JP5222090B2 - Flame retardant resin composition and insulated wire - Google Patents

Description

  TECHNICAL FIELD The present invention relates to a flame retardant resin composition and an insulated wire using the flame retardant resin composition, and particularly to a flame retardant resin composition and an insulation that are suitably used for automobiles, electrical / electronic devices, and the like. It relates to electric wires.

  Various properties such as mechanical properties, flame retardancy, heat resistance, and cold resistance are required for members and insulating materials used in automobiles, electronic / electrical devices, and the like. Conventionally, a polyvinyl chloride compound or a compound containing a halogen-based flame retardant containing a bromine atom or a chlorine atom in the molecule has been mainly used as the material.

  When the above conventional materials are incinerated at the time of disposal, a large amount of corrosive gas may be generated. For this reason, a non-halogen flame retardant material that does not generate corrosive gas has been proposed (see, for example, Patent Document 1). Further, as a non-halogen flame retardant resin composition, a composition using a natural mineral mainly composed of magnesium hydroxide as a flame retardant is known (for example, see Patent Documents 2 to 4).

JP 2004-83612 A Japanese Patent No. 3339154 Japanese Patent No. 3636675 JP 2004-189905 A

  The conventional non-halogen flame retardant resin composition comprising a polyolefin-based resin using a natural mineral mainly composed of magnesium hydroxide as a flame retardant has a problem that it does not have sufficient cold resistance and abrasion resistance. There is a need to improve cold resistance and wear resistance.

  The problem to be solved by the present invention is to solve the above-mentioned problems. When a natural mineral mainly composed of magnesium hydroxide is used as a flame retardant, it has excellent cold resistance and wear resistance. Another object is to provide a flame retardant resin composition and an insulated wire.

  In order to solve the above-mentioned problems, the flame retardant resin composition of the present invention is a flame retardant resin composition containing a flame retardant obtained by pulverizing a natural mineral mainly composed of magnesium hydroxide, and having a functional group. The gist is to contain a polypropylene resin having a rate of 1000 MPa or more.

  In the flame retardant resin composition of the present invention, the functional group is at least one selected from a carboxylic acid group, an acid anhydride group, an epoxy group, a hydroxyl group, an amino group, an alkenyl cyclic imino ether group, and a silane group. It is preferable that the polypropylene resin having the functional group is blended in an amount of 10 to 30 parts by mass with respect to 100 parts by mass of the component excluding the polypropylene resin.

  Moreover, the insulated wire of this invention makes the summary that the insulating layer using said flame-retardant resin composition is formed in the circumference | surroundings of a conductor.

  The flame retardant resin composition of the present invention contains a flame retardant obtained by pulverizing a natural mineral mainly composed of magnesium hydroxide by containing a polypropylene resin having a functional group and an elastic modulus of 1000 MPa or more. Even if it is a composition, the insulated wire excellent in cold resistance and abrasion resistance is obtained.

  Hereinafter, embodiments of the present invention will be described in detail. The flame-retardant resin composition of the present invention is basically composed of a flame retardant, a base resin, and a polypropylene resin having an elastic modulus of 1000 MPa or more (hereinafter sometimes referred to as a flexible resin). In addition to the above components, other additives can be appropriately added to the flame retardant resin composition as necessary within a range that does not lower the cold resistance. Examples of other additives include an antioxidant.

  As the base resin used in the flame retardant resin composition, a so-called non-halogen plastic or rubber not containing a halogen element such as chlorine or bromine is used. As a material preferable as such a base resin, for example, a polyolefin resin is exemplified. Examples of the polyolefin resin include polyethylene resin and polypropylene resin. As the base resin, a resin having no functional group is preferably used.

  The flexible resin used in the flame retardant resin composition is used for imparting flexibility to a coating such as an insulating coating formed from the composition and improving cold resistance and abrasion resistance of the insulated wire. . When the elastic modulus of the flexible resin is less than 1000 MPa, sufficient abrasion resistance and cold resistance cannot be obtained in the insulating coating formed from the composition. The upper limit of the elastic modulus of the flexible resin is preferably 4000 MPa. If the elastic modulus of the flexible resin exceeds 4000 MPa, the insulating coating may be cracked in a low-temperature winding test. A preferable elastic modulus range of the flexible resin is 1500 to 3500 MPa.

