JP2001316537A - Flame-retardant resin composition and molded part using the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a flame-retardant resin composition coping with environmental problems, and to provide a wiring material and other molded articles which use the same. SOLUTION: This flame-retardant resin composition comprising a prescribed amount of (A) a thermoplastic resin component comprising (a) a vinyl aromatic compound-conjugated diene block copolymer, (b) a softening agent, (c) ethylene-α- olefin copolymer, (d1) at least one kind of ethylene-vinyl acetate copolymer, ethylene-(meth)acrylic acid copolymer, and an ethylene-(meth)acrylate copolymer, (e) polypropylene resin, (f) a modified polyethylene resin, and (p) an acrylic rubber, and (g) a prescribed amount of an organic peroxide, (h) a prescribed amount of a cross-linking auxiliary, and (B) a prescribed amount of a metal hydroxide, wherein the metal hydroxide is pretreated with a prescribed amount of silane coupling agent, characterized by being heated and kneaded at a temperature above the melting temperature of (A) the thermoplastic resin component.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a flame-retardant resin composition having excellent mechanical properties, flexibility, heat resistance and flame retardancy without the need for a crosslinking facility at the time of processing, and the composition. And an optical fiber cord and other molded parts. More specifically, the present invention relates to an insulated wire, an electric cable, an electric cord, an optical fiber core, an optical fiber cord or the like used for the internal or external wiring of electric / electronic equipment, or a mold for a power cord or the like. Regarding flame-retardant resin compositions suitable for materials, tubes and sheets, and wiring materials and other molded parts using the same, heat resistance, flexibility, and trauma resistance are not required after processing, without requiring special equipment such as crosslinking equipment. It is a flame-retardant resin composition with excellent resistance, especially when disposing of landfills, burning, etc., without elution of heavy metal compounds, large amounts of smoke and harmful gases, and suitable for recycling after use, BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a flame-retardant resin composition that addresses environmental issues, and a wiring member and other molded parts using the same.

[0002]

2. Description of the Related Art Insulated electric wires, cables, cords, optical fiber cords, optical fiber cords and the like used for internal and external wiring of electric and electronic equipment are provided with flame retardancy, heat resistance, mechanical properties (for example, tensile strength). Characteristics, wear resistance). For this reason, as coating materials used for these wiring materials, polyvinyl chloride (PVC) compounds and polyolefin compounds containing a halogen-based flame retardant containing bromine atoms and chlorine atoms in the molecule are mainly used. Was. However, if these are discarded without proper treatment and landfilled, the plasticizer and heavy metal stabilizer contained in the coating material will elute or if they burn, they will be included in the coating material. In some cases, harmful gases are generated from the halogen compounds, and this problem has been discussed in recent years. For this reason, wiring materials coated with non-halogen flame-retardant materials that are not likely to elute harmful plasticizers or heavy metals, which are feared to affect the environment, or generate halogen-based gas, are being studied. . Non-halogen flame retardant materials exhibit flame retardancy by blending a flame retardant containing no halogen into the resin.
-Ethylene copolymers such as butene copolymer, ethylene-propylene copolymer, ethylene-vinyl acetate copolymer, ethylene-ethyl acrylate copolymer, ethylene-propylene-diene terpolymer, etc. Materials containing a large amount of metal hydrates, such as aluminum hydroxide and magnesium hydroxide, are used as wiring materials for wiring materials.

[0003] Standards such as flame retardancy, heat resistance, and mechanical properties (for example, tensile properties and wear resistance) required for wiring materials of electric and electronic devices are specified by UL, JIS, and the like. In particular, regarding the flame retardancy, the test method changes according to the required level (the use). So in fact,
What is necessary is just to have the flame retardancy according to the required level at least. For example, UL1581 (Reference Standard for Wires, Cables and Flexible Cords (Reference St.)
andard for ElectricWire
s, Cables and Flexible Cor
ds)) vertical combustion test (Vertical)
Frame Test) (VW-1), JIS C
Flame retardancy which passes a horizontal test and a tilt test specified in 3005 (rubber / plastic insulated wire test method). Among them, in the past, when imparting a high degree of flame retardancy to pass non-halogen flame retardant materials such as VW-1 and a tilt test, ethylene / 1-butene copolymer, ethylene / propylene copolymer, Ethylene-vinyl acetate copolymer, ethylene-ethyl acrylate copolymer, 100 parts by weight of a resin component of an ethylene-based copolymer such as ethylene-propylene-diene terpolymer,
It is necessary to mix 150 to 200 parts by weight of a metal hydrate as 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 amount of the metal hydrate (for example, about 120 parts by weight of the metal hydrate as a flame retardant with respect to 100 parts by weight of the resin) and compounding red phosphorus. Has been taken. By the way, at present,
Wiring materials made of polyvinyl chloride compounds or polyolefin compounds containing halogen-based flame retardants used in electronic equipment are used as coating materials. It is used for printing on the surface or coloring several kinds of colors. However, non-halogen-coated materials containing metal hydrate and red phosphorus to achieve both high flame retardancy and mechanical properties can be printed on top of it or colored in any color because of the red phosphorus coloring. Therefore, there is a problem that a wiring member that can easily distinguish types and connection portions cannot be obtained. In addition, the release of phosphorus from flame-retardant materials containing phosphorus after disposal also has an impact on the environment,
For example, pollution of water resources due to eutrophication has become a problem.

[0004] In some cases, wiring materials used in electric and electronic devices are required to have a heat resistance of 80 ° C to 105 ° C, and more preferably 125 ° C under continuous use. In such a case, for the purpose of imparting high heat resistance to the wiring material, a method of crosslinking the coating material by an electron beam crosslinking method, a chemical crosslinking method, or the like has been adopted. However, although the crosslinked wiring material has improved heat resistance of the coating material, it cannot be re-melted, so it is difficult to reuse it.
It has been pointed out that recyclability is poor. For example, when recovering the metal used for the conductor, the coating material often has to be burned, etc., and avoids the environmental problems associated with conventional halogen or phosphorus-containing coating materials. Can not do. Further, special equipment such as an electron beam crosslinking equipment and a chemical crosslinking equipment must be prepared, which leads to an increase in equipment costs and electric wire costs, which is a factor of reducing versatility.

On the other hand, as a method of realizing heat resistance of about 80 ° C. to 105 ° C. with a wiring material that does not perform such crosslinking, there is a method using a resin having a high melting point such as a polypropylene resin. However, although such a resin has good heat resistance, it has poor flexibility, and when the wiring material covering the resin is bent, a phenomenon that the surface is whitened is observed.
At present, this whitening phenomenon is not seen in wiring materials coated with polyvinyl chloride compounds used in electric and electronic equipment. On the other hand, in a wiring material coated with a non-halogen flame-retardant material containing a large amount of metal hydrate, the whitening phenomenon is severe regardless of the presence or absence of crosslinking. So, as wiring material,
There is still a need for improvements in using non-halogen flame retardant materials that are whitened by current bending. Since the working temperature of the wiring material coated with the 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, a heat deformation test and a heat aging test in an atmosphere of 121 ° C are performed for heat resistance of UL80 ° C, and a heat deformation test and a heat aging test in a atmosphere of 136 ° C are performed for heat resistance of UL105 ° C. Is required, the non-halogen flame-retardant material to be substituted is 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 there is a need for the development of recyclable and remoldable molded parts having heat resistance, flexibility, and flame retardancy.

[0006] Wiring for electronic equipment used for electronic equipment is required to pass a particularly strict vertical flame retardant standard (UL1581 VW-1) stipulated by the UL standard. However, even if a high melting point resin such as the above-mentioned polypropylene resin is used and a large amount of metal hydrate is blended, it is difficult to greatly improve the flame retardancy. Does not fit. In addition, the electric wire covering material used for home electric appliances and the like is required to have mechanical properties stipulated by, for example, UL standards.
% And tensile strength of 10.3 MPa or more are required. Particularly in the case of power cords, they are bundled and shipped, so that more excellent flexibility is required. On the other hand, similarly to tubes, electric wire parts, sheets, and molded parts such as power plugs other than electric wires, similar heat deformation characteristics, flame retardancy characteristics, mechanical strength, and flexibility are required. In particular, sheets and tubes for protection and connection of electric wires and for building materials are required to have surface flexibility and not to be damaged, 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-mentioned problems and has excellent flame retardancy, heat resistance, and mechanical properties. An object of the present invention is to provide a flame-retardant resin composition and a molded article which do not generate a large amount of smoke and harmful gas and which respond to recent environmental problems. Furthermore, the present invention satisfies these characteristics and can be reused because the coating material can be re-melted. It is an object of the present invention to provide a flame-retardant resin composition and a wiring member, an optical fiber cord, an optical fiber cord, and other molded parts using the same.

[0008]

