flexibility of the resin composition or the wiring material covering the resin composition deteriorates. The lower limit of this density is not particularly limited, but usually the lower limit is about 0.850 g / cm ³ . Further, as the ethylene / α-olefin copolymer (c), the melt flow index (AS
It is preferable that TM D-1238) is 0.5 to 30 g / 10 minutes.

Examples of the ethylene / α-olefin copolymer in the present invention include those synthesized in the presence of a single-site catalyst, ordinary linear low-density polyethylene, and ultra-low-density polyethylene. Those which are synthesized in the presence of a catalyst are preferable, and the production method thereof is disclosed in JP-A-6-306121 and JP-A-7-500.
Known methods described in Japanese Patent No. 622, etc. can be used. The single-site catalyst has a single polymerization active point and has a high polymerization activity, and is also called a metallocene catalyst or a Kaminsky catalyst. An ethylene / α-olefin copolymer synthesized by using this catalyst. Has a narrow molecular weight distribution and narrow composition distribution. Since the ethylene / α-olefin copolymer synthesized in the presence of such a single-site catalyst has high tensile strength, tear strength, impact strength, etc., it is necessary to highly fill with a metal hydrate. When used as a flammable material (wiring material coating material), there is an advantage that deterioration of mechanical properties due to highly filled metal hydrate can be reduced. On the other hand, when an ethylene / α-olefin copolymer synthesized using a single-site catalyst is used, the melt viscosity increases and the melt tension decreases compared to the case of using a normal ethylene / α-olefin copolymer. However, there is a problem in moldability. In this regard, long-chain branching was introduced by using an asymmetric catalyst as a single-site catalyst (Constrained Geometry Ca
(Tyristical Technology), or by connecting two polymerization tanks during synthesis, two peaks are created in the molecular weight distribution (Advanced Performance).
anceTerpolymer) has improved its moldability.

The ethylene / α-olefin copolymer (c) synthesized in the presence of the single-site catalyst used in the present invention is preferably the one having the above-mentioned molding processability improved. Dow Che
"AFFINITY" and "ENGAG" from Mical
"E" (brand name), "EXACT" (brand name) is marketed by Exxon Chemical, and "Umerit" (brand name) is marketed by Ube Industries.

The blending amount of the component (c) in the thermoplastic resin component (A) is 0 to 80% by weight, preferably 0 to 60%.
%, More preferably 0 to 40% by weight. If the blending amount is too large, not only the flame retardant property is deteriorated, but also the heat deformation property is deteriorated. The component (c) is not an essential component in the present invention, but has a function of improving strength. Particularly in the case of an electric wire that requires high strength or an electric wire having extremely high wear resistance, it is better to add a large amount of component (c). By introducing the component (c), it is possible to maintain particularly high wear resistance and strength. Especially density 0.89
Above, more preferably 0.90 or more, more preferably 0.910 or more, when the ethylene / α-olefin copolymer synthesized in the presence of a single site catalyst is introduced,
High wear resistance and very high strength can be obtained. Furthermore, by adding a large amount of this component, the oil resistance can be greatly improved. It is considered that this is because the introduction of the component (c) increases the crosslink density of the polymer portion. By introducing a large amount of the component (c) such as 40% by weight or more, the soft component is reduced and the flexibility of the composition and the electric wire becomes poor. It is possible to maintain high wear resistance and strength even if magnesium hydroxide is added in an amount of 200 parts by weight or more with respect to 100 parts by weight of the base material. Very useful for required materials and electric wires. Further, ethylene synthesized in the presence of a single-site catalyst having a density of 0.900 or more, and more preferably 0.910 or more.
When a large amount of α-olefin copolymer is introduced, high oil resistance property is obtained. In order to maintain vertical flame retardancy, which is highly flame retardant in the wiring material, the range of the component (c) is preferably 0 to 20% by weight in the resin component (A).

Component (d1) At least one ethylene-vinyl acetate copolymer, ethylene- (meth) acrylic acid copolymer, or ethylene- (meth) acrylic acid ester copolymer is used as the component (d1) of the present invention. Is an ethylene-vinyl acetate copolymer, an ethylene- (meth) acrylic acid copolymer, an ethylene- (meth) acrylic acid ester copolymer (for example, an ethylene-butyl acrylate copolymer, an ethylene-ethyl acrylate copolymer). (Coalescence, ethylene-methyl acrylate copolymer, ethylene-methyl methacrylate copolymer, etc.)
At least one of the above is used. Among these, it is preferable to use an ethylene-vinyl acetate copolymer in order to further improve the flame retardancy. To further improve flame retardancy, the content of copolymerization components other than ethylene should be 23% by weight.
It is preferably not less than 25% by weight, more preferably 25% by weight
As described above, more preferably 28% by weight or more. For example, in the case of ethylene-vinyl acetate copolymer, vinyl acetate (V
The content of the component A) is preferably 23% by weight or more. The MFR is preferably 0.3 or more from the viewpoint of fluidity and 30 or less from the viewpoint of maintaining strength. The blending amount of the component (d1) in the thermoplastic resin component (A) is 5 to 80% by weight, preferably 15 to 65% by weight. If the blending amount of the component (d1) is less than 5% by weight, the flame retardancy decreases. In order to ensure vertical flame retardancy in the wiring material, the compounding amount of the component (d1) is 35% by weight or more in the thermoplastic resin component (A). On the other hand, when the content is more than 80% by weight, the heat deformation characteristics, heat resistance characteristics and extrusion characteristics are remarkably deteriorated.

Component (d2) ethylene-propylene copolymer rubber Ethylene-propylene copolymer rubber (EPM) used as a base resin in the flame-retardant thermoplastic resin composition of the present invention.
Is a rubbery copolymer of ethylene and propylene. Here, the ethylene / propylene copolymer rubber means a rubber having an ethylene component content of usually about 40 to 75% by weight. There is also an ethylene-propylene terpolymer (EPDM) in which a polymer has a repeating unit having an unsaturated group as a third component other than ethylene and propylene, but in the present invention, it is necessary to use an EPM having no double bond. . This is because when EPDM is used, excellent flexibility and elongation, which are the objects of the present invention, are impaired. The EPMs may be used alone or in combination of two or more. Ethylene
The ethylene content of the propylene copolymer rubber is 85-
40% by weight is suitable. Preferably 80-45% by weight
And more preferably 75 to 50% by weight. If the ethylene component content is too low, the resulting resin composition will lack flexibility, and if it is too high, the mechanical strength will decrease. The Mooney viscosity and M _{L1 + 4} (100 ° C.) of the ethylene-propylene copolymer rubber are preferably 10 to 120, more preferably 40 to 100. Mooney viscosity is 10
If it is less than 1, the rubber elasticity of the resulting elastomer composition may be poor. Further, if the number exceeds 120, the molding processability may be deteriorated, and particularly the appearance of the molded product is deteriorated. The ethylene-propylene copolymer rubber used has a weight average molecular weight of 50,000 to 1,000,000.
0 is preferable, and more preferably 70,000 to 500,000.
Is preferred. When the weight average molecular weight is less than 50,000, the resulting composition may have poor rubber elasticity. Further, if a resin having a weight average molecular weight of more than 1,000,000 is used, the molding processability may be deteriorated and the appearance of the molded product may be deteriorated. The blending amount of the ethylene-propylene copolymer rubber is 5 to 50 in the thermoplastic resin component (A).
% By weight, preferably 15-40% by weight.
When the content of component (d2) is less than 5% by weight, elongation, flexibility,
Filler acceptability is reduced. On the other hand, if the amount is too large, the mechanical strength is lowered. In the flame-retardant resin composition of the present invention, at least one kind of the component (d1) and / or the component (d2) is used, and they may be used alone or as a mixture of both. . When mixed and used, the component (d1) is 5 in the thermoplastic resin component (A).
It is preferable that the amount of the component (d2) is -80% by weight and the amount of the component (d2) is 5-50% by weight.

Component (e) Polypropylene Resin Polypropylene resin which can be used in the present invention includes homopolypropylene, ethylene / propylene random copolymer, ethylene / propylene block copolymer, propylene and other small amount of α-olefin. (Eg 1
-Butene, 1-hexene, 4-methyl-1-pentene, etc.) (copolymer) (atactic polypropylene). Here, the ethylene / propylene random copolymer means an ethylene component content of about 1 to 4% by weight, and the ethylene / propylene block copolymer means an ethylene component content of about 5 to 20% by weight.

The polypropylene resin of the component (e) of the present invention has a melting point (Tm) of 1 as measured by a differential scanning calorimeter.
The temperature is 63 ° C. or lower and the heat of fusion of crystal (ΔHm) is 55.
An atactic polypropylene polymer having a J / g or less may be contained as a main component. Here "main component"
Means that the content of component (e) is preferably 50% by weight or more. Here, with reference to FIG. 1, a method for measuring the melting point (Tm) and the heat of crystal fusion (ΔHm) in the present invention will be described. In the present invention, a differential scanning calorimeter of atactic polypropylene polymer (hereinafter abbreviated as DSC)
The measurement is performed under a nitrogen atmosphere at a temperature rising rate of 10 ° C./min according to ordinary conditions. When the atactic polypropylene polymer is a homopolymer, one large endothermic peak is observed as the temperature rises. When the atactic polypropylene polymer is a copolymer of a propylene component and other olefin components, two or more endothermic peaks are observed. The DSC chart shown in FIG. 1 is for an atactic polypropylene polymer composed of a butene-1 component and a propylene component, but two large endothermic peaks are observed. In FIG. 1, the lower temperature peak is butene-
The endothermic peak due to the one component and the higher temperature peak are the endothermic peaks due to the propylene component.
T2 shows the peak top temperature of each endotherm. T2
Generally appears at 138-160 ° C. Before and after the endothermic peak is observed, the calorific value-temperature curve is almost flat, and after the endothermic calorific value-temperature curve is flat from the flat part D to the lower temperature, that is, the straight line where the calorific value becomes constant, that is, the base. Draw a line. The point where the baseline and the curve extended from the endothermic curve having a peak at temperature T2 intersect is B
And The heat of crystal fusion (ΔHm) of the propylene component can be determined from the area surrounded by this baseline and the endothermic curve having a peak at the temperature T2 (and its extension). (Note that A is the leveled part of the calorific value-temperature curve for the endothermic peak due to the butene-1 component. From the endothermic curve having a peak at the baseline and the temperature T1 for the butene-1 component drawn with this as a reference, The point where the extended curve intersects is shown as C.) In the case of a homopolymer, since there is one peak, the area surrounded by the endothermic curve and the baseline becomes the heat of fusion of crystal (ΔHm).

