JP2003157737A - Wire harness protection material and wire harness using the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a wire harness protection material that is superior in heat aging performance and a wire harness using the same. SOLUTION: A tape shape article having an adhesive, a tube shape article and a sheet shape article are manufactured by using a base material which is obtained by adding a plasticizer DOP (dioctylphtalate) 60 pts.wt., a filler 20 pts.wt., and a stabilizer 5 pts.wt. to the PVC resin (polymerization degree P=1300) 100 pts.wt. and by adding to this a copper inhibitor 0.001-5 pts.wt. For the tape shape article, an adhesive which is obtained by adding NR (natural rubber) 30 pts.wt. zinc white 20 pts.wt., and a rosin system resin 80 pts.wt. to the SBR (stylene-butadiene rubber) 70 pts.wt. and by adding to this a copper inhibitor 0.001-5 pts.wt. is provided as an adhesive layer.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a wire harness protective material and a wire harness using the same, and more particularly, to a wire bundle in which electric wires covering an electric conductor containing copper are bundled and which does not contain halogen elements. An electric wire bundle consisting of a halogen-free insulated electric wire (also simply referred to as “HF electric wire”) in which an electric conductor is covered with a polyolefin-based insulating resin material that does not contain or has a halogen element content at least lower than that of vinyl chloride resin (simply “HF alone”). An electric wire bundle (also referred to as "electric wire bundle") or a part thereof is replaced with a PVC insulated electric wire (also simply referred to as "PVC electric wire") in which the electric conductor is covered with polyvinyl chloride (PVC) resin (simply "mixed electric wire bundle"). Also referred to as a), a tape-shaped, tube-shaped or sheet-shaped wire harness protective material with a pressure-sensitive adhesive, which is used as a coating, and HF alone. About wire harness by covering the periphery of the flux or mixed wire bundle.

[0002]

2. Description of the Related Art A wire harness used for wiring for automobiles and other vehicles is also called an assembled electric wire. An electric wire of appropriate specifications and thickness is selected, cut and bundled to form a tube. It is made by passing through or wrapping it with a sheet and taping it together, and then attaching various parts to make a group of parts. As the electric wire, generally, a PVC electric wire in which several copper wires are bundled and covered with a polyvinyl chloride (PVC) resin coating is used. As the copper wire, in addition to annealed soft copper, tin-plated soft copper Lines are used. Further, as the tape, a PVC tape in which an adhesive layer (adhesive layer) is provided on a base material made of PVC resin is widely used, and as other exterior protective materials, a PVC tube and a PVC sheet are widely used. That is, PVC resin is generally used not only for the insulation coating material of electric wires but also for tape, tube, sheet and other electric wire protection materials and wire harness protection materials.

However, for PVC electric wires which have been widely used as insulated electric wires, alternatives have recently been investigated as part of measures against environmental problems. For example, a large amount of inorganic filler as a flame retardant is added to a non-halogen polyolefin. A halogen-free electric wire that has been added has been proposed.

Therefore, the inventors of the present invention have adopted the P
A PVC tube or sheet is attached, and a PVC tube or sheet is attached with an adhesive-attached PVC tape, or a wire harness in which both ends of the sheet are bound, or a PVC tube or sheet is attached to a mixed electric wire bundle, and the PVC tube or sheet is attached with an adhesive-attached PVC tape ( A wire harness in which both ends of (also simply referred to as “PVC protective material”) were bound was produced, and the heat aging performance of each wire harness was examined. As a result, it was found that the heat aging performance of the wire harness of the mixed wire bundle was significantly inferior to the heat aging performance of the wire harness of the HF single wire bundle. The inventors investigated the cause of the difference in the heat aging performance,
We came to think that the cause might be the ionization of copper and the transfer of plasticizer.

First, in the ionization of copper, the water content in the air is P
It occurs by entering the HF wire through the VC protector and ionizing the copper in the copper wire. It is considered that the copper ion has a high oxidation potential and acts as a catalyst to break the chemical bond of the wire coating polymer, thereby deteriorating the wire coating polymer. Further, the ionization of copper also occurs when the plasticizer compounded in the PVC protective material diffuses into the HF electric wire and reacts with the copper of the copper wire to promote the ionization of copper.
It is considered that this copper ion also acts as a catalyst to break the chemical bond of the electric wire coating polymer and deteriorate the electric wire coating polymer.

Incidentally, the HF electric wire usually contains a predetermined amount of a copper damage inhibitor in order to complex and stabilize copper ions generated by the influence of moisture in the air. Therefore, if copper ions are generated even by reacting with the plasticizer as described above, a predetermined amount of the copper damage inhibitor will not be sufficient.

Further, the copper damage inhibitor contained in the HF electric wire dissolves in the plasticizer as it moves from the PVC protective material, so that the HF electric wire has a low concentration gradient P (of the copper damage inhibitor).
Return to the VC protection material. Then, the copper damage inhibitor,
Not only is the copper ion generated by the influence of air stabilized, but also the copper ion generated by the plasticizer is consumed. In addition, the plasticizer transfers the HF electric wire to the PVC protective material. It will be effectively reduced. Therefore, the aging of the HF electric wire is promoted. Moreover, the aging of the PVC protective material is accelerated by the plasticizer flowing out.