The above object has been attained by the following invention. (1) (a) Consisting of at least two polymer blocks A whose main component is a vinyl aromatic compound and at least one polymer block B whose main component is a conjugated diene compound. A block copolymer and / or 3 to 55% by weight of a hydrogenated block copolymer obtained by hydrogenating the same, (b) a softener for non-aromatic rubber 0
0 to 40% by weight, (c) an ethylene / α-olefin copolymer 0 to 80% by weight, (d1) an ethylene-vinyl acetate copolymer, an ethylene- (meth) acrylic acid copolymer, or ethylene- (meth) 5 to 80% by weight of at least one type of acrylate copolymer, (e) 0 to 50% by weight of a polypropylene resin, (f) 0 to 30% by weight of a modified polyethylene resin modified with an unsaturated carboxylic acid or a derivative thereof,
And (g) 0.01 to 0.6 parts by weight of an organic peroxide, and (h) (meth) acrylate based on 100 parts by weight of a thermoplastic resin component (A) comprising 0 to 45% by weight of an acrylic rubber. And / or allylic crosslinking aid in an amount of 0.03 to 1.8 parts by weight, and metal hydrate (B) 50
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 a metal hydrate pretreated with a silane coupling agent with respect to parts by weight; (ii) 100 parts by weight or more of 300 parts by weight of the metal hydrate (B)
When the amount is not more than part by weight, at least half of the metal hydrate (B) is a mixture having a composition of a metal hydrate 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 component is a vinyl aromatic compound
And / or at least one polymer block B whose main component is a conjugated diene compound, and / or a hydrogenated block copolymer obtained by hydrogenating the block copolymer 3 to 30% by weight %, (B) 0 to 20% by weight of a softener for a non-aromatic rubber, (c) 0 to 20% by weight of an ethylene / α-olefin copolymer, (d1) an ethylene-vinyl acetate copolymer, ethylene- ( (Meth) acrylic acid copolymer or at least one kind of ethylene- (meth) acrylic acid ester copolymer, 35 to 80% by weight, (e) polypropylene resin 0 to 35% by weight, (f) unsaturated carboxylic acid or the same. Modified polyethylene resin modified with derivative 0
(G) 0.01 to 0.6 parts by weight of an organic peroxide, based on 100 parts by weight of a thermoplastic resin component (A) comprising (p) an acrylic rubber of 0 to 45% by weight, ) (Meth) acrylate and / or allylic crosslinking aids in an amount of 0.03 to 1.8 parts by weight, and 50 to 300 parts by weight of metal hydrate (B). And (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 a metal hydrate pretreated with a silane coupling agent with respect to parts by weight; (ii) 100 parts by weight or more of 300 parts by weight of the metal hydrate (B)
When the amount is not more than part by weight, at least half of the metal hydrate (B) is a mixture having a composition of a metal hydrate 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 component is a vinyl aromatic compound
And a block copolymer comprising at least one polymer block B whose main component is a conjugated diene compound, 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 softener for non-aromatic rubber, (c) 0 to 80% by weight of ethylene / α-olefin copolymer, (d2) 5 to 50% by weight of ethylene / propylene copolymer rubber % Of (e) a polypropylene resin, and (f) 0 to 30% by weight of a modified polyethylene resin modified with an unsaturated carboxylic acid or a derivative thereof.
(G) Organic peroxide 0.01 to 100 parts by weight
0.6 parts by weight, (h) (meth) acrylate type and / or
Or 0.03 to 1.8 parts by weight of an allylic crosslinking assistant and 50 to 300 parts by weight of a metal hydrate (B), wherein the metal hydrate (B) comprises: When the hydrate (B) is at least 50 parts by weight and less than 100 parts by weight, the thermoplastic resin component (A) 100
25 parts by weight or more of metal hydrate pretreated with a silane coupling agent based on parts by weight; (ii) 100 parts by weight or more of 300 parts by weight of metal hydrate (B)
When the amount is at most 1 part by weight, at least 1 part of the metal hydrate (B)
/ 4 is a mixture having a composition of a metal hydrate pretreated with a silane coupling agent, wherein the mixture is heated and kneaded 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 whose main component is a conjugated diene compound, and / or a hydrogenated block copolymer obtained by hydrogenating the block copolymer 3 to 55% by weight %, (B) 0 to 40% by weight of a softener for a non-aromatic rubber, (c) 0 to 80% by weight of an ethylene / α-olefin copolymer, (d1) an ethylene-vinyl acetate copolymer, ethylene- ( 5 to 80% by weight of at least one of a (meth) acrylic acid copolymer or an ethylene- (meth) acrylate copolymer, (d2) 5 to 50% by weight of an ethylene / propylene copolymer rubber, (e)
A thermoplastic resin component (A) 100 comprising 0 to 50% by weight of a polypropylene resin, (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 an organic peroxide, (h) 0.03 to 1.8 parts by weight of a (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 a metal hydrate pretreated with a silane coupling agent with respect to parts by weight; (ii) 100 parts by weight or more of 300 parts by weight of the metal hydrate (B)
When the amount is not more than part by weight, at least half of the metal hydrate (B) is a mixture having a composition of a metal hydrate 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 component is a vinyl aromatic compound
And at least one polymer block B whose main component is a conjugated diene compound, and / or 3 to 55% by weight of a hydrogenated block copolymer obtained by hydrogenating the block copolymer. %, (B) 0 to 40% by weight of a softener for a non-aromatic rubber, (c) 0 to 80% by weight of an ethylene / α-olefin copolymer, (d1) an ethylene-vinyl acetate copolymer, ethylene- ( (Meth) acrylic acid copolymer or ethylene- (meth) acrylate copolymer at least one of 5 to 80% by weight, 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 a polypropylene resin having an atactic polypropylene polymer whose main component is 55 J / g or less.
% By weight, 100 parts by weight of a thermoplastic resin component (A) comprising (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 an organic peroxide, and (h) 0.03 to
1.8 parts by weight and 50 to 300 parts by weight of the metal hydrate (B), wherein the metal hydrate (B) is: (i) the metal hydrate (B) is 50 parts by weight When it is less than 100 parts by weight, the thermoplastic resin component (A) 100
50 parts by weight or more of a metal hydrate pretreated with a silane coupling agent with respect to parts by weight; (ii) 100 parts by weight or more of 300 parts by weight of the metal hydrate (B)
When the amount is not more than part by weight, at least half of the metal hydrate (B) is a mixture having a composition of a metal hydrate 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 component is a vinyl aromatic compound
And / or at least one polymer block B whose main component is a conjugated diene compound, and / or a hydrogenated block copolymer obtained by hydrogenating the block copolymer 3 to 30% by weight %, (B) 0 to 20% by weight of a softener for non-aromatic rubber, (c) 0 to 20% by weight of an ethylene / α-olefin copolymer, (d1) an ethylene-vinyl acetate copolymer, ethylene- ( 35 to 80% by weight of at least one of a (meth) acrylic acid copolymer or an ethylene- (meth) acrylate 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 a polypropylene resin 0 to 35 containing an atactic polypropylene polymer whose main component is 55 J / g or less.
% By weight, 100 parts by weight of a thermoplastic resin component (A) comprising (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 an organic peroxide, and (h) 0.03 to
1.8 parts by weight and 50 to 300 parts by weight of the metal hydrate (B), wherein the metal hydrate (B) is: (i) the metal hydrate (B) is 50 parts by weight When it is less than 100 parts by weight, the thermoplastic resin component (A) 100
50 parts by weight or more of a metal hydrate pretreated with a silane coupling agent with respect to parts by weight; (ii) 100 parts by weight or more of 300 parts by weight of the metal hydrate (B)
When the amount is not more than part by weight, at least half of the metal hydrate (B) is a mixture having a composition of a metal hydrate 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 component is a vinyl aromatic compound
And / or a block copolymer comprising at least one polymer block B whose main component is a conjugated diene compound, and / or a hydrogenated block copolymer obtained by hydrogenating the block copolymer 3 to 40% by weight %, (B) 0 to 40% by weight of softener for non-aromatic 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 crystal fusion (ΔH
from 0 to 85% by weight of a polypropylene resin having an atactic polypropylene polymer having m) of 55 J / g or less, and from 0 to 30% by weight of (f) a modified polyethylene resin modified with an unsaturated carboxylic acid or a derivative thereof. 100 parts by weight of the thermoplastic resin component (A)
(G) 0.01 to 0.6 parts by weight of an organic peroxide,
(H) 0.03 to 1.8 parts by weight of a (meth) acrylate and / or allylic crosslinking aid and 50 to 300 parts by weight of a metal hydrate (B); (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)
25 parts by weight or more of metal hydrate pretreated with a silane coupling agent based on parts by weight; (ii) 100 parts by weight or more of 300 parts by weight of metal hydrate (B)
When the amount is at most 1 part by weight, at least 1 part of the metal hydrate (B)
/ 4 is a mixture having a composition of a metal hydrate pretreated with a silane coupling agent, wherein the mixture is heated and kneaded 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 component is a vinyl aromatic compound
And at least one polymer block B whose main component is a conjugated diene compound, and / or a hydrogenated block copolymer obtained by hydrogenating the block copolymer 3 to 55% by weight %, (B) 0 to 40% by weight of a softener for a non-aromatic rubber, (c) 0 to 80% by weight of an ethylene / α-olefin copolymer, (d1) an ethylene-vinyl acetate copolymer, ethylene- ( 5 to 80% by weight of at least one of a (meth) acrylic acid copolymer or an ethylene- (meth) acrylate copolymer, (d2) 5 to 50% by weight of an ethylene / propylene copolymer rubber, (e)
Polypropylene resin containing an atactic polypropylene polymer having a melting point (Tm) of 163 ° C. or less and a heat of crystal fusion (ΔHm) of 55 J / g or less as a main component, which is measured by a differential scanning calorimeter. ~
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, based on 100 parts by weight of a thermoplastic resin component (A) (G) 0.01 to 0.6 parts by weight of an organic peroxide, and (h) 0.03 to 0.03 parts by weight of a (meth) acrylate and / or allylic crosslinking aid.
1.8 parts by weight and 50 to 300 parts by weight of the metal hydrate (B), wherein the metal hydrate (B) is: (i) the metal hydrate (B) is 50 parts by weight When it is less than 100 parts by weight, the thermoplastic resin component (A) 100
50 parts by weight or more of a metal hydrate pretreated with a silane coupling agent with respect to parts by weight; (ii) 100 parts by weight or more of 300 parts by weight of the metal hydrate (B)
When the amount is not more than part by weight, at least half of the metal hydrate (B) is a mixture having a composition of a metal hydrate 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 assistant (h) has a general formula

[0016]

Embedded image

(Where R is H or CH ₃ , n
Is an integer of 1 to 9. (1) to (8), which are (meth) acrylate-based crosslinking assistants represented by the following formulas:
Item 10. The flame-retardant resin composition according to any one of Items 1 to 4. (10) The flame-retardant resin composition according to any one of (1) to (9), wherein the metal hydrate (B) is magnesium hydroxide. (11) The flame-retardant resin composition according to any one of (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) 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). The flame-retardant resin composition according to the item [1]. (13) The difficulties described in any one of (1) to (12), wherein 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) At least one selected from zinc borate, zinc stannate and zinc hydroxystannate is used in an amount of 0.5 to 2 based on 100 parts by weight of the thermoplastic resin component (A).
The flame-retardant resin composition according to any one of (1) to (13), which contains 0 parts by weight. (15) The flame-retardant resin composition according to any one of (1) to (14) is provided as a coating layer on the outside of a conductor or an optical fiber or / and an optical fiber core. Molded articles. (16) A molded part obtained by molding the flame-retardant resin composition according to any one of (1) to (14).

(17) Any one of the above items (1) to (14)
In the flame-retardant resin composition according to the above item, (a) at least two polymer blocks A whose main component is a vinyl aromatic compound and at least one polymer block A whose main component is a conjugated diene compound And / or a hydrogenated block copolymer obtained by hydrogenating the same, (b) a softener for non-aromatic rubber, (c) ethylene · α -Olefin copolymer, (d1) ethylene-vinyl acetate copolymer, ethylene- (meth) acrylic acid copolymer, or ethylene-
At least one kind of (meth) acrylate copolymer and / or (d2) an ethylene / propylene copolymer rubber, (e) a polypropylene resin, (f) a modified polyethylene resin modified with an unsaturated carboxylic acid or a derivative thereof, (P) acrylic rubber, (g) organic peroxide,
(H) A (meth) acrylate-based and / or allyl-based cross-linking assistant and a metal hydrate (B) are simultaneously heated and kneaded at a temperature equal to or higher than the melting temperature of the resin components (a) to (f) to perform a cross-linking treatment. A method for producing a flame-retardant resin composition.

(18) Any one of the above items (1) to (14)
The flame-retardant resin composition according to the above item, wherein, as the first step, (a) at least two polymer blocks A mainly composed of a vinyl aromatic compound and a conjugated diene compound and A block copolymer comprising at least one polymer block B, and / or a hydrogenated block copolymer obtained by hydrogenating the same.
(B) softener for non-aromatic rubber, (c) ethylene-α-
At least one of an olefin copolymer, (d1) an ethylene-vinyl acetate copolymer, an ethylene- (meth) acrylic acid copolymer, or an ethylene- (meth) acrylate copolymer and / or (d2) ethylene・ Propylene copolymer rubber, (e) polypropylene resin, (f)
After heating and kneading a modified polyethylene resin modified with an unsaturated carboxylic acid or a derivative thereof and (p) an acrylic rubber to obtain a thermoplastic resin component (A), in a second step, the resin components (A) and (g) are mixed. ) Organic peroxides, (h)
(Meth) acrylate and / or allylic crosslinking aid and metal hydrate (B) are heated and kneaded at a temperature equal to or higher than the melting temperature of the thermoplastic resin component (A) to perform a crosslinking treatment. A method for producing a flame-retardant resin composition.

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

[0022]

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the present invention will be described in detail. 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) is defined as (a) at least two polymer blocks A whose main components are a vinyl aromatic compound, and a conjugated diene compound as a component. A block copolymer composed mainly of at least one polymer block B, and / or a hydrogenated block copolymer obtained by hydrogenating the same, (b) a softener for non-aromatic rubber, c) an ethylene / α-olefin copolymer,
(D1) ethylene-vinyl acetate copolymer, ethylene-
(Meth) acrylic acid copolymer or at least one ethylene- (meth) acrylate copolymer and / or (d2) ethylene / propylene copolymer rubber, (e) polypropylene resin, (f) unsaturated A modified polyethylene resin modified with a carboxylic acid or a derivative thereof,
And (p) an acrylic rubber.