Examples of the atactic polypropylene polymer that can be used in the present invention include amorphous polypropylene and copolymers of propylene and other α-olefins. In the case of amorphous polypropylene, a resin that is a by-product during the production of crystalline polypropylene resin may be used, or it may be produced from a raw material. Further, a copolymer of propylene and other α-olefin can be produced from a raw material so as to contain a predetermined propylene component. In this case, for example, it can be obtained by polymerizing a raw material monomer in the presence of hydrogen and / or in the absence of hydrogen using a titanium-supported catalyst supported on magnesium chloride and triethylaluminum.

The atactic polypropylene polymer used in the present invention can be appropriately selected, but has a melting point of 16
The temperature is 3 ° C. or lower, and the heat of fusion of crystal (ΔHm) is 55.
Those of J / g or less can be used. A copolymer having a melting point of 160 ° C. or lower and a crystal fusion heat amount (ΔHm) of 40 J / g or lower is preferable. As a typical monomer copolymerized with propylene,
Butene-1 is given. Commercially available products of this atactic polypropylene polymer include ATF-132 and ATF.
-133 (all are trade names, manufactured by Ube Industries, Ltd.) and the like can also be used.

The polypropylene resin as the component (e) is
In the present invention, when the thermoplastic resin component (A) is heated and kneaded to produce a partially crosslinked product, a part thereof may be blended after the heating and kneading. The polypropylene resin compounded in (A) before heat kneading is
Due to the presence of the component (g), it is thermally decomposed to have an appropriately low molecular weight. As the polypropylene resin to be blended before heating and kneading, MFR (ASTM-D-1238, L condition, 230
C.) is preferably 0.1 to 25 g / 10 minutes, more preferably 0.1 to 10 g / 10 minutes, still more preferably 0.1.
~ 5 g / 10 min. When the MFR of the polypropylene resin is less than 0.1 g / 10 minutes, the molecular weight of the polypropylene resin does not decrease even after the heat treatment, and the moldability of the obtained resin composition may deteriorate.
If it exceeds g / 10 minutes, the molecular weight becomes too low, and the rubber elasticity of the obtained resin composition may deteriorate. The polypropylene resin to be blended after heating and kneading may be one that meets the conditions at the time of extrusion for forming the coating layer, and has an MFR of preferably 5 to 200 g / 10 minutes, more preferably 8 to 150 g / 10 minutes. , And more preferably 10
~ 100 g / 10 min. When compounded after heating and kneading, if the MFR of the polypropylene resin is less than 5 g / 10 minutes, the moldability of the obtained resin composition may deteriorate, and if the MFR exceeds 200 g / 10 minutes, the obtained resin composition Rubber elasticity may deteriorate.

The blending amount of the component (e) in the thermoplastic resin component (A) is 0 to 50% by weight, preferably 0 to 35.
% By weight. If it exceeds 50% by weight, not only the resin composition becomes extremely hard but also the mechanical strength is lowered,
There is also a problem that the surface of the resin mixture is easily scratched.
However, when atactic polypropylene is used, it is 0 to 85% by weight, preferably 5 to 85% by weight, and more preferably 5 to 5% by weight in the thermoplastic resin component (A).
It can be used in the range of 50% by weight. This is because it is composed of many amorphous components, so that the decrease in mechanical strength can be suppressed even if magnesium hydroxide is added. Further, in the case of atactic polypropylene, the flexibility can be controlled by controlling the amount of the atactic site, and therefore, even if a little more is added, the flexibility can be maintained to some extent. An advantage of adding 50% by weight or more of this atactic polypropylene is improvement in oil resistance.

In order to maintain strength, heat deformation characteristics, extrusion characteristics, etc. while maintaining high vertical flame retardancy in wiring materials, the range of component (e) is component (A).
It is preferably 0 to 35% by weight. When the ethylene-propylene copolymer rubber of the component (d2) is used, the compounding amount of the component (e) in the thermoplastic resin component (A) is
It is preferably 0 to 30% by weight, but 0 to 50% by weight can be used when flexibility is not required. Although the flexibility becomes poor by adding the component (e) in an amount of 30% by weight or more, it becomes possible to maintain the extrudability even if the components (a) and (b) are extremely reduced.
By adding a large amount of the component (c), it becomes possible to obtain a material and an electric wire which are excellent in workability and have oil resistance, high strength and high abrasion resistance. Also in this case, when atactic polypropylene is used, it is 0 to 85% by weight in the thermoplastic resin component (A), and preferably 5 to 80%.
It can be used in an amount of 5% by weight, more preferably 5 to 50% by weight. The component (e) has the function of improving the extrudability of the resin composition while ensuring the heat resistance, but the component (e) can be omitted when high heat resistance is not required. When the component (e) is not used, it is usually
The amount of the component (b) used is adjusted so that the resin composition as a whole has good extrudability. Furthermore, in the wiring material, the heat deformability of the wire rated at UL105 ℃ (136 ℃)
In order to retain the above, it is particularly preferable to use at least one of homopolypropylene and ethylene / propylene block copolymer as the polypropylene resin. As a compounding amount, it is preferable to add at least one of homopolypropylene and an ethylene / propylene block copolymer in the thermoplastic resin component (A) in an amount of 15% by weight or more.

Component (f) Polyolefin Resin Modified with Unsaturated Carboxylic Acid or Derivatives Thereof Polyolefin resins modified with unsaturated carboxylic acids or derivatives thereof include linear polyethylene, ultra low density polyethylene and high density polyethylene. Examples include polyolefin resins. In the present invention, the component (f) is a resin obtained by modifying these resins with an unsaturated carboxylic acid or a derivative thereof (hereinafter, these are collectively referred to as an unsaturated carboxylic acid or the like). Examples of the unsaturated carboxylic acid used for modification include maleic acid, itaconic acid, fumaric acid, and the like.
As the unsaturated carboxylic acid derivative, maleic acid monoester, maleic acid diester, maleic anhydride, itaconic acid monoester, itaconic acid diester, itaconic anhydride, fumaric acid monoester, fumaric acid diester,
Examples thereof include fumaric anhydride. The modification of the polyolefin can be carried out, for example, by heating and kneading the polyolefin and the unsaturated carboxylic acid in the presence of an organic peroxide. The amount of modification with maleic acid is usually about 0.1 to 7% by weight. By adding the polyolefin resin modified with the unsaturated carboxylic acid or its derivative, it is possible to increase the elongation of the obtained resin composition and to maintain the strength, and further it is possible to keep the volume resistivity high. The polyolefin resin modified with an unsaturated carboxylic acid or a derivative thereof has an effect of alleviating deterioration of mechanical properties due to a metal hydrate and an effect of preventing whitening of an electric wire. The compounding amount of the component (f) is 0 to 30% by weight in the component (A). The component (f) is not always an essential component, but it is preferable to add it in order to add the above effects. If the blending amount of the component (f) is too large, not only the flame retardancy is significantly lowered, but also the extrusion characteristics of the electric wire may be significantly lowered.

(P) Component Acrylic rubber Acrylic rubber is ethyl acrylate as a monomer component,
A rubber elastic body obtained by copolymerizing a small amount of a monomer having various functional groups with an alkyl acrylate such as butyl acrylate, and the monomers to be copolymerized are methyl vinyl ketone, acrylic acid, acrylonitrile, and butadiene. Etc. can be used appropriately. Specifically, Nipol
AR (trade name, manufactured by Zeon Corporation), JSR AR (trade name, manufactured by JSR Corporation) and the like can be used. In particular, it is preferable to use methyl acrylate as a monomer component, and in that case, a binary copolymer with ethylene or an unsaturated hydrocarbon having a carboxyl group such as acrylic acid in its side chain is further added. Can be used as a monomer, or a terpolymer in which is added as a third component can be particularly preferably used. Specifically, in the case of a binary copolymer, Baymac D and Baymac DLS, and in the case of a terpolymer, Baymac G, Baymac HG, Baymac LS,
Baymac GLS (trade name, all manufactured by Mitsui DuPont Polychemical Co., Ltd.) can be used. By adding acrylic rubber, the flame retardancy of the composition and molded articles such as electric wires is significantly improved. Further, by blending this acrylic rubber, the peeling property becomes good without stretching the covering material in a beard shape at the time of peeling. In the present invention, the acrylic rubber is 45% by weight or less in the resin component, preferably 3 to 45%.
It can be used in proportions by weight. This is because if the amount of the acrylic rubber exceeds 45% by weight, not only the workability during compounding and extrusion workability but also the elongation is significantly reduced.

Further, it is preferable to use, as the acrylic rubber, a terpolymer copolymer acrylic rubber of ethylene, an alkyl acrylate and an unsaturated hydrocarbon having a side chain of a carboxyl group because the flame retardancy is improved. 3 as the compounding amount
It is preferable to add 3% by weight or more of the original acrylic rubber,
It is more preferably 5% by weight or more, and further preferably 10% by weight or more. Further, this ternary acrylic rubber tends to increase the extrusion load, and it is preferably suppressed to 40% by weight or less, more preferably 35% by weight or less, and further preferably 30% by weight or less. Furthermore, when used in combination with a binary acrylic rubber of ethylene and alkyl acrylate, a foam layer is generated inside during combustion, and a carbonized layer, which is thought to be due to a ternary acrylic rubber, is formed on the surface. Will improve further. Further, by using a terpolymer copolymer acrylic rubber of ethylene, an alkyl acrylate, and an unsaturated hydrocarbon having a carboxyl group in its side chain, the acrylic rubber becomes strong and the mechanical strength is improved.

Component (g) Organic peroxide Examples of the organic peroxide used in the present invention include dicumyl peroxide, di-tert-butyl peroxide and 2,5-dimethyl-2,5-di- (te.
rt-Butylperoxy) hexane, 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-
Examples thereof include chlorobenzoyl peroxide, 2,4-dichlorobenzoyl peroxide, tert-butylperoxybenzoate, tert-butylperoxyisopropyl carbonate, diacetyl peroxide, lauroyl peroxide and tert-butylcumyl peroxide. Of these, 2,5-dimethyl-2,5-di- (tert-butylperoxy) hexane and 2,5-dimethyl-2,5-di-from the viewpoint of odor, coloring and scorch stability. Most preferred is (tert-butylperoxy) hexyne-3. The blending amount of the organic peroxide (e) is the thermoplastic resin component (A).
It is in the range of 0.01 to 0.6 parts by weight, preferably 0.03 to 0.5 parts by weight, relative to 100 parts by weight. By selecting the organic peroxide within this range,
Since the crosslinking does not proceed too much, a partially crosslinked composition excellent in extrudability can be obtained without causing lumps.