Furthermore, the HF electric wire contains a predetermined amount of anti-aging agent, and this anti-aging agent also dissolves in the plasticizer when it migrates from the PVC protective material, and the concentration gradient from the HF electric wire. Decrease due to return to low PVC protectant.
Therefore, the aging of the HF electric wire is promoted. Also, PV
The aging of the C protective material is promoted by the plasticizer flowing out.

Furthermore, the inventors of the present invention have used a tube made of non-halogen polyethylene, polypropylene or the like in the wire bundle,
A heat aging test was also performed on a wire harness in which a sheet (also simply referred to as “HF protective material”) was attached and the tube and the sheet were bound with a non-halogen adhesive tape (HF protective material). Also in this case, it was found that the heat aging performance of the wire harness composed of the mixed wire bundle was significantly inferior to the heat aging performance of the wire harness composed of the HF single wire bundle. The cause is that in the case of a mixed wire bundle,
It is considered that copper ionization and transfer of the plasticizer similar to the above occur between the PVC electric wire and the HF electric wire.

Then, the inventors repeated trial and error in order to utilize the migration of the plasticizer, and found that if the PVC protection material was blended with the copper damage inhibitor at a higher concentration than that of the HF wire,
Since the copper damage inhibitor is soluble in the plasticizer, the copper damage inhibitor can be placed on the plasticizer and diffused into the HF electric wire when the plasticizer migrates, and the consumption amount of the copper damage inhibitor cannot be replenished. I came to think of it.

Further, the inventors of the present invention have prepared an antiaging agent by mixing it in a PVC protective material at the same ratio as the HF electric wire (ratio to the organic polymer) so that the adjacent protective materials and electric wires will be aged. Since the concentration gradient of the inhibitor becomes the same, it has been thought that it is possible to suppress the decrease of the anti-aging agent in the HF electric wire without the anti-aging agent moving even if the plasticizer moves.

The problem to be solved by the present invention is to provide a wire harness in which an HF single wire bundle or a mixed wire bundle in which a part thereof is replaced with a PVC wire is used as a protective material in the form of a tape with an adhesive, a tube, or When a sheet-shaped wire harness protective material is used, by suppressing copper damage to the HF electric wire and by suppressing diffusion of an anti-aging agent between the HF electric wire and the wire harness protective material or PVC electric wire, It is intended to provide a wire harness protective material having excellent heat aging performance and a wire harness using the same. In this way, it is intended to stabilize the wire quality of the wire harness and achieve permanent use.

[0013]

In order to solve this problem, the wire harness protection material according to the first aspect of the present invention is, as described in claim 1, an electric wire covering an electric conductor containing copper. An electric wire bundle consisting of a halogen-free insulated electric wire in which the electric conductor is covered with a halogen-free resin material containing no halogen element or having a halogen element content lower than at least vinyl chloride resin, which is a bundle of electric wires. It is a tape-shaped, tube-shaped or sheet-shaped wire harness protective material with a pressure-sensitive adhesive, which is used by covering a part of an electric wire bundle which is replaced with a PVC insulated electric wire in which the electric conductor is covered with a vinyl chloride resin material. Then, the gist is that the tape-shaped material, the tube-shaped material and the sheet-shaped material with the adhesive contain a copper damage inhibitor.

In the present invention, as the above-mentioned "copper wire",
Besides annealed annealed copper, tin-plated annealed copper wire is used. That is, any electric wire covering an electric conductor containing copper can be applied to the present invention. In addition, as the base polymer used for the wire coating material of the "halogen-free insulated wire", an olefin-based propylene polymer (homopolymer and propylene random or block copolymer),
Polyethylene (high-density polyethylene, linear low-density polyethylene, low-density polyethylene, ultra-low-density polyethylene, etc.), polybutene polymer, ethylene copolymer (ethylene-vinyl acetate copolymer, ethylene-ethyl acrylate copolymer, etc.) Preferred examples thereof include olefin elastomers (polypropylene-ethylene / propylene copolymers, etc.) or copolymers in which unsaturated double bonds in these copolymers are saturated by hydrogenation. These polymers can be used alone or as a mixture of two or more kinds. To this, a flame retardant containing no halogen such as metal hydrate such as magnesium hydroxide or aluminum hydroxide is added as a flame retardant. Then, a copper damage inhibitor, an antiaging agent and, if necessary, a processing aid may be added, and further, crosslinking may be performed to improve heat resistance. In the present invention, it is desired that a copper damage inhibitor and an antioxidant be added. Further, low halogen compounds conceptually include bromide compounds which are flame retardant, and those which impart flame retardancy by using a halogen-containing resin having a halogenation rate lower than that of PVC resin. Also,
In the case of "PVC insulated wire", in order to impart flexibility to the PVC resin and improve the workability of the material, or to reduce the material cost, it has good mixability with the resin, and has good water resistance and electrical insulation. Also contains an excellent plasticizer. An antioxidant may be further added to this.

According to the invention of claim 1 having the above-mentioned structure, since the tape-shaped material, the tube-shaped material and the sheet-shaped material with the adhesive contain a copper damage inhibitor, the halogen-free insulated wire is used. Even if the copper damage preventing agent is consumed, the copper damage preventing agent is replenished to the halogen-free insulated wire from the adhesive-attached tape-shaped material, tube-shaped material, and sheet-shaped material. As a result, copper damage is prevented in advance.