Component (a) Block Copolymer Component (a) of the present invention comprises at least two polymer blocks A mainly composed of a vinyl aromatic compound.
And a block copolymer comprising at least one polymer block B whose main component is a conjugated diene compound, a block copolymer obtained by hydrogenating the block copolymer, or a mixture thereof. BA, BAB
-A, a vinyl aromatic compound-conjugated diene compound block copolymer having a structure such as ABABA, or a hydrogenated product thereof. The above (hydrogenated) block copolymer (hereinafter, the (hydrogenated) block copolymer means a block copolymer and / or a hydrogenated block copolymer) is obtained by adding a vinyl aromatic compound to 5 to 60 parts. % By weight, preferably 20 to 50% by weight. The polymer block A whose main component is a vinyl aromatic compound preferably consists of only the vinyl aromatic compound or more than 50% by weight, preferably 7% by weight.
0% by weight or more of a vinyl aromatic compound and a (hydrogenated) conjugated diene compound (hereinafter, the (hydrogenated) conjugated diene compound means a conjugated diene compound and / or a hydrogenated conjugated diene compound. ). The polymer block B whose main component is a (hydrogenated) conjugated diene compound preferably consists of only the (hydrogenated) conjugated diene compound or comprises more than 50% by weight, preferably 70% by weight %
This is a copolymer block of the above (hydrogenated) conjugated diene compound and a vinyl aromatic compound. In each of the polymer block A whose main component is a vinyl aromatic compound and the polymer block B whose main component is a (hydrogenated) conjugated diene compound, the vinyl aromatic compound in the molecular chain is used. The distribution of repeating units derived from a group III compound or a (hydrogenated) conjugated diene compound may be random, tapered (in which the monomer component increases or decreases along the molecular chain), partially block-like, or any combination thereof. May be. In the case where there are two or more polymer blocks A mainly composed of a vinyl aromatic compound or a polymer block B mainly composed of a (hydrogenated) conjugated diene compound,
Each may have the same structure or different structures.

(Hydrogenated) As the vinyl aromatic compound constituting the block copolymer, one or more kinds are selected from, for example, styrene, α-methylstyrene, vinyltoluene, p-tert-butylstyrene and the like. Of which styrene is preferred. Further, as the conjugated diene compound, for example, one or more kinds are selected from butadiene, isoprene, 1,3-pentadiene, 2,3-dimethyl-1,3-butadiene and the like.
Isoprene and combinations thereof are preferred. Polymer block B whose main component is a conjugated diene compound
Can be arbitrarily selected. For example, a polybutadiene block preferably has a 1,2-microstructure of 20 to 50%, particularly 25 to 45%, and preferably has at least 90% of a butadiene-based aliphatic double bond hydrogenated. In the polyisoprene block, 70 to 1 of the isoprene compound
00% by weight has a 1,4-microstructure and at least 90% of 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 still more preferably 100,000. To 550,000, particularly preferably in the range of 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 either radial or any combination of these.

Many methods have been proposed for producing these (hydrogenated) block copolymers. Typical methods include, for example, the method described in Japanese Patent Publication No. 40-23798. It can be obtained by subjecting a lithium catalyst or Ziegler-type catalyst to block polymerization in an inert solvent. Further, for example, a hydrogenated block copolymer can be obtained by hydrogenating the block copolymer obtained by the above method in an inert solvent in the presence of a hydrogenation catalyst. 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. Can be. In the present invention, a particularly preferred (hydrogenated) block copolymer is a polymer block A containing styrene as a main component, and a polymer block A containing isoprene as a main component and
0-100% by weight have a 1,4-microstructure and at least 90% of the aliphatic double bonds based on the isoprene
Is a hydrogenated block copolymer having a weight average molecular weight of 50,000 to 550,000 and a polymer block B obtained by hydrogenation. More preferably, 90 to 100% by weight of isoprene is the above 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 amount of the component (a) is less than 3% by weight, not only the strength and elongation are significantly reduced, but also the bleeding of the component (b) is generated, the heat deformation property is significantly reduced, and the heat resistance property is also reduced. If the content is more than 55% by weight, not only the extrudability is significantly reduced, but also the flame retardancy, heat shock properties, etc. are significantly reduced. When the ethylene-propylene copolymer rubber of the component (d2) is used, the amount of the component (a) is 3 to 40% by weight in the thermoplastic resin component (A). When using an ethylene-propylene copolymer rubber, in order to suppress the bleeding of the softener for 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, etc., while maintaining the vertical flame retardancy, which is high flame retardancy in the wiring material, the range of the component (a) is 3% of the resin component (A).
It is preferably about 30% by weight.

Component (b) Softener 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 softener can be used. The mineral oil softener used for rubber is a mixture of an aromatic ring, a naphthene ring, and a paraffin chain in which the number of carbon atoms in the paraffin chain accounts for 50% or more of the total number of carbon atoms. Those having 30 to 40% of naphthenic ring carbons are called naphthenics, and those having 30% or more aromatic carbons are called aromatics. The mineral oil-based rubber softener used as the component (b) of the present invention is a paraffin-based or naphthene-based softener in the above category. The use of an aromatic softening agent is not preferred because its use makes the component (a) soluble and inhibits the cross-linking reaction, so that the physical properties of the obtained composition cannot be improved. As the component (b), a paraffin-based component is preferable, and a paraffin-based component having less aromatic ring components is particularly preferable. The properties of these softeners for non-aromatic rubbers 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
What shows 70-300 degreeC is preferable. The compounding 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 reduced, but also the flame retardancy and the heat deformability are greatly reduced. When the ethylene-propylene copolymer rubber of the component (d2) is used, the extrudability is significantly reduced.
In this case, in order to improve the extrudability, the component (b) is preferably at least 5% by weight, more preferably at least 10% by weight. Even in the system to which the ethylene-propylene copolymer rubber is added, when the blending amount of the polypropylene is large, the polypropylene does not participate in the crosslinking at the time of kneading and crosslinking, and furthermore, causes a decrease in the molecular weight and acts as a fluidized bed. (B) Even without the component, it is possible to process without impairing the extrudability. In order to maintain strength, heat deformation characteristics, extrusion characteristics, etc., while maintaining vertical flame retardancy, which is high flame retardancy in wiring materials, the range of component (b) is 0 to 0 in resin component (A). Preferably it is 20% by weight. Part of the component (b) may be added after heat treatment in the presence of an organic peroxide, but may cause bleed-out. 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. 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 them, an ethylene / α-olefin copolymer synthesized in the presence of a single-site catalyst is preferable. The density of the ethylene / α-olefin copolymer (c) is 0.94
0 g / cm ³ or less, more preferably 0.93 / cm ³ or less.
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. If the density increases, it becomes difficult to highly fill the metal hydrate, and a problem arises in that the flexibility of the resin composition and the wiring member coated with the resin composition is reduced. Although there is no particular lower limit on the density, the lower limit is usually about 0.850 g / cm ³ . The ethylene / α-olefin copolymer (c) includes a melt flow index (AS
TMD-1238) is preferably 0.5 to 30 g / 10 min.

The ethylene / α-olefin copolymer in the present invention includes those synthesized in the presence of a single-site catalyst and ordinary linear low-density polyethylene and ultra-low-density polyethylene. A compound synthesized in the presence of a catalyst is preferable.
A known method described in, for example, JP-A-622-622 can be used. The single-site catalyst has a single polymerization active site and has a high polymerization activity, and is also called a metallocene catalyst or a Kaminsky catalyst, and is an ethylene / α-olefin copolymer synthesized using this catalyst. Is characterized by a narrow molecular weight distribution and 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, and the like, it is necessary to use a high level of metal hydrate to prevent non-halogen. When used as a fuel material (coating material for wiring material), there is an advantage that deterioration of mechanical properties due to highly filled metal hydrate can be reduced. On the other hand, when using an ethylene / α-olefin copolymer synthesized using a single-site catalyst, the melt viscosity increases and the melt tension decreases as compared with the case where a normal ethylene / α-olefin copolymer is used. This causes a problem in molding workability. In this regard, long chain branching is introduced using an asymmetric catalyst as a single-site catalyst (Constrained Geometry Ca.
TAC, or two peaks are created in the molecular weight distribution by connecting two polymerization tanks during synthesis (Advanced Performed).
Some of them have improved moldability due to the use of an anterior polymer.

As the ethylene / α-olefin copolymer (c) synthesized in the presence of a single-site catalyst used in the present invention, those having improved moldability are preferred. Dow Che
"AFFINITY" and "ENGAG"
"E" (trade name) is marketed by Exxon Chemical Company as "EXACT" (trade name), and "Umerit" (trade name) is marketed by Ube Industries.

The compounding amount of the component (c) is 0 to 80% by weight, preferably 0 to 60% by weight in the thermoplastic resin component (A).
%, More preferably 0 to 40% by weight. If the compounding amount is too large, not only the flame retardancy properties are reduced, but also the heat deformation properties are reduced. The component (c) is not an essential component in the present invention, but has a function of improving strength. In particular, in the case of wires requiring high strength or wires having very high wear resistance, it is better to add a large amount of the component (c). By introducing the component (c), particularly high wear resistance and strength can be maintained. Especially the density is 0.89
Above, more preferably 0.90 or more, even more preferably 0.910 or more when introducing an ethylene-α-olefin copolymer synthesized in the presence of a single-site catalyst,
High wear resistance and very high strength are obtained. Further, by adding a large amount of this component, oil resistance can be greatly improved. This is presumably because the introduction of the component (c) increases the crosslink density of the polymer portion. By introducing the component (c) as much as 40% by weight or more, the soft component is reduced, and the flexibility of the composition and the electric wire becomes poor. In particular, when used as a base material together with the component (d2), Even if, for example, 200 parts by weight or more of magnesium hydroxide is added to 100 parts by weight of the base material, high wear resistance and strength can be maintained, high flame retardancy, and strength and wear resistance are obtained. It is very useful for required materials and electric wires. Ethylene synthesized in the presence of a single-site catalyst having a density of 0.900 or more, more preferably 0.910 or more.
When a large amount of the α-olefin copolymer is introduced, high oil resistance can be obtained. In order to maintain vertical flame retardancy, which is high flame retardancy 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 of ethylene-vinyl acetate copolymer, ethylene- (meth) acrylic acid copolymer, and ethylene- (meth) acrylate copolymer is used as the component (d1) in the present invention. Are ethylene-vinyl acetate copolymer, ethylene- (meth) acrylic acid copolymer, ethylene- (meth) acrylate copolymer (for example, ethylene-butyl acrylate copolymer, ethylene-ethyl acrylate copolymer) Coalescence, ethylene-methyl acrylate copolymer, ethylene-methyl methacrylate copolymer)
At least one of the following is used. Of these, it is preferable to use an ethylene-vinyl acetate copolymer in order to further improve the flame retardancy. In order to further improve the flame retardancy, the content of a copolymer component other than ethylene is 23% by weight.
Or more, more preferably 25% by weight.
It is more preferably at least 28% by weight. For example, in the case of an ethylene-vinyl acetate copolymer, vinyl acetate (V
A) It is preferable that the component content is 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) is 5 to 80% by weight, preferably 15 to 65% by weight in the thermoplastic resin component (A). When the amount of the component (d1) is less than 5% by weight, the flame retardancy is reduced. In order to ensure the vertical flame retardancy of the wiring material, the amount of the component (d1) is set to 35% by weight or more in the thermoplastic resin component (A). If the content is more than 80% by weight, the heat deformation properties, heat resistance properties, and extrusion properties are significantly reduced.