(H) Component (meth) acrylate-based and / or allyl-based cross-linking aid In the production of the flame-retardant resin composition of the present invention or the thermoplastic resin component (A) used therefor, the presence of an organic peroxide is used. And forms a partially crosslinked structure between the vinyl aromatic thermoplastic elastomer and the ethylene-α-olefin copolymer via the crosslinking aid. The crosslinking aid used at that time is represented by the general formula

[0045]

[Chemical 3]

(Where R is H or CH ₃ and n
Is an integer of 1-9. The (meth) acrylate type crosslinking auxiliary agent represented by these is mentioned. Here, the (meth) acrylate-based crosslinking aid refers to acrylate-based and methacrylate-based crosslinking aids. Specific examples include ethylene glycol dimethacrylate, diethylene glycol dimethacrylate, triethylene glycol dimethacrylate, polyethylene glycol dimethacrylate, trimethylolpropane trimethacrylate, and allyl methacrylate. In addition, those having an allyl group at the terminal such as diallyl fumarate, diallyl phthalate, tetraallyloxyethane and triallyl cyanurate can be used. Among these, (meth) acrylate crosslinking aids in which n is 1 to 6 are particularly preferable, and examples thereof include ethylene glycol diacrylate, triethylene glycol dimethacrylate, and tetraethylene glycol dimethacrylate. In particular, in the present invention, triethylene glycol dimethacrylate is easy to handle, has good compatibility with other components, and has a peroxide solubilizing action, and acts as a dispersion aid of peroxide, so that it is heated. It is most preferable because the crosslinking effect at the time of kneading is uniform and effective, and a partially crosslinked thermoplastic resin having a well-balanced hardness and rubber elasticity can be obtained. By using such a compound, neither insufficient crosslinking nor excessive crosslinking can be expected, and a uniform and efficient partial crosslinking reaction can be expected during heat kneading. The addition amount of the crosslinking aid used in the present invention is 100 parts by weight of the thermoplastic resin component (A).
The range of 0.03 to 1.8 parts by weight is preferable, and the range of 0.05 to 1.6 parts by weight is more preferable. By selecting the cross-linking aid within this range, a composition having excellent extrudability can be obtained without cross-linking proceeding too much to form a partially cross-linked structure with low cross-linking density. The blending amount of the crosslinking aid is preferably about 1.5 to 4.0 times the addition amount of the organic peroxide by weight.

(B) Metal Hydrate The metal hydrate used in the present invention is not particularly limited, but examples thereof include aluminum hydroxide, magnesium hydroxide, hydrated aluminum silicate, hydrated magnesium silicate and basic. A compound having a hydroxyl group or water of crystallization such as magnesium carbonate or hydrotalcite can be used alone or in combination of two or more kinds. Among these metal hydrates, aluminum hydroxide and magnesium hydroxide are preferable. It is necessary that at least part of the metal hydrate is treated with a silane coupling agent, but untreated metal hydrate without surface treatment or metal water treated with other surface treatment agents such as fatty acids. Japanese products can be used in combination as appropriate.

As the silane coupling agent used for the surface treatment of the above metal hydrate, vinyltrimethoxysilane, vinyltriethoxysilane, glycidoxypropyltrimethoxysilane, glycidoxypropyltriethoxysilane, glycid Xypropylmethyldimethoxysilane, methacryloxypropyltrimethoxysilane,
A silane coupling agent having a vinyl group or an epoxy group at the terminal such as methacryloxypropyltriethoxysilane and methacryloxypropylmethyldimethoxysilane.
A silane coupling agent having a mercapto group at the terminal such as mercaptopropyltrimethoxysilane and mercaptopropyltriethoxysilane, aminopropyltriethoxysilane, aminopropyltrimethoxysilane, N-
(Β-aminoethyl) -γ-aminopropyltripropyltrimethoxysilane, N- (β-aminoethyl) -γ
Crosslinkable silane coupling agents such as amino group-containing silane coupling agents such as aminopropyltripropylmethyldimethoxysilane are preferred. Two or more of these silane coupling agents may be used in combination. Here, the vinyl group includes those having a double bond at the terminal such as an acrylic group and a methacrylic group. Among such crosslinkable silane coupling agents, a silane coupling agent having an epoxy group and / or a vinyl group at the terminal is more preferable, and these may be used alone or in combination of two or more. .

The silane coupling agent surface-treated magnesium hydroxide that can be used in the present invention is a non-surface-treated one (such as Kisuma 5 (trade name, manufactured by Kyowa Chemical Co., Ltd. as a commercial product)), stearic acid, Those surface-treated with fatty acids such as oleic acid (Kisuma 5A (trade name, manufactured by Kyowa Chemical Co., Ltd.)), those treated with phosphoric acid ester, etc., surface-treated with the above silane coupling agent,
Alternatively, there are commercially available magnesium hydroxide (Kisuma 5LH, Kisuma 5PH (both are trade names, manufactured by Kyowa Chemical Co., Ltd.), etc.) that have been surface-treated with a silane coupling agent. In addition to the above, silane coupling having a functional group such as a vinyl group or an epoxy group at a terminal is further added to magnesium hydroxide or aluminum hydroxide whose surface is partially pretreated with a fatty acid or a phosphoric ester. It is also possible to use a metal hydrate or the like which has been surface-treated with an agent.

When the metal hydrate is treated with the silane coupling agent, it is necessary to blend the silane coupling agent with the metal hydrate in advance. At this time, the silane coupling agent is appropriately added in an amount sufficient for the surface treatment.
2% by weight is preferred. The silane coupling agent may be an undiluted solution or may be diluted with a solvent.

The amount of the metal hydrate blended is 100 parts by weight of the thermoplastic resin component (A) in the resin composition of the present invention.
50 to 300 parts by weight. In the present invention, when (i) the metal hydrate is 50 parts by weight or more and less than 100 parts by weight, the thermoplastic resin component (A) is used in an amount of 50 parts by weight or more based on 100 parts by weight, and (ii) the metal hydrate. When the amount of the metal hydrate is 100 parts by weight or more, at least half of the amount is a metal hydrate pretreated with a silane coupling agent. It becomes possible to mix a filler with. Although the compounding amount of the metal hydrate when the component (d2) is used without using the component (d1) is 50 to 300 parts by weight with respect to 100 parts by weight of the thermoplastic resin component (A). When (i) the metal hydrate is 50 parts by weight or more and less than 100 parts by weight, 25 parts by weight or more of 100 parts by weight of the thermoplastic resin component (A), and (ii) the metal hydrate is In the case of 100 parts by weight or more and 300 parts by weight or less, a flexible flame retardant resin composition can be obtained by using at least 1/4 of the amount as a metal hydrate pretreated with a silane coupling agent. it can.

When a polyolefin resin such as a normal polyethylene resin or polypropylene resin is used as a base resin and a large amount of metal hydrate is added to satisfy the required flame retardancy, the mechanical strength is lowered. Very big.
On the other hand, the thermoplastic resin component (A) in the present invention
Has a low cross-linking density and the resin components are in a partially cross-linked state through the component (h), and therefore has excellent filler acceptability,
When such a thermoplastic resin component (A) is used as a base resin, a large amount of metal hydrate can be blended. Among them, only when a specific amount of the metal hydrate treated with the silane coupling agent is blended, the base resin of the component (A) and the component (B) are added via the silane coupling agent.
Since the metal hydrate of (1) has an interaction, the decrease in mechanical strength is suppressed to a minimum, whitening hardly occurs when bent, and satisfactory properties can be obtained as a coating material for wiring materials, molded parts, and the like.

Although the details of the reaction mechanism at the time of heating and kneading the resin composition of the present invention are not clear yet, it is considered as follows. That is, when the thermoplastic resin component (A) in the present invention is heated and kneaded, it is present in the presence of the component (g),
Via component (h), component (a), component (c), (d1)
The component and / or the component (d2) and the component (p) are crosslinked. On the other hand, when component (e) is present, (g)
By the action of the components, the melt viscosity of the resin composition can be appropriately adjusted by appropriately lowering the molecular weight, and the melt viscosity of the resin composition can also be adjusted by the component (b). As a result, the composition as a whole becomes a crosslinked product having excellent extrudability. Crosslinking of the composition of the present invention may be carried out in the presence of a small amount of component (g), and it can be referred to as partial crosslinking because it has fewer crosslinking points than ordinary crosslinking. The degree of crosslinking of this flame-retardant resin composition can be represented by the gel fraction and dynamic elastic modulus of the thermoplastic resin component (A) as a guide. The gel fraction can be expressed by the ratio of the weight of the residual solid content to 1 g of the sample after wrapping 1 g of the sample in a 100-mesh wire net and using a Soxhlet extractor for 10 hours in boiling xylene. The dynamic elastic modulus can be expressed by the storage elastic modulus of melt viscoelasticity using a parallel plate. In the present invention, the degree of crosslinking is preferably 30 to 45% by weight, more preferably 40 to 45% by weight in terms of gel fraction, and preferably 10 in terms of storage elastic modulus.
^{It is 5} to 10 ⁷ Pa. When the thermoplastic resin component (A) is filled with a metal hydrate, when a specific amount of the metal hydrate treated with the silane coupling agent is blended with the components (g) and (h) at the same time. As long as it is possible to compound a large amount of metal hydrate without impairing the extrusion processability during molding, while having a high degree of flame retardancy and flexibility, while also having heat resistance, and mechanical properties, A flame-retardant resin composition that can be re-extruded after use and can be recycled can be obtained. The mechanism of the action of the metal hydrate treated with the silane coupling agent is not clear yet, but it is considered as follows. That is, the silane coupling agent bonded to the surface of the metal hydrate by treating with the silane coupling agent has one alkoxy group bonded to the metal hydrate and a vinyl group or an epoxy group present at the other end. The various reactive sites including the above bond with the vinyl aromatic thermoplastic elastomer of the component (a) and the uncrosslinked parts of the component (c), the component (d1), the component (d2) and the component (p). With this, it becomes possible to mix a large amount of metal hydrate without impairing the extrusion moldability, the adhesion between the resin and the metal hydrate becomes strong, and the mechanical strength and wear resistance are good, A flame-retardant resin composition that is not easily scratched is obtained.

(C) Melamine Cyanurate Compound The melamine cyanurate compound used in the present invention preferably has 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 further preferably 5 μm or less. Further, a melamine cyanurate compound surface-treated from the viewpoint of dispersibility is preferably used. As the melamine cyanurate compound that can be used in the present invention,
For example, MCA-0 and MCA-1 (both are trade names, manufactured by Mitsubishi Chemical Co., Ltd.) and those marketed by Chemie Linz Gmbh are available. Examples of the melamine cyanurate compound surface-treated with a fatty acid and the melamine cyanurate compound surface-treated with silane include MC610 and MC640 (both are trade names, manufactured by Nissan Chemical Co., Ltd.). As the melamine cyanurate compound that can be used in the present invention,
For example, melamine cyanurate having the following structure may be mentioned.