In this case, as described in claim 2, the base material of the adhesive-attached tape-shaped material, tube-shaped material and sheet-shaped material can be made of a vinyl chloride resin material. As "vinyl chloride resin material",
In order to give flexibility to the PVC resin and improve the workability of the material, or to reduce the material cost, a plasticizer that has good mixability with the resin and excellent water resistance and electrical insulation Is desirable. This is because when the plasticizer migrates from the adhesive-attached tape-shaped material, the tube-shaped material, and the sheet-shaped material, the copper damage inhibitor is replenished to the HF electric wire.

Alternatively, as described in claim 3,
The base material of the tape-shaped material with adhesive, the tubular material and the sheet-shaped material is made of a halogen-free resin material containing no halogen element or containing halogen element at least lower than vinyl chloride resin. Good. As the base polymer of the “halogen-free resin material”, the same base polymer as the wire-covering material of the halogen-free insulated wire can be used. A low halogen bromide flame retardant is added to this as a flame retardant. A halogen-free flame retardant such as a metal hydrate such as magnesium hydroxide or aluminum hydroxide may be added.

In the case of claim 2 or 3, as described in claim 4, prevention of copper damage contained in the adhesive-attached tape-shaped material, tube-shaped material or sheet-shaped material The content of the agent may be in the range of 0.001 to 5 parts by weight with respect to 100 parts by weight of the base polymer of the base material. Base polymer 1 containing copper anti-corrosion agent as base material
This is because if it is less than 0.001 parts by weight with respect to 00 parts by weight, no effect is obtained, and if it exceeds 5 parts by weight, blooming occurs. Further, the content of the copper damage inhibitor is more preferably in the range of 0.001 part by weight to 3 parts by weight. This is because if the amount exceeds 3 parts by weight, the processability of the product tends to be slightly deteriorated.

In this case, as described in claim 5, it is preferable that the tape-shaped material, the tube-shaped material or the sheet-shaped material with the adhesive contains an antioxidant. This prevents the antiaging agent in the wire coating material of the halogen-free insulated wire from diffusing into the wire harness protection material, and prevents the deterioration of the heat aging performance of the halogen-free insulated wire.

In this case, as described in claim 6, the content of the anti-aging agent contained in the adhesive-attached tape-shaped article, tube-shaped article or sheet-like article is set to the anti-aging agent of the base material. It is preferable that the ratio of the ratio of the anti-aging agent in the electric wire be substantially equal to the ratio of the ratio of the antioxidant in the electric wire. Here, "the ratio amount of the antioxidant of the base material" means the ratio (%) of the antioxidant in the base material to the organic polymer, and "the ratio amount of the antioxidant of the electric wire" means in the electric wire. The ratio (%) of the antiaging agent to the organic polymer. This eliminates the concentration gradient of the antiaging agent between the halogen-free insulated wire and the wire harness protective material, and prevents the diffusion of the antiaging agent.

The wire harness protection material according to the second aspect of the present invention is an electric wire bundle in which electric wires covering an electric conductor containing copper are bundled and does not contain a halogen element at all as described in claim 7. The electric conductor is covered with a vinyl chloride resin material or a part of an electric wire bundle consisting of halogen-free insulated wires in which the electric conductor is covered with a halogen-free resin material whose halogen element content is at least lower than that of vinyl chloride resin. A wire harness protective material which is used by coating around a wire bundle which replaces a PVC insulated wire, wherein the tape-like material with an adhesive contains a copper damage inhibitor in the base material and / or the adhesive. The content of each is set in the range of 0.001 to 5 parts by weight with respect to 100 parts by weight of the base polymer of the base material.

According to the wire harness protection material of the present invention having the above-mentioned structure, since the tape-like material with an adhesive and / or the adhesive contains a copper damage-preventing agent, a halogen-free insulated wire is used. Even if the copper damage preventing agent is consumed, the copper damage preventing agent is replenished to the halogen-free insulated wire from the adhesive tape. As a result, copper damage is prevented in advance. Further, the content of the copper damage inhibitor is 0.001 part by weight to 5 parts by weight with respect to 100 parts by weight of the base polymer of the base material.
The range of parts by weight is that the effect is not effective when the content of the copper damage inhibitor is less than 0.001 part by weight with respect to 100 parts by weight of the base polymer of the base material, and blooms when it exceeds 5 parts by weight. is there. Further, the content of the copper damage inhibitor is 0.001
More preferably, it is in the range of 3 parts by weight to 3 parts by weight. This is because if the amount exceeds 3 parts by weight, the processability of the product tends to be slightly deteriorated.

[0023] In this case, as described in claim 8, the tape-like material with the pressure-sensitive adhesive contains an anti-aging agent in the base material and / or the pressure-sensitive adhesive, and the content of each of the base material and the pressure-sensitive adhesive is set to It is preferable that the ratio amount of the anti-aging agent in (1) is substantially equal to the ratio amount of the anti-aging agent in the electric wire. This prevents the anti-aging agent in the wire coating material of the halogen-free insulated wire from diffusing into the wire harness protection material,
This is because the deterioration of the heat aging performance of the halogen-free insulated wire is prevented.