Component (d2) Ethylene-propylene copolymer rubber Ethylene-propylene copolymer rubber (EPM) used as the 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, the excellent flexibility and elongation, which are the objects of the present invention, are impaired. EPM may be used alone or in combination of two or more. Ethylene-
The ethylene content in the propylene copolymer rubber is 85 to 85.
40% by weight is suitable. Preferably 80 to 45% by weight
And more preferably 75 to 50% by weight. When the content of the ethylene component is too small, the flexibility of the obtained resin composition is insufficient, and when it is too large, the mechanical strength is reduced. The Mooney viscosity and M _{L1 + 4} (100 ° C.) of the ethylene-propylene copolymer rubber are preferably from 10 to 120, more preferably from 40 to 100. Mooney viscosity is 10
If it is less than 3, the obtained elastomer composition may have poor rubber elasticity. Further, when the amount exceeds 120, molding processability may be deteriorated, and particularly, the appearance of a molded product is deteriorated. The weight average molecular weight of the ethylene-propylene copolymer rubber used is 50,000 to 1,000,000.
0, more preferably 70,000 to 500,000.
Is preferable. If the weight average molecular weight is less than 50,000, the resulting composition may have poor rubber elasticity. Further, if the weight average molecular weight exceeds 1,000,000, the moldability is deteriorated, and the appearance of a molded product may be particularly deteriorated. The blending amount of the ethylene-propylene copolymer rubber is from 5 to 50 in the thermoplastic resin component (A).
%, Preferably 15 to 40% by weight.
If the component (d2) is less than 5% by weight, elongation, flexibility,
Filler acceptance decreases. If the amount is too large, the mechanical strength is reduced. In the flame-retardant resin composition of the present invention, at least one of the component (d1) and / or the component (d2) is used, and each may be used alone, or a mixture of both may be used. . When mixed and used, the component (d1) in the thermoplastic resin component (A) is 5%.
Preferably, the content of the component (d2) is 5 to 50% by weight.

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

The melting point (Tm) of the polypropylene resin as the component (e) of the present invention is 1 as measured by a differential scanning calorimeter.
63 ° C. or less and the heat of crystal fusion (ΔHm) is 55
An atactic polypropylene polymer having J / g or less may be contained as a main component. Here "the main component"
The term preferably means that the component (e) is contained in an amount of 50% by weight or more. Here, the method of measuring the melting point (Tm) and the heat of crystal fusion (ΔHm) in the present invention will be described with reference to FIG. In the present invention, a differential scanning calorimeter for atactic polypropylene polymer (hereinafter abbreviated as DSC)
The measurement is carried out under a normal condition under a nitrogen atmosphere at a heating rate of 10 ° C./min. When the atactic polypropylene polymer is a homopolymer, one large endothermic peak is observed as the temperature increases. When the atactic polypropylene polymer is a copolymer of a propylene component and another olefin component, two or more endothermic peaks are observed. The DSC chart shown in FIG. 1 is for an atactic polypropylene polymer comprising a butene-1 component and a propylene component, but has two large endothermic peaks. In FIG. 1, the lower temperature peak is butene-
The endothermic peak due to one component and the higher temperature peak are the endothermic peaks due to the propylene component.
T2 indicates the peak end 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 a straight line such that the caloric value becomes constant from the portion D where the caloric value-temperature curve after the endothermic level becomes lower toward the lower temperature, that is, the base. Draw the line. The point at which the base line intersects with the curve extended from the endothermic curve having a peak at temperature T2
And From the area enclosed by the baseline and the endothermic curve having a peak at the temperature T2 (and an extension thereof), the heat of crystal fusion (ΔHm) of the propylene component can be determined. (Note that A is a level portion of a calorific value-temperature curve for an endothermic peak attributable to the butene-1 component. The point where the extended curve intersects is shown as C.) In the case of the homopolymer, since there is one peak, the area surrounded by the endothermic curve and the baseline is the heat of crystal fusion (ΔHm).

Examples of the atactic polypropylene polymer that can be used in the present invention include amorphous polypropylene and copolymers of propylene with other α-olefins. In the case of amorphous polypropylene, a resin produced as a by-product during the production of a crystalline polypropylene resin may be used, or it may be produced from a raw material. Further, a copolymer of propylene and another 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 the raw material monomer in the presence of hydrogen 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.
3 ° C. or less and a heat of crystal fusion (ΔHm) of 55
J / g or less can be used. Preferably, a copolymer having a melting point of 160 ° C. or less and a heat of crystal fusion (ΔHm) of 40 J / g or less is preferred. As typical monomers copolymerized with propylene,
Butene-1. Commercial products of this atactic polypropylene polymer include ATF-132, ATF
-133 (all trade names, manufactured by Ube Industries) can be used.

The polypropylene resin of 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 heat kneading. The polypropylene resin blended in (A) before the heat kneading is then heated and kneaded,
(G) Due to the presence of the component, it is thermally decomposed and appropriately reduced in molecular weight. As the polypropylene resin to be compounded before heat kneading, MFR (ASTM-D-1238, L condition, 230
C) is preferably 0.1 to 25 g / 10 min, more preferably 0.1 to 10 g / 10 min, and still more preferably 0.1 to 10 g / 10 min.
の も の 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 be deteriorated.
If the amount 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 the heat kneading may be any resin that meets the conditions at the time of extrusion for forming the coating layer, and preferably has an MFR of 5 to 200 g / 10 min, more preferably 8 to 150 g / 10 min. , More preferably 10
の も の 100 g / 10 min. When blended after heat kneading, if the MFR of the polypropylene resin is less than 5 g / 10 minutes, the moldability of the obtained resin composition may be degraded, and if the MFR exceeds 200 g / 10 minutes, the resulting resin composition Rubber elasticity may deteriorate.

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

In order to maintain strength, heat deformation characteristics, extrusion characteristics, etc., while maintaining the vertical flame retardancy, which is high flame retardancy, in the wiring material, the range of component (e) is component (A).
The content 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) is as follows in the thermoplastic resin component (A).
The content is preferably 0 to 30% by weight, but when flexibility is not required, 0 to 50% by weight can be used. By adding 30% by weight or more of the component (e), the flexibility becomes poor. However, even if the component (a) or the component (b) is extremely reduced, the extrusion processability can be maintained,
By adding a large amount of the component (c), it is possible to obtain a material and an electric wire having excellent workability, oil resistance, high strength, and high wear resistance. Also in this case, when using atactic polypropylene, it is 0 to 85% by weight, preferably 5 to 80% by weight in the thermoplastic resin component (A).
% By weight, more preferably 5 to 50% by weight. The component (e) has an effect of improving the extrudability of the resin composition while securing the heat resistance, but when high heat resistance is not required, the component (e) can be omitted. When the component (e) is not used,
The amount of the component (b) is adjusted so that the resin composition as a whole has good extrudability. In addition, UL105 ° C rated electric wire heating deformability of wiring materials (136 ° C)
It is particularly preferable to use at least one of a homopolypropylene and an ethylene / propylene block copolymer as the polypropylene resin in order to maintain the following. As the blending amount, it is preferable to add at least one of homopolypropylene and ethylene / propylene block copolymer in the thermoplastic resin component (A) in an amount of 15% by weight or more.

(F) Component Polyolefin resin modified with unsaturated carboxylic acid or derivative thereof Polyolefin resin modified with unsaturated carboxylic acid or derivative thereof includes linear polyethylene, ultra low density polyethylene, high density polyethylene and the like. Polyolefin resins are mentioned. 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). As the unsaturated carboxylic acid used for the modification, for example, maleic acid, itaconic acid, fumaric acid and the like,
Derivatives of unsaturated carboxylic acids include maleic monoester, maleic diester, maleic anhydride, itaconic monoester, itaconic diester, itaconic anhydride, fumaric monoester, fumaric diester,
And fumaric anhydride. The polyolefin can be modified, for example, by heating and kneading the polyolefin and an 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. The addition of the polyolefin resin modified with the unsaturated carboxylic acid or its derivative has the effect of increasing the elongation of the obtained resin composition and maintaining the strength, and also allows the volume resistivity to be kept high. Modification of this polyolefin resin with an unsaturated carboxylic acid or a derivative thereof also has an effect of alleviating a decrease in mechanical properties due to a metal hydrate and an effect of preventing whitening of electric wires. (F) The compounding quantity of a component is 0 to 30 weight% in (A). The component (f) is not necessarily an essential component, but is preferably added to add the above effects. If the amount of the component (f) is too large, not only the flame retardancy is significantly reduced, but also the extrusion characteristics of the electric wire may be significantly reduced.

(P) Component Acrylic rubber Acrylic rubber is a monomer component containing ethyl acrylate,
It is a rubber elastic body obtained by copolymerizing a small amount of an alkyl acrylate such as butyl acrylate and a monomer having various functional groups, and the copolymerizable monomers include methyl vinyl ketone, acrylic acid, acrylonitrile, and butadiene Etc. can be used as appropriate. 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, in which case, a binary copolymer with ethylene or an unsaturated hydrocarbon having a carboxyl group in the side chain such as acrylic acid. A terpolymer obtained by copolymerizing as a monomer or adding 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 names, all manufactured by Mitsui / Dupont Polychemicals) can be used. By adding acrylic rubber, the flame retardancy of a molded article such as a composition or an electric wire is greatly improved. Further, by blending the acrylic rubber, the peeling property is improved without stretching the coating material like a beard when peeling. In the present invention, the acrylic rubber is 45% by weight or less, preferably 3 to 45% by weight of the resin component.
It can be used in proportions by weight. If the amount of the acrylic rubber exceeds 45% by weight, not only does the processability and extrusion processability during compounding remarkably deteriorate, but also the elongation also remarkably decreases.

Use of a tertiary copolymer acrylic rubber of ethylene, an alkyl acrylate, and an unsaturated hydrocarbon having a carboxyl group in a side chain is preferable as the acrylic rubber because flame retardancy is improved. The amount is 3
It is preferable to add 3% by weight or more of the original acrylic rubber,
It is more preferably at least 5% by weight, further preferably at least 10% by weight. The tertiary acrylic rubber tends to increase the extrusion load, and is preferably controlled 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 foamed layer is formed inside during combustion, and a carbonized layer is formed on the surface, which is considered to be due to the tertiary acrylic rubber. Is further improved. Further, by using a tertiary copolymer acrylic rubber of ethylene, an alkyl acrylate and an unsaturated hydrocarbon having a carboxyl group in the side chain, the rubber becomes strong and the mechanical strength is improved.

(G) Component Organic peroxide The organic peroxide used in the present invention includes, for example, dicumyl peroxide, di-tert-butyl peroxide, 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, 2,5-dimethyl-2,5-di-, in terms of odor, coloring and scorch stability. (Tert-Butylperoxy) hexyne-3 is most preferred. The compounding amount of the organic peroxide (e) depends on the thermoplastic resin component (A).
It is in the range of 0.01 to 0.6 part by weight, preferably 0.03 to 0.5 part by weight, per 100 parts by weight. By selecting organic peroxide within this range,
Since the cross-linking does not proceed too much, a partially cross-linked composition having excellent extrudability without blemishes can be obtained.

Component (h) (Meth) acrylate and / or allylic crosslinking aid In the production of the flame-retardant resin composition of the present invention or the thermoplastic resin component (A) used in the same, an organic peroxide is used. Forms a partially crosslinked structure between the vinyl aromatic thermoplastic elastomer and the ethylene-α-olefin copolymer via a crosslinking aid. In this case, as a crosslinking aid, a general formula

[0045]

Embedded image

(Where R is H or CH ₃ , n
Is an integer of 1 to 9. )). Here, the (meth) acrylate-based crosslinking assistant refers to an acrylate-based and methacrylate-based crosslinking assistant. 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 them, (meth) acrylate-based crosslinking assistants 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, has a peroxide solubilizing effect, and acts as a peroxide dispersing aid, so that This is most preferable because a crosslinking effect at the time of kneading is uniform and effective, and a partially crosslinked thermoplastic resin having a balance between hardness and rubber elasticity can be obtained. By using such a compound, neither insufficient crosslinking nor excessive crosslinking occurs, and a uniform and efficient partial crosslinking reaction can be expected at the time of heating and kneading. The amount of the crosslinking aid used in the present invention is based on 100 parts by weight of the thermoplastic resin component (A).
The range is preferably from 0.03 to 1.8 parts by weight, more preferably from 0.05 to 1.6 parts by weight. By selecting the crosslinking assistant within this range, a partially crosslinked structure having a low crosslinking density can be obtained without excessively progressing crosslinking, and a composition having excellent extrusion properties can be obtained without occurrence of bumps. It is preferable that the compounding amount of the crosslinking aid is about 1.5 to 4.0 times the amount of the organic peroxide to be added by weight ratio.