  The addition amount of the flexible resin is preferably 10 to 30 parts by mass based on 100 parts by mass of the component excluding the flexible resin in the flame retardant resin composition. When the addition amount of the flexible resin is less than 10 parts by mass, there is a possibility that sufficient wear resistance cannot be obtained when an insulating layer of an insulated wire is used. Moreover, when the addition amount of a flexible resin exceeds 30 mass parts, when it is set as the insulating layer of an insulated wire, there exists a possibility that cold resistance may fall. Furthermore, the addition amount of a flexible resin is 12-28 mass parts with respect to 100 mass parts of components except this flexible resin in a flame-retardant resin composition, More preferably, it is 15-25 mass parts.

  As the functional group of the flexible resin, one or more functional groups selected from a carboxyl group, an acid anhydride group, an epoxy group, a hydroxyl group, an amino group, an alkenyl cyclic imino ether group, and a silane group are used. These functional groups may be introduced singly or plurally. By using a resin having a functional group as the flexible resin, adhesion between the insulating layer and the conductor can be improved when the insulating layer of the insulated wire is formed from the flame retardant resin composition.

  Specifically, as a method for introducing a functional group into a polypropylene resin, a method of graft-polymerizing the compound for introducing the functional group onto a polypropylene resin to obtain a graft-modified propylene polymer, a compound for introducing the functional group, and Examples thereof include a method of copolymerizing a propylene compound to obtain a propylene copolymer.

  Specific examples of the compound that introduces a carboxyl group or an acid anhydride group as the functional group include α, β-unsaturated dicarboxylic acids such as maleic acid, fumaric acid, citraconic acid, and itaconic acid, or anhydrides thereof. And unsaturated monocarboxylic acids such as acrylic acid, methacrylic acid, furanic acid, crotonic acid, vinyl acetic acid and pentenoic acid.

  Specific examples of the compound that introduces an epoxy group as the functional group include glycidyl acrylate, glycidyl methacrylate, itaconic acid monoglycidyl ester, butenetricarboxylic acid monoglycidyl ester, butenetricarboxylic acid diglycidyl ester, and butenetricarboxylic acid triglyceride. Glycidyl esters such as glycidyl ester, α-chloroacrylic acid, maleic acid, crotonic acid and fumaric acid, vinyl glycidyl ether, allyl glycidyl ether, glycidyloxyethyl vinyl ether, styrene-p-glycidyl ether, p- Examples thereof include glycidyl styrene.

  Specific examples of the compound that introduces a hydroxyl group as the functional group include 1-hydroxypropyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, and hydroxyethyl (meth) acrylate.

  Specific examples of the compound that introduces an amino group as the functional group include aminoethyl (meth) acrylate, propylaminoethyl (meth) acrylate, dimethylaminoethyl (meth) acrylate, diethylaminoethyl (meth) acrylate, and dibutylamino. Examples include ethyl (meth) acrylate, aminopropyl (meth) acrylate, phenylaminoethyl (meth) acrylate, cyclohexylaminoethyl (meth) acrylate, and the like.

  Specific examples of the compound that introduces an alkenyl cyclic imino ether group as the functional group include 2-vinyl-2-oxazoline, 2-isopropenyl-2-oxazoline, 2-vinyl-5,6-dihydro-4H— 1,3-oxazine, 2-isopropenyl-5,6-dihydro-4H-1,3-oxazine and the like can be mentioned.

  Specific examples of the compound that introduces a silane group as the functional group include unsaturated silane compounds such as vinyltrimethoxysilane, vinyltriethoxysilane, vinyltriacetylsilane, and vinyltrichlorosilane.

  As the flame retardant of the flame retardant resin composition of the present invention, a pulverized natural mineral mainly composed of magnesium hydroxide is used. For example, the flame retardant is dry pulverized with natural brucite using a pulverizer, crusher, ball mill, etc., or pulverized with wet pulverization, etc., and classified as necessary using a cyclone machine or sieve. Can be obtained. The pulverization method is preferably a dry method.

  The particle size of the flame retardant is from 0.1 to 20 μm, preferably from 0.2 to 10 μm, more preferably from 0.5 to 5 μm, in terms of average particle size. When the average particle diameter of the flame retardant is less than 0.1 μm, secondary aggregation is likely to occur, and the mechanical properties are deteriorated. Moreover, when the average particle diameter of a flame retardant exceeds 20 micrometers, when using for the insulating layer of an insulated wire, there exists a possibility that it may become the external appearance defect of an insulating layer.