The wire harness according to the third aspect of the present invention is
An electric wire bundle in which electric wires covering an electric conductor containing copper are bundled, wherein the electric wire bundle contains no halogen element or the halogen element content is at least lower than that of vinyl chloride resin. The wire bundle consisting of a halogen-free insulated wire covered with the electric conductor with a resin material, or the circumference of the wire bundle replaced with a PVC insulated wire covered with the electric conductor with a vinyl chloride resin. The gist of the present invention is that it is covered with the wire harness protection material according to item 8.

According to the wire harness of claim 9 having the above structure, even if the copper damage inhibitor is consumed in the halogen-free insulated wire, the wire harness protection material of claims 1 to 8, that is, A copper-damage-preventing agent is replenished to the halogen-free insulated wire from a tape-shaped material with adhesive, a tube-shaped material or a sheet-shaped material. As a result, copper damage is prevented in advance. Furthermore, since the wire harness protective material contains an anti-aging agent, the anti-aging agent in the wire coating material of the halogen-free insulated wire is prevented from diffusing into the wire harness protective material, and the heat of the halogen-free insulated wire is prevented. The deterioration of aging performance is prevented. Due to these synergistic effects, the wire harness has stable electric wire quality and exhibits good durability over a long period of time.

In this case, as described in claim 10, the insulated wire made of the halogen-free resin material is bundled, or a part of the bundle is replaced by the insulated wire made of the vinyl chloride resin material. It is desirable that the wire covering material of each wire of the wire bundle contains a copper damage inhibitor and / or an antioxidant. This is to prevent deterioration of the heat aging performance of the electric wire.

It is desirable that the copper damage preventing agent and the antiaging agent contained in each electric wire and wire harness protecting material are of the same type. There are various kinds of copper damage inhibitors and antiaging agents, but by using the same kind of each other, replenishment of copper damage preventive agents between halogen-free insulated wires, PVC insulated wires and wire harness protective materials This is because the elution and migration of the antiaging agent can be prevented more effectively.

[0028]

DETAILED DESCRIPTION OF THE INVENTION

The preferred embodiments of the present invention will be described in detail below. First, it was decided to prepare the following three types of insulating material coated electric wires used for various electric wire bundles to which the wire harness protective material according to the present embodiment is applied. The first is
The HF electric wire shown in Table 1A does not contain any halogen element in the electric wire coating material. As shown in Table 1A, in this HF electric wire, the electric wire coating material is mainly composed of a polyolefin-based polypropylene resin, and 80 parts by weight of magnesium hydroxide as a flame retardant is added to 100 parts by weight of the polypropylene resin. 3 parts by weight of the inhibitor (phenolic) and 1 part by weight of the copper damage inhibitor were used. The amount of anti-aging agent added is based on the total weight.
1.63 wt% (3/184 x 100 = 1.63 wt
%) And the ratio amount are 3% (3 ÷ 100 × 100 = 3%) in terms of the content of the anti-aging agent mixed in the HF electric wire with respect to the organic polymer (polypropylene).

[0029]

[Table 1A]

The second is shown in Table 1B and is made of PVC.
It is an electric wire, and the electric wire coating material does not contain an antioxidant at all. In this PVC electric wire, as shown in Table 1B, the electric wire coating material was 40 parts by weight of DINP (diisononyl phthalate) as a plasticizer with respect to 100 parts by weight of a polyvinyl chloride resin (polymerization degree P = 1300).
20 parts by weight of calcium carbonate was used as a filler, and 5 parts by weight of a zinc / calcium-based stabilizer was used as a stabilizer.

[0031]

[Table 1B]

The third is shown in Table 1C and is PVC
An electric wire in which an anti-aging agent is contained in the electric wire coating material (also simply referred to as "PVC anti-electric wire"). As shown in Table 1C, in this PVC old wire, the wire coating material is a polyvinyl chloride resin (degree of polymerization P = 130).
0) 40 parts by weight of DINP (diisononyl phthalate) as a plasticizer, 20 parts by weight of calcium carbonate as a filler, 5 parts by weight of a zinc-calcium type stabilizer as a stabilizer, and 4 parts by weight of an anti-aging agent per 100 parts by weight. What was compounded by 0.5 weight part was used. The amount of the antioxidant added is 2.65 wt% (4.5 ÷ 169.5 × 1) based on the total weight.
00 = 2.65 wt%), and the ratio amount is 3.21% (4.5%) in terms of the content ratio of the anti-aging agent blended in the PVC anti-corrosion wire to the organic polymer (PVC and DINP).
÷ 140 × 100 = 3.21%).