[0055]

[Chemical 4]

In the present invention, the blending amount of the melamine cyanurate compound is 3 to 70 parts by weight, preferably 5 to 40 parts by weight, based on 100 parts by weight of the thermoplastic resin component (A). If the amount of the melamine cyanurate compound is too small, the effect of improving the flame retardancy will not be exhibited, and if it is too large, the mechanical strength, particularly the elongation will be reduced, and the appearance when used as an electric wire will be poor.

(D) At least one selected from zinc borate, zinc stannate and zinc hydroxystannate In the flame-retardant resin composition of the present invention, if necessary, zinc borate, zinc stannate and hydroxystannic acid are added. At least one selected from the group consisting of zinc can be blended, and flame retardancy can be further improved. The use of these compounds increases the rate of shell formation during combustion,
Shell formation becomes stronger. Therefore, the flame retardancy can be dramatically improved together with the melamine cyanurate compound that generates gas from the inside during combustion, and a high degree of flame retardancy can be imparted. The zinc borate, zinc stannate, and zinc hydroxystannate used in the present invention preferably have an average particle size of 5 μm or less, more preferably 3 μm or less. Specific examples of the zinc borate that can be used in the present invention include Alkanex FRC-500 (2Z
nO / 3B ₂ O ₃ .3.5H ₂ O), FRC-600 (all are trade names, manufactured by Mizusawa Chemical Co., Ltd.) and the like. In addition, zinc stannate (ZnSnO ₃ ) and zinc hydroxystannate (ZnS
Examples of n (OH) ₆ ) include Alkanex ZS and Alkanex ZHS (both are trade names, manufactured by Mizusawa Chemical Co., Ltd.). In the present invention, the compounding amount of zinc borate, zinc stannate or zinc hydroxystannate is 0.5 to 20 parts by weight, preferably 2 to 15 parts by weight with respect to 100 parts by weight of the thermoplastic resin component (A). . If the amount is too small, the effect of improving flame retardancy will not be exhibited, and if it is too large, the mechanical strength, particularly elongation, will decrease, and the appearance when used as an electric wire will deteriorate.

The flame-retardant resin composition of the present invention contains various additives commonly used in electric wires, cables, cords, tubes, electric wire parts, sheets and the like, such as antioxidants and metal-free materials. An activator, a flame retardant (auxiliary) agent, a filler, a lubricant and the like can be appropriately added within a range that does not impair the object of the present invention. As antioxidants, amine-based antioxidants such as 4,4'-dioctyl diphenylamine, N, N'-diphenyl-p-phenylenediamine, and polymers of 2,2,4-trimethyl-1,2-dihydroquinoline 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-
Phenolic antioxidants such as (hydroxybenzyl) benzene, bis (2-methyl-4- (3-n-alkylthiopropionyloxy) -5-t-butylphenyl) sulfide, 2-mercaptobenzimidazole and zinc salts thereof, Examples thereof include sulfur-based antioxidants such as pentaerythritol-tetrakis (3-lauryl-thiopropionate). 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'-oxamidobis- (ethyl 3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate) and the like.

Further, as flame retardant (auxiliary) agents and fillers, carbon, clay, zinc oxide, tin oxide, titanium oxide, magnesium oxide, molybdenum oxide, antimony trioxide, silicone compounds, quartz, talc, calcium carbonate, carbonic acid. Examples include magnesium and white carbon. In particular, a silicone compound such as silicone rubber or silicone oil not only imparts and improves flame retardancy, but also in an electric wire / cord, an insulator (a coating layer containing the flame retardant resin composition) and a conductor. By controlling the adhesion force of the cable and imparting lubricity to the cable, it is possible to reduce external damage. Specific examples of such a silicone compound used in the present invention include "SFR-1.
Commercially available products such as "00" (trade name, manufactured by GE), "CF-9150" (trade name, manufactured by Toray Dow Silicone), and the like. When added, the silicone compound is preferably added to the thermoplastic resin component (A) in an amount of 0.
5 to 5 parts by weight are blended. If it is less than 0.5 parts by weight, it has practically no effect on flame retardancy and lubricity, and if it exceeds 5 parts by weight, the appearance of electric wires, cords and cables may be deteriorated, and extrusion molding speed may be reduced, resulting in mass productivity. May get worse. Examples of the lubricant include hydrocarbon-based, fatty acid-based, fatty acid amide-based, ester-based, alcohol-based, metal soap-based and the like.

The above-mentioned additives and other resins can be introduced into the flame-retardant resin composition of the present invention within a range that does not impair the object of the present invention, but at least the thermoplastic resin component (A) is mainly contained. Use as a resin component. Here, the term “main resin component” means that it is usually 7 in the resin component of the flame-retardant resin composition of the present invention.
It means that the thermoplastic resin component (A) occupies 0% by weight or more, preferably 85% by weight or more, and more preferably the total amount of the resin component. Here, in the thermoplastic resin component (A), the components (a), (b), (c), (d1) and / or (d2), (e), (f), and (p) are each as described above. The amount of the thermoplastic resin component (A) used is within the specified range, and the total amount of the components (a) to (f) and (p) is 100.
It becomes weight%.

The method for producing the flame-retardant resin composition of the present invention will be described below. The components (a) to (f), (p), the metal hydrate (B), and the components (g) and (h) are added and kneaded by heating. The kneading temperature is preferably 160 to 240 ° C.
The kneading conditions such as the kneading temperature and the kneading time are set to such an extent that the resin components (a) to (f) and (p) are melted and the organic peroxide acts to realize the required partial crosslinking. , Can be set appropriately. The kneading method can be satisfactorily used as long as it is a method commonly used for rubber, plastics and the like, and as the apparatus, for example, a single-screw extruder, a twin-screw extruder, a roll, a Banbury mixer or various kneaders can be used. Through this step, it is possible to obtain a flame-retardant resin composition in which each component is uniformly dispersed. It is important to pretreat the metal hydrate treated with the silane coupling agent among the mixed metal hydrates with the silane coupling agent in advance. By using a metal hydrate that has been surface-treated in advance, it is possible to add a sufficient amount of metal hydrate to ensure flame retardancy, and especially good mechanical strength and wear resistance. A flame-retardant resin composition that is hard to scratch is obtained. As another method, first, the components (a) to (f) and (p) are heated and kneaded in the first step to obtain a thermoplastic resin component (A). In the second step, the components (g), (h), and the metal hydrate (B) are added to the thermoplastic resin component (A) obtained in the first step, and the mixture is heated and kneaded. The temperature at this time is preferably 160 to 240 ° C. In this case as well, the kneading conditions such as kneading temperature and kneading time are such that the thermoplastic resin component (A) is melted and the contained organic peroxide is partially crosslinked. It can be appropriately set so as to be sufficiently used. As described above, the components (a) to (f) and (p) may be heated and kneaded in advance for microscopic dispersion, and then the components (g) and (h) may be added and kneaded by heating. Also in this case, when the surface-treated metal hydrate is used, it is necessary to finish the surface treatment before blending.

The flame-retardant resin composition of the present invention is suitable for coating and manufacturing of wiring materials used for internal and external wiring of electric / electronic devices, optical fiber cores, molded parts such as optical fiber cords. When the flame-retardant resin composition of the present invention is used as a coating material for a wiring material, it preferably comprises at least one layer of the flame-retardant resin composition of the present invention formed on the outer periphery of a conductor by extrusion coating. There is no particular limitation except that it has a coating layer. For example, as the conductor, a known arbitrary wire such as a single wire or a twisted wire of annealed copper can be used. As the conductor, in addition to the bare wire, a tin-plated conductor or a conductor having an enamel coating insulating layer may be used. The wiring material of the present invention can be produced by extrusion-coating the flame-retardant resin composition of the present invention around conductors or insulated wires using a general-purpose extrusion coating device. At this time, the temperature of the extrusion coating apparatus is preferably about 180 ° C. in the cylinder part and about 200 ° C. in the crosshead part. In the wiring material of the present invention, the thickness of the insulating layer (coating layer made of the flame-retardant resin composition of the present invention) formed around the conductor is not particularly limited, but is usually about 0.15 mm to 5 mm.

In the wiring material of the present invention, it is preferable that the flame-retardant resin composition of the present invention, which is a partially cross-linked product, is extrusion coated to form a coating layer as it is, but further improvement of heat resistance is required. For the purpose, it is possible to crosslink the coating layer after extrusion. However, this cross-linking treatment makes it difficult to reuse the coating layer as an extruded material. As a method for crosslinking, a conventional electron beam irradiation crosslinking method or a chemical crosslinking method can be adopted. In the case of electron beam crosslinking method,
The flame-retardant resin composition of the present invention is extrusion-molded to form a coating layer, which is then crosslinked by irradiation with an electron beam by a conventional method. The appropriate electron beam dose is 1-30 Mrad,
In order to efficiently crosslink, the flame-retardant resin composition constituting the coating layer, methacrylate compounds such as trimethylolpropane triacrylate, allyl compounds such as triallyl cyanurate, maleimide compounds, divinyl compounds, etc. You may mix | blend the polyfunctional compound of these as a crosslinking aid. In the case of the chemical cross-linking method, organic flame retardant resin composition is mixed with organic peroxide as a cross-linking agent, and extrusion molding is performed to form a coating layer, and then cross-linking is performed by a heat treatment by a conventional method.

The shape of the molded part of the present invention is not limited, and examples thereof include a power plug, a connector, a sleeve, a box, a tape base material, a tube and a sheet. The molded part of the present invention is molded from the flame-retardant resin composition of the present invention by a usual molding method such as injection molding. Also, sheets, tubes and the like can be extruded in the same manner as the wire coating. Further, like the electric wire, it may be crosslinked by a chemical crosslinking method or an electron beam crosslinking method. When an injection-molded product such as a wire component is obtained as the molded component of the present invention, the cylinder temperature is 220.
Injection molding can be performed at a temperature of about 230C and a head temperature of about 230C. As the injection molding device, an injection molding machine used for molding ordinary PVC resin or the like can be used for molding.

The optical fiber core wire or optical cord of the present invention can be used as a coating layer of the flame-retardant resin composition of the present invention by using a general-purpose extrusion coating device, around the optical fiber strand, or in the tensile fiber. Is produced by extrusion coating around the optical fiber core wire which is vertically attached or twisted.
At this time, the temperature of the extrusion coating device is 18
It is preferable that the temperature is 0 ° C. and the crosshead portion is about 200 ° C. The optical fiber core wire of the present invention may be used as it is without further providing a coating layer around it depending on the application. The optical fiber core wire or cord of the present invention includes, as a coating layer of the flame-retardant resin composition of the present invention, all those coated on the outer circumference of the optical fiber element wire or core wire, and particularly its structure is restricted. Not something to do. The thickness of the coating layer, the type of tensile strength fiber that is vertically attached or twisted to the optical fiber core wire,
The amount and the like vary depending on the type and application of the optical fiber cord, and can be set appropriately.