(B) Metal Hydrate The metal hydrate used in the present invention is not particularly limited. Examples thereof include aluminum hydroxide, magnesium hydroxide, aluminum silicate hydrate, magnesium silicate hydrate, and basic hydrate. Compounds having a hydroxyl group or water of crystallization such as magnesium carbonate and hydrotalcite can be used alone or in combination of two or more. Of these metal hydrates, aluminum hydroxide and magnesium hydroxide are preferred. It is necessary that the metal hydrate be at least partially treated with a silane coupling agent, but the metal water treated with another surface treatment agent such as an untreated metal hydrate or a fatty acid that has not been surface-treated. Japanese products can be appropriately used in combination.

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

The surface-treated magnesium hydroxide which can be used in the present invention includes those having no surface treatment (commercially available products such as Kisuma 5 (trade name, manufactured by Kyowa Chemical Co., Ltd.)), stearic acid, and the like. Those surface-treated with a fatty acid such as oleic acid (Kisuma 5A (trade name, manufactured by Kyowa Chemical Co., Ltd.), etc.), those treated with a phosphate ester, and the like, which are surface-treated with the silane coupling agent;
Alternatively, there is a commercially available magnesium hydroxide surface-treated with a silane coupling agent (Kisuma 5LH, Kisuma 5PH (both trade names, manufactured by Kyowa Chemical Co., Ltd.)). In addition, in addition to the above, a silane coupling having a functional group such as a vinyl group or an epoxy group at the end of magnesium hydroxide or aluminum hydroxide, the surface of which is partially pre-treated with a fatty acid or a phosphate ester in advance. Metal hydrates and the like that have been surface-treated with an agent can also be used.

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

The amount of the metal hydrate is based on 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, 50 parts by weight or more based on 100 parts by weight of the thermoplastic resin component (A); When the amount of the metal hydrate is 100 parts by weight or more, at least half of the metal hydrate is pretreated with a silane coupling agent, so that the strength does not decrease even when a large amount of the metal hydrate is added. Can be blended with the filler. When the component (d2) is used without using the component (d1), the blending amount of the metal hydrate is also 50 to 300 parts by weight based on 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 based on 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, at least 1/4 of the metal hydrate is pretreated with a silane coupling agent to obtain a flexible flame-retardant resin composition. it can.

When a general polyolefin resin such as a polyethylene resin or a polypropylene resin is used as a base resin, and a large amount of a metal hydrate is added to satisfy the required flame retardancy, the mechanical strength is reduced. Very large.
In contrast, the thermoplastic resin component (A) in the present invention
Is excellent in filler receptivity because the crosslink density is low and the resin components are in a partially crosslinked state via the component (h).
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 a metal hydrate treated with a silane coupling agent is blended, the base resin of the component (A) and the component (B) via the silane coupling agent
Since the metal hydrate has an interaction, a decrease in mechanical strength is suppressed to a minimum, whitening does not easily occur when the metal hydrate is bent, and characteristics satisfactory as a coating material of a wiring material, a molded part, and the like can be obtained.

The details of the reaction mechanism during heating and kneading of the resin composition of the present invention are not yet clear, but are considered as follows. That is, the thermoplastic resin component (A) in the present invention, when heated and kneaded, in the presence of the component (g),
Via component (h), component (a), component (c), (d1)
The component and / or component (d2) and component (p) are crosslinked. On the other hand, when component (e) is present, (g)
The melt viscosity of the resin composition can be appropriately adjusted by appropriately reducing the molecular weight by the action of the component, 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 the component (g), and can be referred to as partial crosslinking since the crosslinking point is smaller than that of ordinary crosslinking. The degree of crosslinking of the flame-retardant resin composition can be represented by the gel fraction and the dynamic elastic modulus of the thermoplastic resin component (A) as a standard. 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 extracting it in boiling xylene using a Soxhlet extractor for 10 hours. The dynamic elastic modulus can be represented by a 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 to 45% by weight in terms of storage modulus.
⁵ is a ~10 ⁷ Pa. When the thermoplastic resin component (A) is filled with a metal hydrate, a specific amount of the metal hydrate treated with a silane coupling agent is blended simultaneously with the component (g) and the component (h). As long as it is possible to mix a large amount of metal hydrate without impairing the extrusion processability at the time of molding, while having high flame retardancy and flexibility, while having heat resistance, and mechanical properties, It is possible to obtain a flame-retardant resin composition which can be re-extruded after use and can be recycled. The details of the mechanism by which the metal hydrate treated with the silane coupling agent acts are not yet clear, but are considered as follows. That is, the silane coupling agent bonded to the surface of the metal hydrate by treating with the silane coupling agent binds one of the alkoxy groups to the metal hydrate and removes the vinyl or epoxy group present at the other end. The first various reactive sites are bonded to the vinyl aromatic thermoplastic elastomer of the component (a) and the uncrosslinked portions of the components (c), (d1), (d2) and (p). As a result, a large amount of metal hydrate can be compounded without impairing the extrusion moldability, the adhesion between the resin and the metal hydrate is strengthened, and the mechanical strength and wear resistance are good. A flame-retardant resin composition that is resistant to damage is obtained.

(C) Melamine Cyanurate Compound The melamine cyanurate compound used in the present invention preferably has a small 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 still more preferably 5 μm or less. Further, a melamine cyanurate compound which has been subjected to a surface treatment from the viewpoint of dispersibility is preferably used. As the melamine cyanurate compound that can be used in the present invention,
For example, there are MCA-0 and MCA-1 (both trade names, manufactured by Mitsubishi Chemical Corporation) and those marketed by Chemie Linz GmbH. 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 trade names, manufactured by Nissan Chemical Industries, Ltd.). As a melamine cyanurate compound that can be used in the present invention,
For example, melamine cyanurate having the following structure may be mentioned.

[0055]

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In the present invention, the compounding 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 is not exhibited.

(D) at least one selected from zinc borate, zinc stannate and zinc hydroxy stannate, if necessary, the flame retardant resin composition of the present invention may contain zinc borate, zinc stannate and hydroxy stannate. At least one selected from the group consisting of zinc can be blended, and the flame retardancy can be further improved. The use of these compounds increases the rate of shell formation during combustion,
Shell formation becomes stronger. Therefore, together with the melamine cyanurate compound that generates gas from the inside during combustion, the flame retardancy can be dramatically improved, and a high degree of flame retardancy can be provided. The average particle diameter of zinc borate, zinc stannate and zinc hydroxystannate used in the present invention is preferably 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, for example, Alcanex FRC-500 (2Z
_{nO / 3B 2 O 3 · 3.5H} 2 O), FRC-600 ( all trade names, manufactured by Mizusawa Chemical Co., Ltd.), and the like. Further, zinc stannate (ZnSnO ₃ ), 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 amount of zinc borate, zinc stannate or zinc hydroxystannate is 0.5 to 20 parts by weight, preferably 2 to 15 parts by weight, based on 100 parts by weight of the thermoplastic resin component (A). . If the amount is too small, the effect of improving the flame retardancy will not be exhibited, and if it is too large, the mechanical strength, particularly elongation, will be reduced, and the appearance of the electric wire will be poor.

The flame-retardant resin composition of the present invention contains various additives generally used in electric wires, cables, cords, tubes, electric wire parts, sheets and the like, for example, antioxidants, metal additives. An activator, a flame retardant (auxiliary) agent, a filler, a lubricant and the like can be appropriately compounded within a range that does not impair the purpose of the present invention. As antioxidants, amine antioxidants such as polymers of 4,4'-dioctyl diphenylamine, N, N'-diphenyl-p-phenylenediamine, and 2,2,4-trimethyl-1,2-dihydroquinoline 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-tert-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, And 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, 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 a flame retardant (auxiliary) agent and a filler, carbon, clay, zinc oxide, tin oxide, titanium oxide, magnesium oxide, molybdenum oxide, antimony trioxide, silicone compound, quartz, talc, calcium carbonate, carbonate Magnesium, white carbon and the like. In particular, silicone compounds such as silicone rubber and silicone oil not only impart and improve flame retardancy, but also provide an insulator (a coating layer containing the flame-retardant resin composition) and a conductor for electric wires and cords. By controlling the adhesion force of the cable and imparting lubricity to the cable, there is an effect of reducing external damage. Specific examples of the silicone compound used in the present invention include “SFR-1
And commercial products such as "00" (trade name, manufactured by GE) and "CF-9150" (trade name, manufactured by Dow Silicone Toray). When added, the silicone compound is preferably added in an amount of 0.1 to 100 parts by weight of the thermoplastic resin component (A).
5 to 5 parts by weight are blended. If the amount is less than 0.5 part by weight, there is substantially no effect on flame retardancy and lubricity. May be worse. Examples of the lubricant include hydrocarbons, fatty acids, fatty acid amides, esters, alcohols, and metallic soaps.

The above-mentioned additives and other resins can be introduced into the flame-retardant resin composition of the present invention as long as the object of the present invention is not impaired. At least the thermoplastic resin component (A) is mainly used. Resin component. Here, the term “main resin component” refers to the resin component of the flame-retardant resin composition of the present invention, which is usually 7
It means that the thermoplastic resin component (A) accounts for 0% by weight or more, preferably 85% by weight or more, and more preferably the entire 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 thermoplastic resin component (A) has an amount of use within the specified range, and the total amount of the components (a) to (f) and (p) is 100.
% By weight.

Hereinafter, a method for producing the flame-retardant resin composition of the present invention will be described. Components (a) to (f), (p), metal hydrate (B), and components (g) and (h) are added and kneaded with heat. 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 necessary partial crosslinking. Can be set as appropriate. As a kneading method, any method commonly used for rubber, plastics and the like can be used satisfactorily, and examples of the apparatus include a single-screw extruder, a twin-screw extruder, a roll, a Banbury mixer, and various kneaders. By this step, a flame-retardant resin composition in which each component is uniformly dispersed can be obtained. It is important that the metal hydrate treated with the silane coupling agent among the metal hydrates to be blended is previously treated with the silane coupling agent. By using a metal hydrate that has been subjected to a surface treatment in advance, it is possible to mix a sufficient amount of the metal hydrate to ensure flame retardancy, and it has particularly good mechanical strength and abrasion resistance. Thus, a flame-retardant resin composition that is hardly damaged can be obtained. As another method, first, the components (a) to (f) and (p) are heated and kneaded in a first step to obtain a thermoplastic resin component (A). In the second step, the components (g) and (h) and the metal hydrate (B) are added to the thermoplastic resin component (A) obtained in the first step, followed by heating and kneading. The temperature at this time is preferably 160 to 240 ° C., and also in this case, the kneading conditions such as the kneading temperature and the kneading time are such that the thermoplastic resin component (A) is melted and the contained organic peroxide is partially crosslinked. It can be set appropriately so as to be sufficiently used. In this way, the components (a) to (f) and (p) may be heated and kneaded in advance to cause micro-dispersion, and then the components (g) and (h) may be added and heated and kneaded. Also in this case, when using a metal hydrate surface-treated, 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 molded parts such as wiring materials used for internal and external wiring of electric and electronic equipment, optical fiber cores, optical fiber cords and the like. When the flame-retardant resin composition of the present invention is used as a covering material for a wiring material, the resin composition 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 other than having a coating layer. For example, any known conductor such as a soft copper single wire or a stranded wire can be used as the conductor. In addition to the bare wire, a tin-plated conductor or a conductor having an enamel-coated insulating layer may be used as the conductor. The wiring member of the present invention can be produced by extrusion-coating the flame-retardant resin composition of the present invention around conductors and insulated wires using a general-purpose extrusion coating device. The temperature of the extrusion coating apparatus at this time is preferably about 180 ° C. in the cylinder section and about 200 ° C. in the crosshead section. In the wiring member 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 crosslinked product, is extrusion-coated to form a coating layer as it is, but it is also necessary to further improve heat resistance. It is also possible to crosslink the coating layer after extrusion for the purpose of. However, when this crosslinking treatment is performed, it is difficult to reuse the coating layer as an extruded material. As a method for performing crosslinking, an electron beam irradiation crosslinking method or a chemical crosslinking method according to a conventional method can be employed. In the case of the electron beam crosslinking method,
The flame-retardant resin composition of the present invention is extruded to form a coating layer, and then irradiated with an electron beam in a conventional manner to perform crosslinking. The dose of the electron beam is suitably 1 to 30 Mrad,
In order to efficiently perform crosslinking, the flame-retardant resin composition constituting the coating layer includes a methacrylate compound such as trimethylolpropane triacrylate, an allyl compound such as triallyl cyanurate, a maleimide compound, and a divinyl compound. May be blended as a crosslinking aid. In the case of the chemical crosslinking method, the flame retardant resin composition is blended with an organic peroxide as a crosslinking agent, extruded to form a coating layer, and then subjected to crosslinking by a conventional heat treatment.