[0033]

[Table 1C]

In each of these three types of insulated electric wires, seven annealed copper wires having a diameter of 0.32 mm are twisted together to form a copper stranded wire having an outer diameter of about 1.0 mm.
~ Covered with each insulating material shown in Table 1C. For example, as the first HF electric wire, a resin composition shown in Table 1A was mixed with a biaxial kneader at a mixing temperature of 250 ° C. to form a pellet-shaped composition with a pelletizer, and the pellet composition was adjusted to 0. It is extruded to a thickness of 3 mm, and is formed around an electric conductor composed of seven stranded wires as an electric wire coating layer. The extrusion temperature at that time is 25
It is 0 ° C. Also, the second PVC wire and the third P wire
The VC anti-insulation wire was prepared by mixing the resin compositions shown in Table 1B or 1C at a mixing temperature of 180 ° C. with a twin-screw kneader to form a pelletized composition with a pelletizer, and using a extruder to obtain a VC composition. It is extruded to a thickness of 3 mm, and is formed around an electric conductor composed of seven stranded wires as an electric wire coating layer. The extrusion temperature is 180 ° C.

Next, the following five types of wire bundles to which the wire harness protective material according to this embodiment is applied are prepared. The first is the HF electric wire 30 in Table 1A.
It is an HF single wire bundle consisting of a book, and the other four are shown in Table 1.
HF electric wire of A and PVC electric wire of Table 1B or PVC of Table 1C
It is a mixed wire bundle consisting of an old wire. Various wire bundles
In all cases, the total number of electric wires is 30, but for mixed electric wire bundles, the mixing ratio (“the number of PVC electric wires or PVC protection wires: the number of HF electric wires”) is “25: 5”, respectively.
"Book", "20: 10", "10: 20" and "5: 25".

Next, the composition and test results of the wire harness protective material used in various examples will be described. First, Tables 2 to 5 show the compositions and test results of PVC adhesive tapes, tubes and sheets as wire harness protective materials, and Tables 2 to 3 contain copper damage inhibitors. Tables 4 to 5 correspond to those containing a copper damage inhibitor and an antioxidant.

[0037]

[Table 2]

[0038]

[Table 3]

[0039]

[Table 4]

[0040]

[Table 5]

Various compositions will be described. The tapes, tubes and sheets with PVC adhesives shown in Tables 2 to 5 are all polyvinyl chloride (PVC) resin (polymerization degree P
= 1300) as a base polymer is used. As the base material, 60 parts by weight of DOP (dioctyl phthalate) as a plasticizer, 20 parts by weight of calcium carbonate as a filler, and 100 parts by weight of PVC resin are used. A stabilizer containing 5 parts by weight of a zinc / calcium-based stabilizer was used. In the compounds shown in Tables 2 to 3, those containing no copper damage inhibitor at all ( Each conventional product), a product containing an appropriate amount of a copper damage inhibitor (Products 1-1 to 1-5 and 2-1 to 2-5 of this example) and a copper damage inhibitor in an excessive amount. Things (Comparative example products 1 and 2)
And the compounds shown in Tables 4 to 5 are those in which the copper damage inhibitor and the antioxidant are not mixed at all (each conventional product), the copper damage inhibitor and the aging. Those containing an appropriate amount of the inhibitor (Products 3-1 to 3-5 and 4-1 to 4-5 of this Example) and those containing an excessive amount of the copper damage inhibitor (Product 3 of Comparative Example and 4) was prepared. Incidentally, PVC
The blending amount of the anti-aging agent for the base material of the tube, tape and sheet is adjusted so as to be substantially equal to the above-mentioned proportion of 3% of the anti-aging agent for the HF electric wire. Here, the content rate to the organic polymer (PVC and DOP) is defined as a ratio amount, and the ratio amount is 3.12% (5/160 × 1).
00 = 3.12%).

In each of the tapes with a PVC pressure-sensitive adhesive shown in Tables 2 and 4, a pressure-sensitive adhesive made of a rubber-based material such as styrene-butadiene rubber (SBR) or NR was applied to the entire one side surface of the base material. The pressure-sensitive adhesive applied to the surface of the substrate is 30 parts by weight of NR (natural rubber), 20 parts by weight of zinc white, and 80 parts by weight of rosin resin with respect to 70 parts by weight of SBR (styrene-butadiene rubber). In the composition shown in Table 2, the compound containing no copper damage inhibitor (conventional product) and the compound containing an appropriate amount of copper damage inhibitor ( The products of the present examples 1-1 to 1-5) and a product (comparative example product 1) in which a copper damage inhibitor was excessively blended were prepared. In the products shown in Table 4, copper was added to the formulation. No anti-aging agent or anti-aging agent ( Coming products), those containing a suitable amount of copper inhibitor and antioxidant (embodiment articles 3-1～3-
5), which contains an excessive amount of copper damage inhibitor (comparative example product 3)
Prepared. The thickness of the pressure-sensitive adhesive layer was 0.02 mm, and the total thickness of the base material and the pressure-sensitive adhesive layer was 0.13 mm.
mm. The amount of the antioxidant on the base material of the PVC tube, the tape and the sheet is adjusted to be substantially equal to the above-mentioned proportion of 3% of the antioxidant on the HF electric wire. Here, the content rate with respect to the organic polymer (SBR, NR, and rosin-based resin) is defined as a ratio amount, and the ratio amount is adjusted to 3.3% (6/180 × 100 = 3.3%).

That is, a PVC tape with an adhesive containing the copper damage inhibitor and the antiaging agent shown in Tables 4 to 5,
The tube and the sheet correspond to the base material and, if applicable, the pressure-sensitive adhesive layer thereof, and the antioxidant shown in Tables 2 to 3, respectively.