  The amount of the flame retardant added is usually 30 to 250 parts by mass with respect to 100 parts by mass of the base resin. The amount of the flame retardant added is preferably 50 to 200 parts by mass, more preferably 60 to 180 parts by mass with respect to 100 parts by mass of the base resin.

  Moreover, the surface of the pulverized product may be surface-treated with a surface treatment agent for the flame retardant. As the surface treating agent, a homopolymer of α-olefin such as 1-heptene, 1-octene, 1-nonene, 1-decene, a mutual copolymer, or a mixture thereof is used. The surface treatment agent may be modified.

  Modification of the flame retardant surface treatment agent is, for example, a method of using an unsaturated carboxylic acid or a derivative thereof as a modifying agent and introducing a carboxyl group (acid) into the polymer such as the above-mentioned α-olefin polymer to modify the acid. Is mentioned. Specific examples of the modifier include maleic acid and fumaric acid as unsaturated carboxylic acid, and maleic anhydride (MAH), maleic acid monoester, maleic acid diester and the like as derivatives thereof. As the modifier, maleic acid and maleic anhydride are preferable. These modifiers may be used alone or in combination of two or more. Examples of the acid modification method for introducing an acid into the surface treatment agent include graft polymerization and a direct method. The acid modification amount is usually about 0.1 to 20% by mass, preferably 0.2 to 10% by mass, and more preferably 0.2 to 0.2% by mass with respect to the polymer as the amount of the modifier used. 5% by mass.

  The surface treatment method for treating the flame retardant with the surface treatment agent is not particularly limited, and various treatment methods can be used. Examples of the surface treatment method of the flame retardant include a method performed simultaneously with the pulverization of the flame retardant, and a method of mixing the previously pulverized flame retardant and the surface treatment agent and treating them later. Moreover, as a processing method, any of the wet processing method using a solvent and the dry processing method which does not use a solvent may be sufficient.

  Solvents used for wet processing of the flame retardant include aliphatic hydrocarbons such as pentane, hexane, and heptane, and aromatic hydrocarbons such as benzene, toluene, and xylene. Further, the surface treatment of the flame retardant may be a method in which a surface treatment agent is added to the flame retardant and the resin at the time of preparing the flame retardant resin composition and the composition is kneaded at the same time.

  It does not specifically limit as a manufacturing method of the said flame retardant resin, A well-known method can be used. The flame-retardant resin composition can be produced by, for example, melting and kneading with a conventional kneader such as a Banbury mixer, a pressure kneader, a kneading extruder, a twin-screw kneading extruder, and a roll and uniformly dispersing it. .

  The flame-retardant resin composition can be used as a member or an insulating material used in automobiles, electronic / electrical devices, and is particularly suitably used as a material for forming an insulating layer of an insulated wire.

  The insulated wire of the present invention is flame retardant by covering the conductor by extruding the flame retardant resin composition around the conductor using an electric wire extrusion molding machine or the like used for production of a normal insulated wire. An insulating layer using the resin composition is formed around the conductor. The conductor used for an insulated wire can utilize what is used for a normal insulated wire. Moreover, the diameter of the conductor of an insulated wire, the thickness of an insulating layer, etc. are not specifically limited, According to the use etc. of an insulated wire, it can determine suitably. The insulating layer may be a single layer or may be composed of two or more layers.

Examples of the present invention and comparative examples are shown below.
Example 1
50 parts by mass of a polypropylene resin (trade name “EC7”, manufactured by Nippon Polypro Co., Ltd.) with no functional group introduced as a base resin, magnesium hydroxide obtained by pulverizing natural minerals as a flame retardant (trade name “Magsees, manufactured by Kamishima Chemical Co., Ltd.) N1 ") 49 parts by mass, a flexible resin having an elastic modulus of 2000 MPa, an acid anhydride group introduced polypropylene resin (trade name" AT2377 "manufactured by Mitsui Chemicals), 15 parts by mass, antioxidant (Ciba Specialty Chemicals) 1 part by mass (trade name “Irganox 1010”, manufactured by the company) was mixed at 200 ° C. using a twin-screw kneader, and then molded into a pellet by a pelletizer to obtain a flame-retardant resin composition pellet. . An insulating layer made of a flame retardant resin composition is formed by extruding the pellets at a thickness of 0.2 mm on the outer periphery of a conductor of a annealed copper wire (cross-sectional area: 0.5 mm ² ) by twisting seven annealed copper wires with an extrusion molding machine. Thus, an insulated wire coated with a conductor was obtained.