2 to 4 show structural examples of the optical fiber core wire and the cord of the present invention. FIG. 2 is a cross-sectional view of an embodiment of the optical fiber core wire of the present invention in which a coating layer 2 made of a flame-retardant resin composition is provided directly on the outer circumference of the optical fiber element wire 1.
FIG. 3 is a cross-sectional view of an embodiment of the optical fiber cord of the present invention in which a coating layer 5 is formed on the outer periphery of one optical fiber core wire 3 in which a plurality of tensile strength fibers 4 are vertically attached. FIG. 4 shows an optical fiber cord of the present invention in which a plurality of tensile strength fibers 4 are vertically attached to the outer peripheries of two optical fiber core wires 3 and 3 and a coating layer 6 is further formed on the outer perimeter thereof (optical fiber two-core cord). 2) is a cross-sectional view of one embodiment of FIG.

[0067]

The present invention will be described in more detail based on the following examples, but the invention is not intended to be limited thereto. The numbers indicate parts by weight unless otherwise specified.

Examples 1 to 72, Comparative Examples 1 to 24 Hydrogenated styrene / ethylene / propylene / styrene copolymer (SEPS) as component (a), paraffin oil as component (b), and Table 1 as component (c). ~ 11 ethylene / 1-octene copolymer having a density of 0.87 g / cm ³ (c-1), an ethylene / 1-octene copolymer having a density of 0.915 g / cm ³ (c-2), a density of 0 .926g
/ Cm ³ ethylene / hexene copolymer (c-3), density 0.913 g / cm ³ ethylene / hexene copolymer (c-4), density 0.898 g / cm ³ ethylene / hexene copolymer Table 1 as the components (c-5) and (d1)
11. The ethylene-vinyl acetate copolymer (d-1) having a vinyl acetate (VA) component content of 33% by weight, and the ethylene-vinyl acetate copolymer (d-) having a VA component content of 41% by weight.
2), an ethylene-vinyl acetate copolymer (d-3) having a VA component content of 28% by weight, and an ethylene-ethyl acrylate copolymer (d-4) having an ethyl acrylate (EA) component content of 25% by weight. ), An ethylene-vinyl acetate copolymer (d-10) having a VA component content of 70% by weight, and an ethylene / propylene copolymer rubber having an ethylene component content of 73% by weight shown in Tables 1 to 11 as the (d2) component (EPM) (d-
5), ethylene / propylene copolymer rubber (EPM) (d-6) having an ethylene component content of 52% by weight, ethylene / propylene terpolymer (EPDM) (d-7) (66) having an ethylene component content of 66% by weight, Table 1 to 1 as e) component
1 block polypropylene (e-1), random polypropylene (e-2), homopolypropylene (e-
3), atactic polypropylene (e-4), (f)
Maleic acid-modified polyethylene as a component, ethylene methyl acrylate copolymer acrylic rubber (p-1) as a component (p), ternary acrylic rubber (p-2), 2,5-dimethyl- as a component (g) 2,5-di (t-butylperoxy) -hexane, (h) component of triethylene glycol dimethacrylate, and (B) component of vinylsilane surface-treated magnesium hydroxide (B-
1), magnesium hydroxide surface-treated with fatty acid (B-
2) or untreated magnesium hydroxide (B-3) and a silane coupling agent were used, and the composition was prepared by setting the respective components to the compounding amounts shown in Tables 1 to 11.

In Examples 4, 8, 14, 34, 36 and 39, the components (a) to (f) were dry blended at room temperature and kneaded by heating with a Banbury mixer at 200 ° C. to obtain a thermoplastic resin. Ingredient (A) was prepared. Subsequently, the organic peroxide (g), the cross-linking aid (h) and the metal hydrate (B) were charged, kneaded with a Banbury mixer, and discharged to obtain a flame-retardant resin composition. The discharge temperature was 200 ° C. In Examples 19 and 20, (B) metal hydrate was placed in a blender, and the silane coupling agent was added dropwise with stirring to perform silane treatment of the metal hydrate in advance. The metal hydrate surface-treated with the silane coupling agent thus obtained and all other components were dry blended at room temperature, heated and kneaded with a Banbury mixer at 200 ° C., and discharged. A flammable resin composition was obtained. The discharge temperature was 200 ° C. In the other Examples and Comparative Examples (excluding Comparative Examples 12 and 13), all components were dry blended at room temperature, heated and kneaded using a Banbury mixer at 200 ° C., and discharged. Got The discharge temperature was 200 ° C. In Comparative Example 12, each component except the organic peroxide and the silane coupling agent was heated and kneaded with a Banbury mixer, and then the organic peroxide and the silane coupling agent were added and kneaded. In Comparative Example 13, all components except the metal hydrate were kneaded with a Banbury mixer, and then the metal hydrate was mixed, kneaded and discharged to obtain a flame-retardant resin composition.

From the obtained resin composition, by pressing,
A 1 mm sheet corresponding to each example and comparative example was prepared.
Next, a conductor (conductor diameter: 1.14 mmφ tin-plated annealed copper twisted wire structure: 30 pieces /
0.18 mmφ) is extrusion-coated with a resin composition for insulation coating that has been melted in advance, and
46, an insulated electric wire having an outer diameter of 2.74 mm corresponding to Comparative Examples 1 to 28 was manufactured. For some electric wires, a conductor (conductor diameter: 1.14 mmφ tinned annealed copper twisted wire structure: 3
0 / 0.18 mmφ) is extrusion-coated with a resin composition for insulation coating that has been melted in advance, and the corresponding outer diameter is 2.
A 1 mm insulated wire was produced. This electric wire is a sample used for abrasion resistance test 2. In addition, using a general-purpose extrusion coating device, the composition obtained was attached to the outer circumference of an optical fiber nylon core wire (3) having an outer diameter (φ) of 0.90 mm, to which tensile strength fibers (aramid fibers) (4) were attached. The optical fiber cord of the structure of FIG. 3 extruded and coated with 0.35 mm, and the light of the structure of FIG. 2 in which the composition was directly coated on the optical fiber element wire (1) of φ0.25 mm to have an outer diameter of 0.9 mm. Fiber core wires were produced (Examples 1, 8, 26, 46). In addition, Example 1
On the terminal for the power plug to which the two electric wires produced in
Using the composition of Example 17 shown in Table 3, injection molding was performed by an injection molding machine to mold a power plug. This power plug was molded at an injection temperature of 230 ° C.

Each of the obtained sheets was evaluated for tensile properties (elongation (%) and tensile strength (MPa)), heat deformation properties, and hardness, and the results are also shown in Tables 1-11. Each property was performed based on JIS K 6723, and the heat deformation test was performed at 121 ° C. Hardness is JIS K 7215
It was measured based on A type. Regarding each characteristic of the sheet, elongation is 100% or more and tensile strength is 10 MPa or more, and heat deformation is 30% or less, and hardness is 9 for those requiring more flexibility.
A value of 5A or less was passed, and those not requiring flexibility were used as reference values. The flexibility was evaluated by the test method whose schematic diagram is shown in FIG. 7. A sample (12) was prepared by cutting each insulated wire to a length of 20 cm, one end of which was fixed to a vertically standing wall (13), and the difference between the fixed position and the height of the other end lowered by its own weight. L (cm) was measured. If the height difference (L) is less than 1 cm, x is 1 cm or more and 3 c
When it is less than m, it is indicated by Δ, and when it is 3 cm or more, it is indicated by ◯. ×
Those having poor flexibility cannot be put to practical use as insulated wires. The insulated electric wire wound around the heat shock resistant self-diameter mandrel was left in a thermostatic chamber at 120 ° C. for 1 day, then taken out from the thermostatic layer and observed for cracks. Further, for the coating layer of each obtained insulated wire, tensile properties,
Abrasion resistance, horizontal burning test, vertical burning test, 60 ° slant burning test, thermal deformation rate test, whitening test (whether there is a whitening phenomenon), extrudability test, and appearance observation were performed to evaluate each characteristic and the results are shown. The results are also shown in Tables 1 to 11. Tensile property is the strength (tensile strength) of the insulator (coating layer) of each insulated wire.
(MPa) and elongation at break (%) were measured under the conditions of a marked line interval of 25 mm and a pulling speed of 50 mm / min. 100% growth
As described above, the strength needs to be 10 MPa or more. The abrasion resistance 1 was evaluated by using an electric wire having an outer diameter of 2.74 mm and using a test apparatus whose front view is shown in FIG. An insulated electric wire (7), which is cut to a length of 75 cm, is stripped of the insulating coating layers (7a) at both ends and is exposed to the conductor (7b), is fixed by a clamp (9) on a horizontal table (8), A load of 1 to 50 mm per minute (1
0) The number of blade reciprocations required until the blade (11) reciprocates (in the direction of the arrow in the figure) while applying 700 gf and the insulating coating layer is removed by abrasion and the blade contacts the conductor of the electric wire. Was measured. A front view of the blade is shown in FIG. 6. The blade (11) has an angle of 90 °.
Width of 3m due to the two surfaces (11a, 11b)
m blade portion is formed, and the radius of curvature (R) of the tip portion of the blade portion is 0.125 mm. When the number of reciprocations of the blade before the blade came into contact with the conductor of the electric wire was 1000 times or more, it was ○, when it was 500 times or more and less than 1000 times, it was △, and when it was less than 500 times, it was rejected. It is shown by x. The grades Δ and ◯ are acceptable and practically acceptable.

The abrasion resistance 2 was evaluated by using an electric wire having an outer diameter of 2.1 mm and using a test apparatus whose front view is shown in FIG.
An insulated electric wire (7), which is cut to a length of 75 cm, is stripped of the insulating coating layers (7a) at both ends and is exposed to the conductor (7b), is fixed by a clamp (9) on a horizontal table (8), 50 mm per minute over the length of 10 mm in the axial direction of the insulated wire
The blade (11) is reciprocated (in the direction of the arrow in the figure) while applying a load (10) of 700 gf at a speed of 60 times, and the insulating coating layer is removed by abrasion and the blade comes into contact with the conductor of the wire. The number of reciprocating blades required until then was measured. A front view of the blade is shown in FIG.
1) has two surfaces (11) so that the angle formed is 90 °.
a, 11b) forms a blade having a width of 3 mm, and the radius of curvature (R) of the tip of the blade is 0.125 mm.
The number of reciprocations of the blade before the blade contacted the conductor of the electric wire was 800 times or more, ◯, 400 times or more and less than 800 times was Δ, and less than 400 times was rejected. It is shown by x. Abrasion resistance 2 was evaluated as an index of abrasion resistance, and abrasion resistance 2 was evaluated as ○.
The ones have very excellent wear resistance.