Next, Tables 2 to 2 produced as described above
Tests and evaluations were performed on the conventional products, the products of the examples, and the products of the comparative examples shown in Table 5. First, the test method will be described. As the sample, the tape with PVC adhesive, the tube, and the sheet shown in each table were wound around the above-mentioned total of five types of HF single wire bundles and mixed wire bundles, respectively. The test was conducted as follows. That is, these samples were left in a constant temperature bath at 150 ° C. for 96 hours, and then the HF electric wire was taken out and wound with a 10φ mandrel to confirm the presence or absence of cracks in the covered portion.

Next, the test results will be described. Table 2
The test results in Table 5 are all distinguished only by the blending amount of the copper damage inhibitor, and do not refer to the type of wire bundle. This is because the difference in the type of wire bundle and the mixing ratio did not affect the test results. After all, the test results showed that the tape, the tube and the sheet with the PVC adhesive had good appearances in the conventional products, but it was judged that the HF electric wires had cracks and were defective (x), and in the comparative example products 1 to 4, Although the electric wire was not cracked, the tape with the PVC adhesive, the tube, and the sheet were judged to be defective (x) due to blooming. Then, the products of this example 1-1 to 1-5, 2-1 to 2-5, 3-1 to 3
For all of -5 and 4-1 to 4-5, the electric wire was not cracked, and the appearance was good (O), and it was determined that
The result that the overall evaluation was good (◯) was obtained.

From the above, a wire harness protective material (adhesive) mainly composed of a PVC resin material in which an appropriate amount of a copper damage inhibitor is mixed around an HF single wire bundle or a mixed wire bundle in which electric wires covering an annealed copper wire are bundled It has been found that good heat aging performance can be obtained for the HF electric wire by winding a tape-shaped material with an agent, a tube-shaped material and a sheet-shaped material. This is because even if the copper damage prevention agent contained in the HF electric wire is consumed, the copper damage prevention agent contained in the wire harness protective material spreads on the plasticizer on the HF electric wire, so that It is considered that this is because the copper damage inhibitor is replenished.

If the anti-aging agent of the HF electric wire is contained in the wire harness protective material in an amount substantially equal to that of the anti-aging agent contained in the HF electric wire, the anti-aging agent of the HF electric wire becomes a plasticizer. It will not be extracted due to influence. this is,
By making the proportion of the anti-aging agent in the wire harness protective material almost equal to the proportion of the anti-aging agent in the HF electric wire, even if the plasticizer migrates to the HF electric wire, the concentration gradient (of the anti-aging agent) is related. It is considered that this is because the antiaging agent of the HF electric wire is not extracted.

Tables 6 to 9 show the compositions and test results of tapes, tubes and sheets with an HF adhesive as a wire harness protective material, and Tables 6 to 7 contain copper damage inhibitors. Tables 8 to 9 correspond to those containing a copper damage inhibitor and an antioxidant.

[0049]

[Table 6]

[0050]

[Table 7]

[0051]

[Table 8]

[0052]

[Table 9]

Various compositions will be described. The tapes, tubes and sheets with HF adhesive shown in Table 6 to Table 9 are
Both use a base material made of a polyolefin resin as a base polymer. As the base material, 3 parts by weight of a bromine-based flame retardant is added to 100 parts by weight of the polyolefin resin.
Further, using 1.5 parts by weight of antimony trioxide, the compositions shown in Tables 6 to 7 in which no copper damage inhibitor is added to the composition (each conventional product) , Those containing an appropriate amount of copper damage inhibitor (Products 5-1 to 5-5 and 6-1 to 6-5 of this example) and those containing excess copper damage inhibitor (Comparative product) 5 and 6) are prepared and shown in Tables 8 to 9, the compound does not contain a copper damage inhibitor and an antioxidant at all (conventional products), copper damage An appropriate amount of an inhibitor and an antiaging agent are blended (Products 7-1 to 7-5 and 8 of this Example)
-1 to 8-5) and those in which the copper damage inhibitor was excessively blended (Comparative Products 7 and 8) were prepared. In addition, the compounding amount of the antioxidant of the base material of the HF tube, the tape and the sheet is
It is adjusted to be approximately equal to the above-mentioned proportion of the anti-aging agent of the HF electric wire of 3%. Here, the content ratio to the organic polymer (polyolefin) is defined as a ratio amount, and the ratio amount is 3.5% (3.5 / 100 × 100).
= 3.5%).