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, a tube, a sheet and the like. 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. Sheets and tubes can also be extruded in the same manner as for covering electric wires. Further, similarly to the electric wire, the crosslinking may be performed by a chemical crosslinking method or an electron beam crosslinking method. In addition, when obtaining an injection molded product such as an electric wire component as the molded component of the present invention, the cylinder temperature 220
Injection molding can be performed at a temperature of about 230C and a head temperature of about 230C. As an injection molding apparatus, molding can be performed by using an injection molding machine used for molding ordinary PVC resin or the like.

The optical fiber core wire or the optical cord of the present invention can be formed by using a general-purpose extrusion coating apparatus, using the flame-retardant resin composition of the present invention as a coating layer, around an optical fiber, or a tensile strength fiber. Is extruded around a stranded or twisted optical fiber core.
At this time, the temperature of the extrusion coating apparatus was 18
It is preferable that the temperature is 0 ° C. and about 200 ° C. in the crosshead portion. The optical fiber core wire of the present invention is used as it is without providing a coating layer further around depending on the application. In addition, the optical fiber core wire or cord of the present invention includes all those coated with the flame retardant resin composition of the present invention as a coating layer on the outer periphery of the optical fiber wire or core wire, and particularly restricts its structure. It does not do. The thickness of the coating layer, the type of tensile strength fiber to be vertically laid or twisted on the optical fiber core,
The amount and the like differ depending on the type and use of the optical fiber cord, and can be appropriately set.

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

[0067]

EXAMPLES Hereinafter, the present invention will be described in more detail with reference to Examples, but the present invention is not limited thereto. In addition, numerals show a weight part unless there is particular description.

Examples 1 to 72, Comparative Examples 1 to 24 Hydrogenated styrene / ethylene / propylene / styrene copolymer (SEPS) as the component (a), paraffin oil as the component (b), and Table 1 as the component (c) The ethylene / 1-octene copolymer having a density of 0.87 g / cm ³ (c-1), the ethylene / 1-octene copolymer having a density of 0.915 g / cm ³ (c-2), and 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 (C-5), Table 1 as the component (d1)
11, an ethylene-vinyl acetate copolymer (d-1) having a vinyl acetate (VA) component content of 33% by weight, and an 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 as listed 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) having an ethylene component content of 66% by weight, e) Tables 1-1 as components
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), tertiary acrylic rubber (p-2) as component (p), 2,5-dimethyl- as component (g) 2,5-di (t-butylperoxy) -hexane, triethylene glycol dimethacrylate as the component (h), and magnesium hydroxide (B-
1) Magnesium hydroxide (B-
2) Alternatively, using untreated magnesium hydroxide (B-3) and a silane coupling agent, the components were prepared in the amounts shown in Tables 1 to 11 to prepare compositions.

In Examples 4, 8, 14, 34, 36 and 39, the components (a) to (f) were dry-blended at room temperature and heated and kneaded at 200 ° C. using a Banbury mixer to obtain a thermoplastic resin. Component (A) was prepared. Subsequently, the organic peroxide (g), the crosslinking 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, the metal hydrate was previously subjected to silane treatment by placing the metal hydrate (B) in a blender and dropping a silane coupling agent with stirring. The metal hydrate surface-treated with the silane coupling agent thus obtained and all other components are dry-blended at room temperature, heated and kneaded at 200 ° C. using a Banbury mixer, discharged, and discharged. A flammable resin composition was obtained. The discharge temperature was 200 ° C. In the other Examples and Comparative Examples (except Comparative Examples 12 and 13), all the components were dry-blended at room temperature, heated and kneaded at 200 ° C. using a Banbury mixer, discharged, and discharged. I got The discharge temperature was 200 ° C. In Comparative Example 12, components other than the organic peroxide and the silane coupling agent were heated and kneaded with a Banbury mixer, and then the organic peroxide and the silane coupling agent were charged 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,
1 mm sheets corresponding to the respective examples and comparative examples were prepared.
Next, a conductor (conductor diameter: 1.14 mmφ tinned soft copper stranded wire, composed of 30 wires /
0.18 mmφ), and extrusion-coated with a resin composition for insulating coating previously melted,
46, an insulated 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 soft copper stranded wire, composition: 3
0 / 0.18 mmφ), extrusion-coated with a resin composition for insulating coating previously melted, and a corresponding outer diameter of 2.
1 mm insulated wires were manufactured. This electric wire is a sample used for the wear resistance test 2. Further, using a general-purpose extrusion coating apparatus, the obtained composition was coated on the outer periphery of an optical fiber nylon core wire (3) having an outer diameter (φ) of 0.90 mm and a tensile strength fiber (aramid fiber) (4). An optical fiber cord having the structure of FIG. 3 extruded and coated at 0.35 mm, and a light having the structure of FIG. 2 having an outer diameter of 0.9 mm by directly coating the composition on an optical fiber (1) having a diameter of 0.25 mm. Fiber cores were produced (Examples 1, 8, 26, 46). Example 1
On the power plug terminal that connects the two wires made in
Using the composition of Example 17 described in Table 3, injection molding was performed by an injection molding machine to form a power plug. This power plug was molded at an injection temperature of 230 ° C.

For each of the obtained sheets, tensile properties (elongation (%) and tensile strength (MPa)), heat deformation properties, and hardness were evaluated. The results are shown in Tables 1 to 11. Each characteristic was performed based on JIS K 6723, and the heating deformation test was performed at 121 ° C. Hardness is JIS K 7215
Measured based on A type. For each property of the sheet, elongation was 100% or more, tensile strength 10MPa or more was accepted, deformation of heating was accepted 30% or less, and hardness was 9 for those requiring more flexibility.
5A or less was accepted, and those that did not require flexibility were used as reference values. The flexibility was evaluated by the test method shown schematically in FIG. Each insulated wire was cut to a length of 20 cm to obtain a sample (12), one end of which was fixed to a vertically upright 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, then x, 1 cm or more, 3 c
When the length is less than m, the result is indicated by △, and when the length is 3 cm or more, the result is indicated by ○. ×
Is inferior in flexibility and cannot be put to practical use as an insulated wire. Heat shock resistance After leaving the insulated wire wound around a mandrel having a self-diameter in a thermostat at 120 ° C. for one day, it was taken out of the thermostatic layer, and the presence or absence of cracks was observed. In addition, for the coating layer of each obtained insulated wire, tensile properties,
Abrasion resistance, horizontal burn test, vertical burn test, 60 ° tilt burn test, heating deformation test, whitening test (presence or absence of whitening phenomenon), extrusion test, appearance observation are performed, and each characteristic is evaluated. The results are shown in Tables 1 to 11. The tensile properties are 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 mark interval of 25 mm and a tensile 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 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 wire (7) cut into a length of 75 cm, stripped of the insulating coating layers (7a) at both ends and exposing the conductor (7b) is fixed on a horizontal stand (8) with a clamp (9), Load (1) at a speed of 50-60 times per minute over a length of 10 mm or more in the axial direction of the insulated wire
0) The blade (11) was reciprocated while applying 700 gf (in the direction of the arrow in the figure), and the number of reciprocation of the blade required until the insulating coating layer was removed by abrasion and the blade contacted the conductor of the electric wire. Was measured. FIG. 6 shows a front view of the blade. The blade (11) has an angle of 90 °.
3m width by two surfaces (11a, 11b) so that
m, and the radius of curvature (R) of the tip of the blade is 0.125 mm. When the number of reciprocation of the blade until the blade contacted the conductor of the electric wire was 1000 times or more, ○, when 500 times or more and less than 1000 times Δ, and when less than 500 times was rejected Indicated by x. 、 And レ ベ ル are practically acceptable levels and are acceptable.

The abrasion resistance 2 was evaluated using an electric wire having an outer diameter of 2.1 mm using a test apparatus whose front view is shown in FIG.
An insulated wire (7) cut into a length of 75 cm, stripped of the insulating coating layers (7a) at both ends and exposing the conductor (7b) is fixed on a horizontal base (8) with a clamp (9), Over 50mm / min over the length of 10mm or more in the axial direction of the insulated wire
The blade (11) is reciprocated (in the direction of the arrow in the drawing) while applying a load (10) of 700 gf at a speed of 60 times, so that the insulating coating layer is removed by abrasion and the blade comes into contact with the conductor of the electric wire. The number of reciprocation of the blade required up to that point was measured. FIG. 6 shows a front view of the blade.
1) has two surfaces (11) so that the angle between them is 90 °.
a, 11b) to form a blade having a width of 3 mm, and the radius of curvature (R) at the tip of the blade is 0.125 mm.
When the number of reciprocations of the blade until the blade came into contact with the conductor of the electric wire was 800 times or more, ○, when 400 times or more and less than 800 times, Δ Indicated by x. Wear resistance 2 was evaluated as an index of wear resistance.
Are very wear-resistant.

In the horizontal combustion test, J
A horizontal combustion test specified in ISC 3005 was performed, and those that self-extinguished within 30 seconds were counted as passed, and the results were indicated by the number of passed out of 10. In the 60-degree combustion test, a 60 ° inclined combustion test specified in JIS C 3005 was performed for each insulated wire, and those that self-extinguished within 30 seconds were counted as passed, and the number of passes out of 10 was shown. The vertical combustion test is a UL1581 vertical combustion test (U
W-1). For flame retardancy,
It is not necessary to pass all of the three types of flame retardancy tests, and a test in which all specimens pass the horizontal combustion test pass the combustion test. The heating deformation rate was determined by performing a heating deformation test (Deformation Test) of UL1581 at a temperature of 121 ° C.
The test was performed under a load of 500 gf. The results are shown as a 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
When each insulated wire was wound around a mandrel of a self-diameter, evaluation was made as to whether whitening occurred. When the film was wrapped six times and there was no whitening even once, ○ indicates that whitening occurred once or more and five times or less, and X indicates that whitening occurred six times or more. X is not preferable in practical use. The extrudability test was performed by extruding with an extruder having a diameter of 30 mm, and the motor load was extruded within the normal range and the appearance was good, and the extrusion load was slightly large and the appearance was slightly poor. Those having extremely large extrusion load and difficult or impossible to extrude were evaluated as x. 、 And レ ベ ル are practically acceptable levels and are acceptable.

The appearance of the insulated wire was visually inspected for the presence or absence of a change in the outer diameter and the condition of the surface. The occurrence of bleeding and the occurrence of bleeding are indicated by x.
An oil resistance test was performed at 70 ° C. for 4 hours based on JIS 3005. Residual elongation and residual tensile strength are 65% or more and 70% or more, respectively.