Examples 2 and 3
As shown in the column of the component composition of the flame retardant resin composition in Table 1, the addition amount of the flexible resin of Example 1 was changed to 20 parts by mass (Example 2) and 25 parts by mass (Example 3). Except for the above, an insulated wire was produced in the same manner as in Example 1.

Examples 4-6
As shown in the column of the composition of the flame retardant resin composition in Table 1, the flexible resin of Example 1 is made of a polypropylene resin having an elastic modulus of 2200 MPa and an acid anhydride group (trade name “AT2378, manufactured by Mitsui Chemicals, Inc.). )), And the addition amount was 15 parts by mass (Example 4), 20 parts by mass (Example 5), and 25 parts by mass (Example 6). Manufactured.

Comparative Examples 1-3
The flexibility-imparting resin of Example 1 was changed to a polypropylene resin (trade name “QB550” manufactured by Mitsui Chemicals, Inc.) having an elastic modulus of 500 MPa and an acid anhydride group introduced, and the addition amount was 15 parts by mass (Comparative Example 1). ), 20 parts by mass (Comparative Example 2), and 25 parts by mass (Comparative Example 3), an insulated wire was produced in the same manner as in Example 1.

  Using the insulated wires obtained in the examples and comparative examples, a cold resistance test and an abrasion resistance test were performed. The test results are shown in Table 1. The cold resistance test method and the abrasion resistance test method are as follows.

[Cold resistance test method]
This was performed in accordance with JIS C3055. That is, the insulated wires of Examples and Comparative Examples were cut into 38 mm lengths to make test pieces, the test pieces were mounted on a cold resistance tester, cooled to a predetermined temperature, hit with a hitting tool, The condition after hitting was observed. Using five test pieces, the temperature at which all five test pieces were broken was defined as the cold resistant temperature.

[Abrasion resistance test method]
The test was conducted by a blade reciprocation method in accordance with the automobile technical standard “JASO D611-94”. That is, the insulated wire of an Example and a comparative example was cut out to 750 mm length, and it was set as the test piece. Then, at a room temperature of 23 ± 5 ° C., the blade is reciprocated at a speed of 50 mm / min with a length of 10 mm or more in the axial direction with respect to the coating material (insulating layer) of the test piece, and the number of reciprocations until contact with the conductor. Was measured. At this time, the load applied to the blade was 7N. About the frequency | count, the thing 200 times or more was set as the pass ((circle)), and the thing less than 200 times was set as the disqualification (x).

* 1: Polypropylene resin manufactured by Nippon Polypro Co., Ltd.
* 2: Made by Mitsui Chemicals, polypropylene resin having acid anhydride group, elastic modulus 2000 MPa
* 3: Made by Mitsui Chemicals, polypropylene resin having an acid anhydride group, elastic modulus 2200 MPa
* 4: Made by Mitsui Chemicals, polypropylene resin with acid anhydride group, elastic modulus 500 MPa
* 5: Magnesium hydroxide from Kamishima Chemical Co., Ltd., crushed natural mineral * 6: Antioxidant, manufactured by Ciba Specialty Chemicals

As shown in Table 1, Examples 1 to 6 had good cold resistance of −30 ° C. or −35 ° C., and the wear resistance was acceptable. In Comparative Examples 1 to 3, the cold resistance was −25 ° C. or −20 ° C., which was worse than the examples, and the wear resistance was unacceptable.

Claims (3)

A flame retardant resin composition comprising a flame retardant obtained by pulverizing a natural mineral mainly composed of magnesium hydroxide, a polypropylene resin having a functional group and a flexural modulus of 1000 MPa or more, and a base resin , A flame retardant resin composition comprising 10 to 30 parts by mass of a polypropylene resin having a group based on 100 parts by mass of a component excluding the polypropylene resin .   2. The functional group is at least one selected from a carboxylic acid group, an acid anhydride group, an epoxy group, a hydroxyl group, an amino group, an alkenyl cyclic imino ether group, and a silane group. The flame-retardant resin composition as described. The insulated wire using the flame-retardant resin composition of Claim 1 or 2 is formed around the conductor, The insulated wire characterized by the above-mentioned.