The horizontal burning test is conducted according to J
A horizontal burning test specified in IS C 3005 was performed, and the one that self-erased within 30 seconds was counted as a pass, and the result was shown as the number of passes out of 10. In the 60-degree combustion test, each insulated wire was subjected to a 60 ° inclined combustion test specified in JIS C 3005, and the self-extinguishing test within 30 seconds was counted as a pass, and the result was shown as the number of passes out of 10. The vertical combustion test is based on the UL1581 vertical combustion test (U
W-1). Regarding flame retardance,
It is not necessary to pass all of the three types of flame retardant tests, and those in which all the specimens pass the horizontal burning test are considered to pass the burning test. The heat deformation rate was measured by UL1581 heat deformation test (Deformation Test) at a temperature of 121 ° C.
The load was 500 gf. The results are shown by the ratio (%) of deformation after heating to that before heating. If this value is 50% or more, it cannot be put to practical use. Whether there is a whitening phenomenon,
It was evaluated whether or not whitening occurred when each insulated wire was wound around a self-diameter mandrel. Wound 6 times, no whitening was observed, and 1 if 1 or more and 5 times or less occurred, and x if 6 or more times. Poor ones are not preferable for practical use. In the extrudability test, extruding was carried out with an extruder of 30 mmφ, and extruding was performed within the normal range of the motor load and good appearance was ○, extruding load was slightly large or appearance was slightly bad △, The case where the extrusion load was extremely large and the extrusion was difficult or impossible was evaluated as x. The grades Δ and ○ are acceptable and practically acceptable.

Regarding the appearance, the presence or absence of a change in the outer diameter of the insulated wire and the state of the surface were visually inspected, and those that were good were evaluated as ◯, the outer diameter was unstable and the surface was rough, and the surface was rough. The occurrence of bleeding and the occurrence of bleeding are indicated by x.
For the oil resistance, an oil resistance test was performed at 70 ° C. for 4 hours based on JIS 3005. The residual elongation and the residual tensile strength are 65% or more and 70% or more, respectively.

The compounds shown in Tables 1 to 16 are as follows.
I used the one. (A) Thermoplastic resin component Component (a): hydrogenated block copolymer Manufacturing company: Kuraray Product Name: Septon 4077 Type: Styrene / Ethylene / Propylene / Styrene Copolymer
Coalescing Styrene component content: 30% by weight Content of isoprene component: 70% by weight Weight average molecular weight: 320,000 Molecular weight distribution 1.23 Hydrogenation rate: 90% or more Component (b): Non-aromatic softening agent for rubber Manufacturer: Idemitsu Kosansha Product name: Diana Process Oil PW-90 Type: Paraffin oil Weight average molecular weight: 540 Aromatic component content: 0.1% or less Component (c): Single-site catalyst system ethylene / α-ole
Fin copolymer (C-1) Manufacturer: Dow Chemical Japan Product Name: Engage EG8100 Type: Ethylene / 1-octene copolymer Density: 0.870g / cm³ (C-2) Manufacturer: Dow Chemical Company Product name: Affinity FM1570 Type: Ethylene / 1-octene copolymer Density: 0.915g / cm³ (C-3) Manufacturing company: Ube Industries Product Name: Yumerit 2525F Type: ethylene-hexene copolymer Density: 0.926g / cm³ (C-4) Manufacturing company: Nippon Polychem Product Name: KF-271 Type: ethylene-hexene copolymer Density: 0.913g / cm³ (C-5) Manufacturing company: Nippon Polychem Product Name: KF-360 Type: ethylene-hexene copolymer Density: 0.898g / cm³

Component (d1) (D-1) Manufacturer: Mitsui DuPont Polychemical Product name: EV-170 Type: Ethylene / vinyl acetate copolymer VA component content: 33% by weight (D-2) Manufacturer: Mitsui DuPont Polychemical Product name: EV-40LX Type: Ethylene / vinyl acetate copolymer VA component content: 41% by weight (D-3) Manufacturer: Mitsui DuPont Polychemical Product Name: V-421 Type: Ethylene / vinyl acetate copolymer VA component content: 28% by weight (D-4) Manufacturer: Mitsui DuPont Polychemical Product name: A714 Type: Ethylene / ethyl acrylate copolymer EA component content: 25% by weight (D-10) Manufacturer: Bayer Product name: Levaprene 700HV Type: Ethylene / vinyl acetate copolymer VA component content: 70% by weight

Component (d2) (D-5) Manufacturing company: JSR Product name: EP07P Type: Ethylene / Propylene Copolymer Rubber (EPM) Ethylene component content: 73% by weight (D-6) Manufacturing company: JSR Product name: EP11 Type: Ethylene / Propylene Copolymer Rubber (EPM) Ethylene component content: 52% by weight (D-7) Manufacturing company: JSR Product name: EP57P Type: Ethylene / Propylene terpolymer (EPDM) Ethylene component content: 66% by weight

Component (e): polypropylene resin (E-1) Manufacturing company: Tokuyama Product name: PN610S Type: Block polypropylene Density: 0.9g / cm³ Melting point: 163 ° C Crystal fusion heat: 79 J / g (E-2) Manufacturer: Grand Polymer Product name: F227D Type: Random polypropylene Density: 0.9g / cm³ Melting point: 154 ° C Heat of fusion of crystals: 69 J / g (E-3) Manufacturer: Grand Polymer Product name: CJ-700 Type: Homo polypropylene Density: 0.9g / cm³ Melting point: 166 ° C Heat of fusion of crystals: 89 J / g (E-4) Manufacturing company: Ube Industries Product Name: ATF-133 Melting point: 153 ° C Heat of fusion of crystals: 34 J / g Component (f): Maleic acid-modified polyethylene Manufacturing company: Mitsui Chemicals Product Name: Admer XE070 Type: Maleic acid modified polyethylene (LLDPE) Ingredient (p): Acrylic rubber (P-1) Binary acrylic rubber Manufacturer: Mitsui DuPont Polychemical Product Name: Bay Mac DLS (P-2) ternary acrylic rubber Manufacturer: Mitsui DuPont Polychemical Product Name: Bay Mac GLS

Component (g): Organic peroxide manufacturer: NOF Corporation Trade name: Perhexa 25B Type: 2,5-dimethyl-2,5-di (t-butylperoxy) -hexane Component (h): Crosslinking aid Agent manufacturing company: Shin Nakamura Chemical Co., Ltd. Product name: NK ester 3G Type: Triethylene glycol dimethacrylate

(B) Metal hydrate (B-1) Manufacturer: Kyowa Chemical Co., Ltd. Product name: Kisuma 5LH Type: Magnesium hydroxide surface-treated with a silane coupling agent having a vinyl group at the end (B-2) Manufacturer: Kyowa Chemical Co., Ltd. Product Name: Kisuma 5B Type: Fatty Acid Treated Magnesium Hydroxide (B-3) Manufacturer: Kyowa Chemical Company Product Name: Kisuma 5 Type: Untreated Magnesium Hydroxide

Other ingredients Melamine cyanurate manufacturer: Nissan Chemical Co., Ltd. Product name: MC640 Type: Melamine cyanurate Zinc hydroxystannate Manufacturer: Mizusawa Chemical Co., Ltd. Product name: Alkanex ZHS Type: Zinc hydroxystannate silane Coupling agent TSL8350 (trade name) Manufacturing company: Toshiba Silicone Co., Ltd. Type: Silane coupling agent TSL8370 (trade name) having an epoxy group at the end Manufacturing company: Toshiba Silicone Co., Ltd. Silane coupling agent phenol having a vinyl group at the end Antioxidant manufacturing company: Ciba Geigy product name: Irganox 1010 Type: pentaerythrityl-tetrakis (3- (3,5
-Di-t-butyl-4-hydroxyphenyl) propionate) Lubricant manufacturer: Hoechst, Inc. Product name: Wax OP Type: Montanic acid saponified ester wax

[0082]

[Table 1]

[0083]

[Table 2]

[0084]

[Table 3]

[0085]

[Table 4]

[0086]

[Table 5]

[0087]

[Table 6]

[0088]

[Table 7]

[0089]

[Table 8]

[0090]

[Table 9]

[0091]

[Table 10]

[0092]

[Table 11]

[0093]

[Table 12]

[0094]

[Table 13]

[0095]

[Table 14]

[0096]

[Table 15]

[0097]

[Table 16]

As is clear from the results shown in Tables 1 to 16, the flame-retardant resin composition obtained in Examples 1 to 72 and the sheet, electric wire, optical fiber core wire and optical fiber cord using the same are required. It has good elongation and tensile strength, and has good combustion test, wear resistance test, whitening test, and heat distortion rate.
Furthermore, it has excellent extrudability with no practical problems and is excellent in flexibility. Examples 1-8, 10, 12, 13, 18-2
In 0, 22 to 25, 55 to 61, those having further excellent flame retardancy that pass the vertical flame retardancy test are obtained. In Example 17, the material contracted after molding hardly occurred, and a molded plug having a good appearance was obtained. Furthermore, the flame of the burner used in the flame retardant test specified by JIS C 3005 was applied to the power plug for 15 seconds.
Extinguishing was confirmed instantly when the flame was pulled away. On the other hand, in Comparative Examples 1 to 24, whether uniform kneading or extrusion cannot be performed,
Alternatively, there is a problem in any of elongation, tensile strength, whitening property, extrudability, flexibility, hardness, flame retardancy, wear resistance, and heat deformability, and an electric wire having all good properties has not been obtained. The compound of Comparative Example 12 obtained by adding magnesium hydroxide without pretreatment with a silane coupling agent and then adding a silane coupling agent and an organic peroxide was difficult to re-mold, and the surface of the sheet was also hard. There were many, and extrusion was impossible. In Comparative Example 13 in which vinylsilane-treated magnesium hydroxide was added after the partial crosslinking reaction was completed, the effect of improving the mechanical properties of the electric wire was not sufficiently obtained. It can be seen that the metal hydrate is not effective unless it is added before or at the same time as the partial crosslinking reaction.

[0099]

The flame-retardant resin composition of the present invention is composed of a non-halogen flame-retardant material and does not contain phosphorus, and has excellent mechanical properties, flame retardancy, heat resistance and flexibility. Moreover, no harmful heavy metal compounds elute, a large amount of smoke, and no harmful gas (corrosive gas) are generated at the time of disposal such as landfill or combustion. Further, the wiring material of the present invention is excellent in mechanical properties, flame retardancy and heat resistance, and also excellent in flexibility, and in particular, does not whiten even when bent. As described above, the wiring material of the present invention has excellent characteristics as a non-halogen flame-retardant wiring material containing no phosphorus, which can achieve both flexibility and mechanical strength. Furthermore, the coating layer of the wiring material of the present invention can be formed by using a remeltable material as the coating material while having a high heat resistance of UL105 ° C. Therefore, it is a cross-linked product which is a current coating material. This makes it possible to provide a wiring material that is more recyclable than a covered wiring material. From the above, the wiring material of the present invention is very useful as a wiring material for electric / electronic devices in consideration of environmental problems, such as a power cable. The flame-retardant resin composition of the present invention is also suitable as a coating material for such wiring materials, optical fiber core wires, optical fiber cords, etc., as a material for molded parts, and as a tube or tape material. It is something.