The compounds shown in Tables 1 to 16 are as follows:
Was used. (A) Thermoplastic resin component Component (a): hydrogenated block copolymer Manufacturer: Kuraray Co., Ltd. Product name: Septon 4077 Type: styrene / ethylene / propylene / styrene copolymer
Merged Styrene component content: 30% by weight Isoprene component content: 70% by weight Weight average molecular weight: 320,000 Molecular weight distribution 1.23 Hydrogenation rate: 90% or more Component (b): Softening for non-aromatic rubber Agent Manufacturer: Idemitsu Kosan Co., Ltd. Product Name: Diana Process Oil PW-90 Type: Paraffinic oil Weight average molecular weight: 540 Content of aromatic component: 0.1% or less Component (c): Single-site catalytic ethylene / α -I
Fin copolymer (c-1) Manufacturer: Dow Chemical Japan Co., Ltd. Product name: Engage EG8100 Type: Ethylene / 1-octene copolymer Density: 0.870 g / cm^Three  (C-2) Manufacturer: Dow Chemical Company Product name: Affinity FM1570 Type: Ethylene / 1-octene copolymer Density: 0.915 g / cm^Three  (C-3) Manufacturing company: Ube Industries, Ltd. Product name: Yumerit 2525F Type: ethylene-hexene copolymer Density: 0.926 g / cm^Three  (C-4) Manufacturer: Nippon Polychem Co., Ltd. Product name: KF-271 Type: Ethylene-hexene copolymer Density: 0.913 g / cm^Three  (C-5) Manufacturer: Nippon Polychem Co., Ltd. Product name: KF-360 Type: Ethylene-hexene copolymer Density: 0.898 g / cm^Three

Component (d1) (d-1) Manufacturer: Mitsui Dupont Polychemicals Product name: EV-170 Type: ethylene / vinyl acetate copolymer VA component content: 33% by weight (d-2) Manufacturer: Mitsui Dupont Polychemicals Product name: EV-40LX Type: Ethylene-vinyl acetate copolymer VA component content: 41% by weight (d-3) Manufacturer: Mitsui Dupont Polychemicals Product name: V-421 Type: Ethylene / acetic acid Vinyl copolymer VA component content: 28% by weight (d-4) Manufacturer: DuPont Mitsui Polychemicals 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) Manufacturer: JSR Trade name: EP07P Type: Ethylene propylene copolymer rubber (EPM) Ethylene component content: 73% by weight (d-6) Manufacturer: JSR product Name: EP11 Type: Ethylene propylene copolymer rubber (EPM) Ethylene component content: 52% by weight (d-7) Manufacturer: JSR Trade name: EP57P Type: Ethylene propylene terpolymer (EPDM) Ethylene component content : 66% by weight

Component (e): polypropylene resin (e-1) Manufacturer: Tokuyama Corporation Product name: PN610S Type: block polypropylene Density: 0.9 g / cm^Three  Melting point: 163 ° C Heat of crystal fusion: 79 J / g (e-2) Manufacturer: Grand Polymer Company Product name: F227D Type: random polypropylene Density: 0.9 g / cm^Three  Melting point: 154 ° C Crystal heat of fusion: 69 J / g (e-3) Manufacturer: Grand Polymer Company Name: CJ-700 Type: Homopolypropylene Density: 0.9 g / cm^Three  Melting point: 166 ° C Heat of crystal melting: 89 J / g (e-4) Manufacturer: Ube Industries, Ltd. Product name: ATF-133 Melting point: 153 ° C Heat of crystal melting: 34 J / g Component (f): Maleic acid-modified polyethylene Production Company: Mitsui Chemicals, Inc. Product name: ADMER XE070 Type: Maleic acid-modified polyethylene (LLDPE) Component (p): Acrylic rubber (p-1) Binary acrylic rubber Manufacturer: DuPont Mitsui Polychemicals Product name: Baymac DLS (p -2) Tertiary acrylic rubber Manufacturer: Mitsui Dupont Polychemicals Product name: Baymac GLS

Component (g): Organic peroxide Manufacturer: Nippon Yushi Co., Ltd. Trade name: Perhexa 25B Type: 2,5-dimethyl-2,5-di (t-butylperoxy) -hexane Component (h): Crosslinking aid Agent Manufacturer: 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 terminal (B-2) Manufacturer: Kyowa Chemical Company 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 components 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) Manufacturer: Toshiba Silicone Co., Ltd. Type: Silane coupling agent having an epoxy group at the end TSL8370 (trade name) Manufacturer: Toshiba Silicone Co., Ltd. Type: Silane coupling agent having a vinyl group at the end Phenol Manufacturer: Ciba-Geigy Company Product name: Irganox 1010 Type: pentaerythrityl-tetrakis (3- (3,5
-Di-t-butyl-4-hydroxyphenyl) propionate) Lubricant Manufacturer: Hoechst Company name: Wax OP Type: Saponified montanic acid 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 of Tables 1 to 16, the flame-retardant resin compositions obtained in Examples 1 to 72 and the sheets, electric wires, optical fiber cores and optical fiber cords using the same were necessary. It has elongation and tensile strength, and all of the combustion test, abrasion resistance test, whitening test, and heat deformation rate are good.
Furthermore, it has an extruding property that is practically satisfactory and has excellent flexibility. Examples 1 to 8, 10, 12, 13, 18 and 2
In Examples 0, 22 to 25, and 55 to 61, those having even better flame retardancy, which passed the vertical flame retardancy test, were obtained. Further, in Example 17, the material shrinkage hardly occurred after molding, and a molded plug having a good appearance was obtained. Furthermore, the flame of the burner used in the flame retardancy test specified in JIS C 3005 was applied to the power plug for 15 seconds.
The fire was instantly extinguished when the flame was separated. On the other hand, in Comparative Examples 1 to 24, uniform kneading or extrusion cannot be performed,
Alternatively, there is a problem with any of elongation, tensile strength, whitening property, extrudability, flexibility, hardness, flame retardancy, abrasion resistance, and heat deformability, and an electric wire having all favorable properties has not been obtained. In addition, 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 is difficult to re-mold, and the sheet surface is uneven. 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 effect is not recognized unless the metal hydrate is added before or simultaneously with the partial crosslinking reaction.

[0099]

The flame-retardant resin composition of the present invention is a non-halogen flame-retardant material and is composed of a phosphorus-free material, and has only excellent mechanical properties, flame retardancy, heat resistance and flexibility. In addition, no harmful heavy metal compounds are eluted, and a large amount of smoke and harmful gas (corrosive gas) is not generated at the time of disposal such as landfill or combustion. Further, the wiring member of the present invention is excellent in mechanical properties, flame retardancy and heat resistance, is also excellent in flexibility, and is not particularly whitened by bending. As described above, the wiring material of the present invention has excellent characteristics that can achieve both flexibility and mechanical strength as a non-halogen flame-retardant wiring material containing no phosphorus. Furthermore, since the coating layer of the wiring material of the present invention can be formed using a remeltable material as the coating material while having a high heat resistance of UL 105 ° C., it is a crosslinked material which is the current coating material. This makes it possible to provide a wiring material that is more recyclable than a coated wiring material. As described above, the wiring member of the present invention is very useful as a wiring member for electric / electronic devices in consideration of environmental issues, for example, a power cable. Further, the flame-retardant resin composition of the present invention is also suitable as a coating material for such wiring materials, optical fiber cords, optical fiber cords, etc., as a material for molded parts, and also as a tube or tape material. It is something.

[Brief description of the drawings]

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

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

FIG. 3 is a cross-sectional view of one embodiment of the optical fiber cord of the present invention in which a coating layer is formed on the outer periphery of one optical fiber core wire to which a plurality of tensile fibers are longitudinally 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 fibers are vertically attached to the outer periphery of two optical fiber core wires and a coating layer is further formed on the outer periphery 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. 5;

FIG. 7 is a schematic view showing a test method of flexibility.

[Explanation of symbols]

 DESCRIPTION OF SYMBOLS 1 Optical fiber wire 2 Coating layer 3 Optical fiber core wire 4 Tensile fiber 5 Coating layer 6 Coating layer 7 Insulated electric wire 7a Insulating coating layer 7b Conductor 8 units 9 Clamp 10 Load 11 Blade 11a, 11b Blade surface of blade

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat ゛ (Reference) 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 Masami Nishiguchi 1-15-3-705 Taihei, Sumida-ku, Tokyo (72) Invention Person Hitoshi Yamada 4-3-1-B215, Tatsumidaihigashi, Ichihara-shi, Chiba (72) Inventor Dai 3-25 Tatsumidaihito, Ichihara-shi, Chiba F-term (reference) 2H050 BB07W BB09W BB10W BB17W BB19W BD03 4F071 AA12X AA13 AA15X AA20X A21 AA22X AA28X AA33 AA33X AA71 AA75 AA76 AA78 AB18 AC08 AC10 AC11 AC12 AC16 AE02 AE03 AE07 AE17 AF47 AH 12 BB03 BC01 BC05 BC07 4J002 AE05X BB05Y BB06Z BB07Z BB08Z BB12U BB14U BB15U BB15Z BB21U BG04U BP01W BP02U DE078 DE148 DE189 DE268 DE288 DJ008 DK009 EH077 EK036 EK046 FB0 EK046 EK0 018

Claims (18)