The HF adhesive tapes shown in Tables 6 and 8 are the same as the PVC adhesive tapes, that is, styrene-butadiene rubber (SBR) is applied to the entire one side surface of the base material. An adhesive made of a rubber-based material such as NR or NR is applied. The adhesive applied to the surface of the base material is 30 parts by weight of NR (natural rubber) with respect to 70 parts by weight of SBR (styrene-butadiene rubber). A mixture of 20 parts by weight of zinc oxide and 80 parts by weight of rosin resin was used, and in the composition shown in Table 6, a composition containing no copper damage inhibitor (conventional product). ), And an appropriate amount of a copper damage inhibitor (the product 5 of this example)
-1 to 5-5), a product (comparative example product 5) in which a copper damage inhibitor was excessively blended was prepared, and in the products shown in Table 8, the copper damage inhibitor and aging were added to the formulation. One containing no inhibitor (conventional product), one containing an appropriate amount of copper damage inhibitor and antiaging agent (Products 7-1 to 7-5 of this example), and one containing excessive copper damage inhibitor The prepared product (Comparative example product 7) was prepared. The thickness of the adhesive layer is 0.02 mm, and the total thickness of the base material and the adhesive layer is 0.13 mm. In addition, the amount of the antioxidant of the HF tube, the tape and the sheet is the above-mentioned ratio of the antioxidant of the HF wire 3
It is adjusted to be almost equal to%. Here, the content rate to the organic polymer (SBR, NR and rosin-based resin) is defined as a percentage amount, and the percentage amount is 3.3%.
It is adjusted to (6/180 × 100 = 3.3%).

That is, the HF tape with adhesive, tube and sheet containing the copper damage inhibitor and the antiaging agent shown in Tables 8 to 9 are used as the base material and, if applicable, the adhesive layer. Respectively correspond to the formulations shown in Tables 6 to 7 with the addition of an antioxidant.

Next, Table 6 to Table 6 produced as described above.
Tests and evaluations were performed on the conventional product, each of the example products and the comparative example product shown in Table 9. First, the test method will be described. As a sample, the tape with HF adhesive, the tube, and the sheet shown in each table were wound around the above-mentioned total of five types of HF single wire bundles and mixed wire bundles, respectively. The test was conducted as follows. That is, these samples were left in a constant temperature bath at 150 ° C. for 96 hours, and then the HF electric wire was taken out and wound with a 10φ mandrel to confirm the presence or absence of cracks in the covered portion.

Next, the test results will be described. The test results in Tables 6 to 9 are all distinguished only by the blending amount of the copper damage inhibitor, and do not refer to the type of electric wire bundle. This is because the difference in the type of wire bundle and the mixing ratio did not affect the test results. After all, the test result shows that the tape, the tube and the sheet with the HF adhesive had good appearances in the conventional products, but it was judged that the HF electric wire had cracks and was defective (x). The wire did not crack, but HF
The adhesive-attached tape, tube and sheet caused blooming and were judged to be defective (x). And this example product 5
-1 to 5-5, 6-1 to 6-5, 7-1 to 7-5, 8-
No cracks are generated in the electric wire in any of 1 to 8-5,
The appearance was judged to be good (◯), and the result of good overall evaluation (◯) was obtained.

From the above, a wire harness protective material mainly composed of a brominated polyolefin resin material in which an appropriate amount of a copper damage inhibitor is blended around an HF single wire bundle or a mixed wire bundle in which electric wires covering an annealed copper wire are bundled (Tape with adhesive,
If you wrap a tube or sheet)
It has been found that good heat aging performance can be obtained for HF wires. It is considered that the copper damage due to the influence of moisture in the air and the adhesive can be suppressed also by the wire harness protective material.

If the anti-aging agent of the HF electric wire is contained in the wire harness protective material in an amount substantially equal to that of the anti-aging agent contained in the HF electric wire, the anti-aging agent of the HF electric wire protects the wire harness. There is no transfer to wood. This is because it is considered that the concentration gradient becomes equal by making the proportion amount of the antiaging agent almost equal to the proportion amount of the antiaging agent of the HF electric wire.

The present invention is not limited to the above-described embodiments, and various modifications can be made without departing from the spirit of the present invention. For example, in the above-mentioned various examples, the PVC resin type and the polyolefin type are shown as the wire harness protective material, but the composition is not limited to those of the examples. Further, as the polyolefin-based wire harness protective material, a material containing a small amount of a bromine-based flame retardant (low halogen-based material) is shown, but a wire harness protective material containing no halogen element at all may be used.

In short, the gist of the present invention is to prevent copper damage to the HF electric wire coating material by blending a copper damage preventive agent for these adhesive-attached tape-like material, tube-like material or sheet-like material as a wire harness protection material. By replenishing the agent or in a state in which it can be replenished, the HF electric wire and the wire harness protective material or the PVC electric wire can be used both in the state of being used as the HF single electric wire and in the state of being mixed with the PVC electric wire. It is to avoid the adverse effect during the period, to achieve stable wire quality as a wire harness and to achieve permanent use by extending the life of the wire.

[0062]

The wire harness protective material according to the first aspect of the present invention is such that the tape-like material, the tube-like material or the sheet-like material with the adhesive contains a copper damage inhibitor. The wire bundle is a bundle of wires covering an electric conductor containing copper, and is effective in suppressing the copper damage of the wire bundle made of a halogen-free insulated wire.

The wire harness protective material according to claim 2 is a halogen-free insulated wire since the base material of the tape-shaped material, the tube-shaped material or the sheet-shaped material with the adhesive is a vinyl chloride resin material. Even if the copper damage inhibitor is consumed, the copper damage inhibitor can be replenished from the base material to the halogen-free insulated wire.

In the wire harness protection material according to the third aspect of the present invention, since the base material of the adhesive-attached tape-shaped material, tube-shaped material or sheet-shaped material is made of a halogen-free resin material, moisture in the air or There is an effect that copper damage due to the influence of an adhesive or the like can be suppressed.