[Brief description of drawings]

FIG. 1 is a DSC chart of an atactic polypropylene polymer composed of a butene-1 component and a propylene component.

FIG. 2 is a cross-sectional view of an embodiment of the optical fiber core wire of the present invention in which a coating layer is provided directly on the outer circumference of an optical fiber element wire.

FIG. 3 is a cross-sectional view of an example of an optical fiber cord of the present invention in which a coating layer is formed on the outer periphery of one optical fiber core wire in which a plurality of tensile strength fibers are vertically attached.

FIG. 4 is a cross-sectional view of another embodiment of the optical fiber cord of the present invention in which a plurality of tensile strength fibers are vertically attached to the outer peripheries of two optical fiber core wires, and a coating layer is further formed on the outer peripheries thereof.

FIG. 5 is a front view of a wear resistance test apparatus.

FIG. 6 is a front view of the blade in the wear resistance test apparatus shown in FIG.

FIG. 7 is a schematic diagram showing a flexibility testing method.

[Explanation of symbols]

1 Optical fiber strand 2 coating layer 3 Optical fiber core 4 tensile strength fiber 5 coating layer 6 coating layer 7 insulated wire 7a Insulation coating layer 7b conductor 8 units 9 clamps 10 load 11 blade 11a, 11b Blade surface of blade

─────────────────────────────────────────────────── ─── Continued Front Page (51) Int.Cl. ⁷ Identification Code FI C08K 5/10 C08K 5/10 5/14 5/14 5/3477 5/3477 9/06 9/06 C08L 23/12 C08L 23 / 12 23/16 23/16 23/26 23/26 31/04 31/04 S 33/02 33/02 33/06 33/06 33/08 33/08 53/02 ZAB 53/02 ZAB 91/00 91/00 G02B 6/44 301 G02B 6/44 301A H01B 7/295 H01B 7/34 B (72) Inventor Hitoshi Yamada 4-3-1-Tatsumidai Higashi, Ichihara-shi, Chiba 215 (72) Inventor Dai Hashimoto 3-25 Tatsumidai Higashi, Ichihara-shi, Chiba (56) Reference JP-A-60-100302 (JP, A) JP-A-63-289717 (JP, A) JP-A-2-145633 (JP, A) JP-A 4-270746 (JP, A) JP 5-25331 (JP, A) JP 5-43770 (JP, A) JP 9-33770 (JP, A) JP 2001-60414 (JP, A) JP 59-6236 (JP, A) JP 6-93143 (JP, A) JP 8-176394 (JP, A) JP 8-225713 (JP, A) Kaihei 9-302156 (JP, A) JP 10-87902 (JP, A) (58) Fields investigated (Int. Cl. ⁷ , DB name) C08L 23/00 C08L 53/02

Claims (18)