[Claims] 1. (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 whose main component is a conjugated diene compound, and / or a hydrogenated block copolymer obtained by hydrogenating the same, 3 to 55% by weight, (B) 0 to 40% by weight of a softener for non-aromatic rubber, (c) 0 to 80% by weight of an ethylene / α-olefin copolymer, (d1) an ethylene-vinyl acetate copolymer, ethylene- (meth) 5 to 80% by weight of an acrylic acid copolymer or an ethylene- (meth) acrylate copolymer, (e) 0 to 50% by weight of a polypropylene resin, and (f) an unsaturated carboxylic acid or a derivative thereof. Modified modified polyethylene resin 0-3
0% by weight and (p) 100 parts by weight of a thermoplastic resin component (A) composed of 0 to 45% by weight of an acrylic rubber,
(G) 0.01 to 0.6 parts by weight of an organic peroxide,
(H) 0.03 to 1.8 parts by weight of a (meth) acrylate and / or allylic crosslinking aid and 50 to 300 parts by weight of a metal hydrate (B); (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)
50 parts by weight or more of a metal hydrate pretreated with a silane coupling agent with respect to parts by weight; (ii) 100 parts by weight or more of 300 parts by weight of the metal hydrate (B)
When the amount is not more than part by weight, at least half of the metal hydrate (B) is a mixture having a composition of a metal hydrate 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 component is a vinyl aromatic compound,
A block copolymer comprising at least one polymer block B whose main component is a conjugated diene compound, and / or 3 to 30% by weight of a hydrogenated block copolymer obtained by hydrogenating the same. (B) 0 to 20% by weight of softener for non-aromatic rubber, (c) 0 to 20% by weight of ethylene / α-olefin copolymer, (d1) Ethylene-vinyl acetate copolymer, ethylene- (meth) 35 to 80% by weight of at least one of acrylic acid copolymer or ethylene- (meth) acrylate copolymer, (e) 0 to 35% by weight of polypropylene resin, (f) unsaturated carboxylic acid or its derivative. Modified modified polyethylene resin 0
30% by weight and (p) 0 to 45% by weight of acrylic rubber
(G) 0.01 to 0.6 parts by weight of an organic peroxide, and (h) (meth) acrylate and / or allylic crosslinking aid with respect to 100 parts by weight of a thermoplastic resin component (A) consisting of The metal hydrate (B) is contained in an amount of from 03 to 1.8 parts by weight and the metal hydrate (B) in an amount of 50 to 300 parts by weight. When the amount is not less than 100 parts by weight and less than 100 parts by weight, the thermoplastic resin component (A) 100
50 parts by weight or more of a metal hydrate pretreated with a silane coupling agent with respect to parts by weight; (ii) 100 parts by weight or more of 300 parts by weight of the metal hydrate (B)
When the amount is not more than part by weight, at least half of the metal hydrate (B) is a mixture having a composition of a metal hydrate 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 component is a vinyl aromatic compound,
A block copolymer comprising at least one polymer block B whose main component is a conjugated diene compound, and / or 3 to 40% by weight of a hydrogenated block copolymer obtained by hydrogenating the same. (B) 0 to 40% by weight of a softener for non-aromatic rubber, (c) 0 to 80% by weight of an ethylene / α-olefin copolymer, (d2) 5 to 50% by weight of an ethylene / propylene copolymer rubber, (E) 0 to 50% by weight of a polypropylene resin, and (f) a modified polyethylene resin 0 modified with an unsaturated carboxylic acid or a derivative thereof.
(G) Organic peroxide 0.01 to 100 parts by weight of the thermoplastic resin component (A) comprising 30 to 30% by weight.
0.6 parts by weight, (h) (meth) acrylate type and / or
Or 0.03 to 1.8 parts by weight of an allylic crosslinking assistant and 50 to 300 parts by weight of a metal hydrate (B), wherein the metal hydrate (B) comprises: When the hydrate (B) is at least 50 parts by weight and less than 100 parts by weight, the thermoplastic resin component (A) 100
25 parts by weight or more of metal hydrate pretreated with a silane coupling agent based on parts by weight; (ii) 100 parts by weight or more of 300 parts by weight of metal hydrate (B)
When the amount is at most 1 part by weight, at least 1 part of the metal hydrate (B)
/ 4 is a mixture having a composition of a metal hydrate pretreated with a silane coupling agent, wherein the mixture is heated and kneaded 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 component is a vinyl aromatic compound,
A block copolymer comprising at least one polymer block B whose main component is a conjugated diene compound, 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 softener for non-aromatic rubber, (c) 0 to 80% by weight of ethylene / α-olefin copolymer, (d1) ethylene-vinyl acetate copolymer, ethylene- (meth) 5 to 80% by weight of at least one of acrylic acid copolymer or ethylene- (meth) acrylate copolymer, (d2) 5 to 50% by weight of ethylene / propylene copolymer rubber, (e) polypropylene resin 0 A thermoplastic resin comprising (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, and (h) 0.03 to 1. (meth) acrylate and / or allylic crosslinking aid, based on 100 parts by weight of the fat component (A). 8 parts by weight and 50 to 300 parts by weight of the metal hydrate (B), wherein the metal hydrate (B) comprises: (i) 50 to 100 parts by weight 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 a metal hydrate pretreated with a silane coupling agent with respect to parts by weight; (ii) 100 parts by weight or more of 300 parts by weight of the metal hydrate (B)
When the amount is not more than part by weight, at least half of the metal hydrate (B) is a mixture having a composition of a metal hydrate 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 component is a vinyl aromatic compound;
A block copolymer comprising at least one polymer block B whose main component is a conjugated diene compound, and / or a hydrogenated block copolymer obtained by hydrogenating the same, 3 to 55% by weight, (B) 0 to 40% by weight of a softener for non-aromatic rubber, (c) 0 to 80% by weight of an ethylene / α-olefin copolymer, (d1) an ethylene-vinyl acetate copolymer, ethylene- (meth) 5 to 80% by weight of an acrylic acid copolymer or an ethylene- (meth) acrylate copolymer, and (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 crystal fusion (ΔH
m) 0 to 85% by weight of a polypropylene resin containing an atactic polypropylene polymer as a main component having a value of 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 (G) 0.01 to 0.6 parts by weight of an organic peroxide, (h) (meth) acrylate based on 100 parts by weight of a thermoplastic resin component (A) comprising 0 to 45% by weight of an acrylic rubber And / or 0.03 to allylic crosslinking aid
1.8 parts by weight and 50 to 300 parts by weight of the metal hydrate (B), wherein the metal hydrate (B) is: (i) the metal hydrate (B) is 50 parts by weight When it is less than 100 parts by weight, the thermoplastic resin component (A) 100
50 parts by weight or more of a metal hydrate pretreated with a silane coupling agent with respect to parts by weight; (ii) 100 parts by weight or more of 300 parts by weight of the metal hydrate (B)
When the amount is not more than part by weight, at least half of the metal hydrate (B) is a mixture having a composition of a metal hydrate 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 component is a vinyl aromatic compound,
A block copolymer comprising at least one polymer block B whose main component is a conjugated diene compound, and / or 3 to 30% by weight of a hydrogenated block copolymer obtained by hydrogenating the same. (B) 0-20% by weight of softener for non-aromatic rubber, (c) 0-20% by weight of ethylene / α-olefin copolymer, (d1) ethylene-vinyl acetate copolymer, ethylene- (meth) 35-80% by weight of at least one of acrylic acid copolymer or ethylene- (meth) acrylate copolymer, (e) melting point (Tm) of polypropylene component measured by differential scanning calorimeter is 163 ° C. or less And the heat of crystal fusion (△
Hm) is a polypropylene resin 0 to 35 containing an atactic polypropylene polymer whose main component is 55 J / g or less.
% By weight, 100 parts by weight of a thermoplastic resin component (A) comprising (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 an organic peroxide, and (h) 0.03 to
1.8 parts by weight and 50 to 300 parts by weight of the metal hydrate (B), wherein the metal hydrate (B) is: (i) the metal hydrate (B) is 50 parts by weight When it is less than 100 parts by weight, the thermoplastic resin component (A) 100
50 parts by weight or more of a metal hydrate pretreated with a silane coupling agent with respect to parts by weight; (ii) 100 parts by weight or more of 300 parts by weight of the metal hydrate (B)
When the amount is not more than part by weight, at least half of the metal hydrate (B) is a mixture having a composition of a metal hydrate 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 component is a vinyl aromatic compound,
A block copolymer comprising at least one polymer block B whose main component is a conjugated diene compound, and / or 3 to 40% by weight of a hydrogenated block copolymer obtained by hydrogenating the same. (B) 0 to 40% by weight of a softener for non-aromatic rubber, (c) 0 to 80% by weight of an ethylene / α-olefin copolymer, (d2) 5 to 50% by weight of an 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 crystal fusion (ΔH
from 0 to 85% by weight of a polypropylene resin having an atactic polypropylene polymer having m) of 55 J / g or less, and from 0 to 30% by weight of (f) a modified polyethylene resin modified with an unsaturated carboxylic acid or a derivative thereof. 100 parts by weight of the thermoplastic resin component (A)
(G) 0.01 to 0.6 parts by weight of an organic peroxide,
(H) 0.03 to 1.8 parts by weight of a (meth) acrylate and / or allylic crosslinking aid and 50 to 300 parts by weight of a metal hydrate (B); (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)
25 parts by weight or more of metal hydrate pretreated with a silane coupling agent based on parts by weight; (ii) 100 parts by weight or more of 300 parts by weight of metal hydrate (B)
When the amount is at most 1 part by weight, at least 1 part of the metal hydrate (B)
/ 4 is a mixture having a composition of a metal hydrate pretreated with a silane coupling agent, wherein the mixture is heated and kneaded 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 component is a vinyl aromatic compound;
A block copolymer comprising at least one polymer block B whose main component is a conjugated diene compound, 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 softener for non-aromatic rubber, (c) 0 to 80% by weight of ethylene / α-olefin copolymer, (d1) ethylene-vinyl acetate copolymer, ethylene- (meth) 5 to 80% by weight of at least one of acrylic acid copolymer or ethylene- (meth) acrylate copolymer, (d2) 5 to 50% by weight of ethylene / propylene copolymer rubber, (e) Differential scanning calorie An atactic polypropylene polymer having a melting point (Tm) of 163 ° C. or less and a heat of crystal fusion (ΔHm) of 55 J / g or less, which is measured by a meter, is mainly used. Polypropylene resins 0 to
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, based on 100 parts by weight of a thermoplastic resin component (A) (G) 0.01 to 0.6 parts by weight of an organic peroxide, and (h) 0.03 to 0.03 parts by weight of a (meth) acrylate and / or allylic crosslinking aid.
1.8 parts by weight and 50 to 300 parts by weight of the metal hydrate (B), wherein the metal hydrate (B) is: (i) the metal hydrate (B) is 50 parts by weight When it is less than 100 parts by weight, the thermoplastic resin component (A) 100
50 parts by weight or more of a metal hydrate pretreated with a silane coupling agent with respect to parts by weight; (ii) 100 parts by weight or more of 300 parts by weight of the metal hydrate (B)
When the amount is not more than part by weight, at least half of the metal hydrate (B) is a mixture having a composition of a metal hydrate 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 assistant (h) has a 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 represented by the following formula: The flame-retardant resin composition according to claim 1. 10. The flame-retardant resin composition according to claim 1, wherein the metal hydrate (B) is magnesium hydroxide. 11. The flame-retardant resin composition according to claim 1, 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, an ethylene- (meth) acrylic acid copolymer, or an ethylene-vinyl acetate copolymer.
5. The method according to claim 1, wherein at least one kind (d1) of the (meth) acrylate copolymer is an ethylene-vinyl acetate copolymer having a vinyl acetate component content of 25% by weight or more. The flame-retardant resin composition according to 5, 6, or 8. 13. The flame retardant according to claim 1, wherein 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). Resin composition. 14. A thermoplastic resin component (A) containing 0.5 to 20 parts by weight of at least one selected from zinc borate, zinc stannate and zinc hydroxystannate based on 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. A flame-retardant resin composition according to any one of claims 1 to 14, wherein the flame-retardant resin composition has a coating layer on the outside of a conductor or an optical fiber or / and an optical fiber core. Molded articles. 16. A molded part obtained by molding the flame-retardant resin composition according to claim 1. Description: 17. The flame-retardant resin composition according to any one of claims 1 to 14, wherein (a) at least two polymer blocks A mainly composed of a vinyl aromatic compound. A block copolymer comprising at least one polymer block B whose main component is a conjugated diene compound, and / or a hydrogenated block copolymer obtained by hydrogenating the same; Softener for aromatic rubber, (c) ethylene / α-olefin copolymer,
(D1) ethylene-vinyl acetate copolymer, ethylene-
(Meth) acrylic acid copolymer or at least one ethylene- (meth) acrylate copolymer and / or (d2) ethylene / propylene copolymer rubber, (e) polypropylene resin, (f) unsaturated A modified polyethylene resin modified with a carboxylic acid or a derivative thereof,
(P) acrylic rubber, (g) organic peroxide,
(H) A (meth) acrylate-based and / or allyl-based cross-linking assistant and a metal hydrate (B) are simultaneously heated and kneaded at a temperature equal to or higher than the melting temperature of the resin components (a) to (f) to perform a cross-linking treatment. A method for producing a flame-retardant resin composition. 18. The flame-retardant resin composition according to any one of claims 1 to 14, wherein, as the first step, (a) at least two polymers mainly composed of a vinyl aromatic compound. 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 softener for non-aromatic rubber, (c) an ethylene / α-olefin copolymer, (D1) at least one of an ethylene-vinyl acetate copolymer, an ethylene- (meth) acrylic acid copolymer, or an ethylene- (meth) acrylic acid ester copolymer
The 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, After obtaining the plastic resin component (A), in a second step, the resin component (A) and (g) an organic peroxide, (h) a (meth) acrylate-based and / or allylic cross-linking assistant, and a metal hydrate A method for producing a flame-retardant resin composition, comprising heating and kneading the product (B) at a temperature equal to or higher than the melting temperature of the thermoplastic resin component (A), followed by crosslinking treatment.