(57) [Claims] 1. (a) at least two polymer blocks A whose main constituent is a vinyl aromatic compound,
A block copolymer comprising at least one polymer block B containing a conjugated diene compound as a main component, and / or a hydrogenated block copolymer obtained by hydrogenating the block copolymer in an amount of 3 to 55% by weight, (B) 0 to 40% by weight of a non-aromatic softening agent for rubber, (c) 0 to 80% by weight of ethylene / α-olefin copolymer, (d1) ethylene-vinyl acetate copolymer, ethylene- (meth). At least one kind of acrylic acid copolymer or ethylene- (meth) acrylic acid ester copolymer 5 to 80% by weight, (e) polypropylene resin 0 to 50% by weight, (f) unsaturated carboxylic acid or its derivative Modified modified polyethylene resin 0-3
0 parts by weight, and (p) 0 to 45 parts by weight of the acrylic rubber, based on 100 parts by weight of the thermoplastic resin component (A),
(G) 0.01 to 0.6 parts by weight of organic peroxide,
(H) 0.03 to 1.8 parts by weight of a (meth) acrylate-based and / or allyl-based cross-linking aid, and 50 to 300 parts by weight of a metal hydrate (B). (B) includes (i) when the metal hydrate (B) is 50 parts by weight or more and less than 100 parts by weight, the thermoplastic resin component (A) 100
50 parts by weight or more of the metal hydrate pretreated with the silane coupling agent based on parts by weight; (ii) 100 parts by weight or more of the metal hydrate (B) 300
In the case of less than or equal to parts by weight, at least half of the metal hydrate (B) is a mixture having a composition in which the metal hydrate is pretreated with a silane coupling agent, and the thermoplastic resin component (A) A flame-retardant resin composition characterized by being heated and kneaded at a melting temperature or higher. 2. (a) at least two polymer blocks A whose main constituent is a vinyl aromatic compound,
A block copolymer comprising at least one polymer block B containing a conjugated diene compound as a main component, and / or a hydrogenated block copolymer obtained by hydrogenating the block copolymer in an amount of 3 to 30% by weight, (B) 0 to 20% by weight of a non-aromatic softening agent for rubber, (c) 0 to 20% by weight of ethylene / α-olefin copolymer, (d1) ethylene-vinyl acetate copolymer, ethylene- (meth). At least one kind of acrylic acid copolymer or ethylene- (meth) acrylic acid ester copolymer 35 to 80% by weight, (e) polypropylene resin 0 to 35% by weight, (f) unsaturated carboxylic acid or its derivative Modified polyethylene resin 0
30% by weight, and (p) acrylic rubber 0 to 45% by weight
0.01 to 0.6 parts by weight of (g) organic peroxide, (h) (meth) acrylate-based and / or allyl-based cross-linking aid per 100 parts by weight of the thermoplastic resin component (A). The content of the metal hydrate (B) is from 03 to 1.8 parts by weight, and the metal hydrate (B) is contained from 50 to 300 parts by weight. When the amount is 100 parts by weight or more and less than 100 parts by weight, the thermoplastic resin component (A) 100 is used.
50 parts by weight or more of the metal hydrate pretreated with the silane coupling agent based on parts by weight; (ii) 100 parts by weight or more of the metal hydrate (B) 300
In the case of less than or equal to parts by weight, at least half of the metal hydrate (B) is a mixture having a composition in which the metal hydrate is pretreated with a silane coupling agent, and the thermoplastic resin component (A) A flame-retardant resin composition characterized by being heated and kneaded at a melting temperature or higher. 3. (a) at least two polymer blocks A whose main constituent is a vinyl aromatic compound,
A block copolymer comprising at least one polymer block B containing a conjugated diene compound as a main component, and / or a hydrogenated block copolymer obtained by hydrogenating the block copolymer in an amount of 3 to 40% by weight, (B) 0 to 40% by weight of a non-aromatic softening agent for rubber, (c) 0 to 80% by weight of ethylene / α-olefin copolymer, (d2) 5 to 50% by weight of ethylene / propylene copolymer rubber, (E) 0 to 50% by weight of polypropylene resin, and (f) modified polyethylene resin modified with unsaturated carboxylic acid or its derivative 0
To (g) organic peroxide 0.01 to 100 parts by weight of the thermoplastic resin component (A) consisting of 30 to 30% by weight.
0.6 parts by weight, (h) (meth) acrylate-based and /
Or 0.03 to 1.8 parts by weight of an allylic crosslinking aid and 50 to 300 parts by weight of a metal hydrate (B), and the metal hydrate (B) is (i) the metal. When the hydrate (B) is 50 parts by weight or more and less than 100 parts by weight, the thermoplastic resin component (A) 100
25 parts by weight or more of the metal hydrate pretreated with the silane coupling agent based on parts by weight; (ii) 100 parts by weight or more of the metal hydrate (B) 300
In the case of less than or equal to parts by weight, at least 1 of the metal hydrate (B)
/ 4 amount is a mixture having a composition which is a metal hydrate pretreated with a silane coupling agent, and is obtained by heating and kneading at a melting temperature of the thermoplastic resin component (A) or higher. Flame-retardant resin composition. 4. (a) at least two polymer blocks A whose main constituent is a vinyl aromatic compound,
A block copolymer comprising at least one polymer block B containing a conjugated diene compound as a main component, and / or a hydrogenated block copolymer obtained by hydrogenating the block copolymer in an amount of 3 to 55% by weight, (B) 0 to 40% by weight of a non-aromatic softening agent for rubber, (c) 0 to 80% by weight of ethylene / α-olefin copolymer, (d1) ethylene-vinyl acetate copolymer, ethylene- (meth). At least one type of acrylic acid copolymer or ethylene- (meth) acrylic acid ester copolymer 5 to 80% by weight, (d2) ethylene / propylene copolymer rubber 5 to 50% by weight, (e) polypropylene resin 0 Of 50 to 50% by weight, (f) 0 to 30% by weight of a modified polyethylene resin modified with an unsaturated carboxylic acid or a derivative thereof, and (p) 0 to 45% by weight of an acrylic rubber are thermoplastics. With respect to 100 parts by weight of the fat component (A), 0.01 to 0.6 parts by weight of (g) organic peroxide, (h) (meth) acrylate-based and / or allyl-based crosslinking aid 0.03 to 1. 8 parts by weight and 50 to 300 parts by weight of the metal hydrate (B), and the metal hydrate (B) is (i) 50 parts by weight or more and 100 parts by weight or more of the metal hydrate (B). If the amount is less than 100 parts by weight, the thermoplastic resin component (A) 100
50 parts by weight or more of the metal hydrate pretreated with the silane coupling agent based on parts by weight; (ii) 100 parts by weight or more of the metal hydrate (B) 300
In the case of less than or equal to parts by weight, at least half of the metal hydrate (B) is a mixture having a composition in which the metal hydrate is pretreated with a silane coupling agent, and the thermoplastic resin component (A) A flame-retardant resin composition characterized by being heated and kneaded at a melting temperature or higher. 5. (a) at least two polymer blocks A whose main constituent is a vinyl aromatic compound,
A block copolymer comprising at least one polymer block B containing a conjugated diene compound as a main component, and / or a hydrogenated block copolymer obtained by hydrogenating the block copolymer in an amount of 3 to 55% by weight, (B) 0 to 40% by weight of a non-aromatic softening agent for rubber, (c) 0 to 80% by weight of ethylene / α-olefin copolymer, (d1) ethylene-vinyl acetate copolymer, ethylene- (meth). 5-80% by weight of at least one type of acrylic acid copolymer or ethylene- (meth) acrylic acid ester copolymer, (e) melting point (T of polypropylene component measured by differential scanning calorimeter
m) is 163 ° C. or less, and the heat of fusion of crystal (ΔH
m) is 0 to 85% by weight of a polypropylene resin whose main component is an atactic polypropylene polymer having 55 J / g or less, (f) 0 to 30% by weight of a modified polyethylene resin modified with an unsaturated carboxylic acid or a derivative thereof, and (P) 0.01 to 0.6 part by weight of organic peroxide, (h) (meth) acrylate based on 100 parts by weight of the thermoplastic resin component (A) consisting of 0 to 45% by weight of acrylic rubber. And / or allylic crosslinking assistant 0.03 to
1.8 parts by weight and 50 to 300 parts by weight of the metal hydrate (B), and the metal hydrate (B) is (i) 50 parts by weight of the metal hydrate (B). Above 100 parts by weight, the thermoplastic resin component (A) 100
50 parts by weight or more of the metal hydrate pretreated with the silane coupling agent based on parts by weight; (ii) 100 parts by weight or more of the metal hydrate (B) 300
In the case of less than or equal to parts by weight, at least half of the metal hydrate (B) is a mixture having a composition in which the metal hydrate is pretreated with a silane coupling agent, and the thermoplastic resin component (A) A flame-retardant resin composition characterized by being heated and kneaded at a melting temperature or higher. 6. (a) at least two polymer blocks A whose main constituent is a vinyl aromatic compound,
A block copolymer comprising at least one polymer block B containing a conjugated diene compound as a main component, and / or a hydrogenated block copolymer obtained by hydrogenating the block copolymer in an amount of 3 to 30% by weight, (B) 0 to 20% by weight of a non-aromatic softening agent for rubber, (c) 0 to 20% by weight of ethylene / α-olefin copolymer, (d1) ethylene-vinyl acetate copolymer, ethylene- (meth). 35-80% by weight of at least one kind of acrylic acid copolymer or ethylene- (meth) acrylic acid ester copolymer, and (e) the melting point (Tm) of the polypropylene component measured by a differential scanning calorimeter is 163 ° C. or less. And the heat of crystal fusion (△
Hm) is 55 J / g or less, and polypropylene resin 0 to 35 whose main component is an atactic polypropylene polymer
% By weight, (f) 0 to 30% by weight of a modified polyethylene resin modified with an unsaturated carboxylic acid or its derivative, and (p) 0 to 45% by weight of an acrylic rubber based on 100 parts by weight of a thermoplastic resin component (A). (G) 0.01 to 0.6 parts by weight of organic peroxide, (h) (meth) acrylate-based and / or allyl-based crosslinking aid 0.03 to
1.8 parts by weight and 50 to 300 parts by weight of the metal hydrate (B), and the metal hydrate (B) is (i) 50 parts by weight of the metal hydrate (B). Above 100 parts by weight, the thermoplastic resin component (A) 100
50 parts by weight or more of the metal hydrate pretreated with the silane coupling agent based on parts by weight; (ii) 100 parts by weight or more of the metal hydrate (B) 300
In the case of less than or equal to parts by weight, at least half of the metal hydrate (B) is a mixture having a composition in which the metal hydrate is pretreated with a silane coupling agent, and the thermoplastic resin component (A) A flame-retardant resin composition characterized by being heated and kneaded at a melting temperature or higher. 7. (a) at least two polymer blocks A whose main constituent is a vinyl aromatic compound,
A block copolymer comprising at least one polymer block B containing a conjugated diene compound as a main component, and / or a hydrogenated block copolymer obtained by hydrogenating the block copolymer in an amount of 3 to 40% by weight, (B) 0 to 40% by weight of a non-aromatic softening agent for rubber, (c) 0 to 80% by weight of ethylene / α-olefin copolymer, (d2) 5 to 50% by weight of ethylene / propylene copolymer rubber, (E) The melting point (T) of the polypropylene component measured by a differential scanning calorimeter
m) is 163 ° C. or less, and the heat of fusion of crystal (ΔH
m) from 0 to 85% by weight of a polypropylene resin whose main component is an atactic polypropylene polymer having 55 J / g or less, and (f) from 0 to 30% by weight of a modified polyethylene resin modified with an unsaturated carboxylic acid or a derivative thereof. To 100 parts by weight of the thermoplastic resin component (A)
(G) 0.01 to 0.6 parts by weight of organic peroxide,
(H) 0.03 to 1.8 parts by weight of a (meth) acrylate-based and / or allyl-based cross-linking aid, and 50 to 300 parts by weight of a metal hydrate (B). (B) includes (i) when the metal hydrate (B) is 50 parts by weight or more and less than 100 parts by weight, the thermoplastic resin component (A) 100
25 parts by weight or more of the metal hydrate pretreated with the silane coupling agent based on parts by weight; (ii) 100 parts by weight or more of the metal hydrate (B) 300
In the case of less than or equal to parts by weight, at least 1 of the metal hydrate (B)
/ 4 amount is a mixture having a composition which is a metal hydrate pretreated with a silane coupling agent, and is obtained by heating and kneading at a melting temperature of the thermoplastic resin component (A) or higher. Flame-retardant resin composition. 8. (a) at least two polymer blocks A whose main constituent is a vinyl aromatic compound,
A block copolymer comprising at least one polymer block B containing a conjugated diene compound as a main component, and / or a hydrogenated block copolymer obtained by hydrogenating the block copolymer in an amount of 3 to 55% by weight, (B) 0 to 40% by weight of a non-aromatic softening agent for rubber, (c) 0 to 80% by weight of ethylene / α-olefin copolymer, (d1) ethylene-vinyl acetate copolymer, ethylene- (meth). At least one kind of acrylic acid copolymer or ethylene- (meth) acrylic acid ester copolymer 5 to 80% by weight, (d2) ethylene / propylene copolymer rubber 5 to 50% by weight, (e) differential scanning calorie Mainly composed of an atactic polypropylene polymer having a polypropylene component melting point (Tm) of 163 ° C. or less and a crystal fusion heat amount (ΔHm) of 55 J / g or less measured by a meter. Polypropylene resins 0 to
With respect to 100 parts by weight of a thermoplastic resin component (A) consisting of 85% by weight, (f) 0 to 30% by weight of a modified polyethylene resin modified with an unsaturated carboxylic acid or a derivative thereof, and (p) 0 to 45% by weight of an acrylic rubber. (G) 0.01 to 0.6 parts by weight of organic peroxide, (h) (meth) acrylate-based and / or allyl-based crosslinking aid 0.03 to
1.8 parts by weight and 50 to 300 parts by weight of the metal hydrate (B), and the metal hydrate (B) is (i) 50 parts by weight of the metal hydrate (B). Above 100 parts by weight, the thermoplastic resin component (A) 100
50 parts by weight or more of the metal hydrate pretreated with the silane coupling agent based on parts by weight; (ii) 100 parts by weight or more of the metal hydrate (B) 300
In the case of less than or equal to parts by weight, at least half of the metal hydrate (B) is a mixture having a composition in which the metal hydrate is pretreated with a silane coupling agent, and the thermoplastic resin component (A) A flame-retardant resin composition characterized by being heated and kneaded at a melting temperature or higher. 9. The cross-linking aid (h) has the general formula: (Wherein R is H or CH ₃ and n is an integer of 1 to 9), which is a (meth) acrylate-based crosslinking aid. The flame-retardant resin composition according to item 1. 10. The flame-retardant resin composition according to any one of claims 1 to 9, wherein the metal hydrate (B) is magnesium hydroxide. 11. The flame-retardant resin composition according to any one of claims 1 to 10, wherein the silane coupling agent is a silane compound having a vinyl group and / or an epoxy group at a terminal. 12. An ethylene-vinyl acetate copolymer, ethylene- (meth) acrylic acid copolymer, or ethylene-
At least one kind (d1) of the (meth) acrylic acid ester copolymer is an ethylene-vinyl acetate copolymer having a vinyl acetate component content of 25% by weight or more, 5. The flame-retardant resin composition according to 5, 6, or 8. 13. The flame-retardant material according to claim 1, which contains 3-70 parts by weight of melamine cyanurate with respect to 100 parts by weight of the thermoplastic resin component (A). Resin composition. 14. 0.5 to 20 parts by weight of at least one selected from zinc borate, zinc stannate and zinc hydroxystannate is contained with respect to 100 parts by weight of the thermoplastic resin component (A). The flame-retardant resin composition according to any one of claims 1 to 13. 15. The flame-retardant resin composition according to any one of claims 1 to 14 as a coating layer on the outside of a conductor or an optical fiber element wire or / and an optical fiber core wire. Molded article. 16. A molded part obtained by molding the flame-retardant resin composition according to any one of claims 1 to 14. 17. The flame-retardant resin composition according to claim 1, wherein (a) at least two polymer blocks A whose main component is a vinyl aromatic compound. A block copolymer comprising at least one polymer block B containing a conjugated diene compound as a main component, and / or a hydrogenated block copolymer obtained by hydrogenating the same, (b) Aromatic rubber softening agent, (c) ethylene / α-olefin copolymer,
(D1) ethylene-vinyl acetate copolymer, ethylene-
At least one type of (meth) acrylic acid copolymer or ethylene- (meth) acrylic acid ester copolymer and / or (d2) ethylene / propylene copolymer rubber, (e) polypropylene resin, (f) unsaturated Modified polyethylene resin modified with carboxylic acid or its derivative,
(P) acrylic rubber, (g) organic peroxide,
(H) A (meth) acrylate-based and / or an allyl-based crosslinking aid and a metal hydrate (B) are simultaneously heated and kneaded at a melting temperature of the resin components (a) to (f) or higher to perform a crosslinking treatment. A method for producing a flame-retardant resin composition, comprising: 18. The flame-retardant resin composition according to claim 1, wherein in the first step, (a) at least two polymers containing a vinyl aromatic compound as a main constituent component. Block A and at least one polymer block B mainly composed of a conjugated diene compound
And / or a hydrogenated block copolymer obtained by hydrogenating the same, (b) a non-aromatic softening agent for rubber, (c) an ethylene / α-olefin copolymer, (D1) At least one of ethylene-vinyl acetate copolymer, ethylene- (meth) acrylic acid copolymer, or ethylene- (meth) acrylic acid ester copolymer
Seed and / or (d2) ethylene / propylene copolymer rubber, (e) polypropylene resin, (f) modified polyethylene resin modified with unsaturated carboxylic acid or its derivative, and (p) acrylic rubber are heated and kneaded to heat. After obtaining the plastic resin component (A), in the second step, the resin component (A) and (g) organic peroxide, (h) (meth) acrylate-based and / or allyl-based crosslinking aid, and metal hydration A method for producing a flame-retardant resin composition, which comprises subjecting the material (B) to heating / kneading at a melting temperature of the thermoplastic resin component (A) or higher to carry out a crosslinking treatment.