In the wire harness protection material according to claim 4, the content of the copper damage inhibitor contained in the tape-shaped material, the tube-shaped material or the sheet-shaped material with the adhesive is 100 weight% of the base polymer of the base material. 0.001 parts by weight to parts
Since the amount is in the range of 5 parts by weight, there is an effect that the deterioration of the heat aging performance can be prevented.

The wire harness protection material according to claim 5 is a tape-shaped material, a tube-shaped material or a sheet-shaped material with an adhesive containing an antioxidant.
There is an effect that the deterioration of the electric wire can be prevented.

In the wire harness protective material according to claim 6, the content of the antioxidant contained in the tape-shaped material, the tube-shaped material or the sheet-shaped material with the adhesive is determined by the ratio of the antioxidant of the base material. Since the amount is made substantially equal to the proportion amount of the anti-aging agent of the electric wire, there is an effect that diffusion of the anti-aging agent from the halogen-free insulated electric wire to the wire harness protective material is prevented.

The wire harness protective material according to claim 7 is a tape-like base material with an adhesive and / or an adhesive material containing a copper damage inhibitor, and therefore an electrical conductor containing copper. Which is a bundle of electric wires for covering the electric wire, wherein the electric conductor bundle is covered with a halogen-free resin material to prevent copper damage from the electric wire bundle, and further, the base material and / or Alternatively, the content of the copper damage inhibitor contained in the adhesive material is set to 0.001 part by weight to 5 parts by weight with respect to 100 parts by weight of the base polymer of the base material. This has the effect of preventing the decrease.

The wire harness protection material according to claim 8 prevents deterioration of the wire because the base material and / or the adhesive material of the tape-like material with the adhesive contains an antioxidant. Furthermore, the content of the antioxidant contained in the base material and / or the pressure-sensitive adhesive may be adjusted so that the ratio of the antioxidant of the base material becomes substantially equal to the content of the antioxidant of the electric wire. Therefore, there is an effect that the diffusion of the anti-aging agent from the halogen-free insulated wire to the wire harness protection material is prevented.

A wire harness according to a ninth aspect is an electric wire bundle in which electric wires covering an electric conductor containing copper are bundled,
Claim the wire bundle consisting of a halogen-free insulated wire in which the electric conductor is covered with a halogen-free resin material or a part of the wire bundle in which a part thereof is replaced with a PVC insulated wire covered with the electric conductor in a vinyl chloride resin material. Since it is covered with the wire harness protective material according to items 1 to 8, there is an effect that the deterioration of heat aging performance can be prevented and the service life becomes long.

A wire harness according to a tenth aspect of the present invention is an electric wire bundle formed by bundling insulated electric wires made of a halogen-free resin material or a part of the electric wire bundle made by bundling an insulated electric wire made of the vinyl chloride resin material. Since the electric wire coating material contains a copper damage inhibitor and / or an antiaging agent, it is possible to replenish the copper damage preventive agent from the PVC anti-aging electric wire to the HF electric wire as well as from the HF electric wire. This has the effect of suppressing the diffusion of the anti-aging agent into the electric wire.

─────────────────────────────────────────────────── ─── Continuation of front page (51) Int.Cl. ⁷ Identification code FI theme code (reference) H02G 1/06 501 H02G 1/06 501B 3/04 3/04 J 3/38 3/28 F (72) Inventor Mamoru Kondo 1-14 Nishi-Suehiro-cho, Yokkaichi-shi, Mie Sumitomo Wiring Systems Co., Ltd. (72) Inventor Tatsuya Hase 1-1-14 Nishi-Suehiro-cho, Yokkaichi-shi, Mie Sumitomo Wiring Systems Co., Ltd. (72) Inventor Exit Yoshiharu 1-14 Nishisuehiro-cho, Yokkaichi-shi, Mie Sumitomo Wiring Systems Co., Ltd. (72) Inventor Jun Yoshimoto 1-1-14 Nishisuehiro-cho, Yokkaichi-shi, Mie Sumitomo Wiring Co., Ltd. (72) Inventor Tetsuya Nakamura 1-14 Nishisuehiro-cho, Yokkaichi-shi, Mie Sumitomo Wiring Systems Co., Ltd. (72) Inventor Motoya Kawakita 1-1-14 Nishisuehiro-cho, Yokkaichi-shi, Mie Sumitomo Wiring Systems Co., Ltd. (72) Takatsugu Yamashita West end of Yokkaichi City, Mie Prefecture 1-14 Machi Sumitomo Wiring Systems Co., Ltd. (72) Inventor Hiroshi Hayami 1-1-3 Shimaya, Konohana-ku, Osaka City Sumitomo Electric Industries, Ltd. F-term (reference) 4J002 BB031 BB041 BB111 BB151 BB171 BB201 BP021 EJ017 FD077 FD206 GQ01 5G309 AA11 5G333 AA03 AA10 AB16 AB29 CB15 CB16 CC04 5G357 DA01 DB03 DC12 DD01 DD05 DG06 5G363 AA05 BA02 DA16 DC02

Claims (10)

[Claims] 1. An electric wire bundle in which electric wires covering an electric conductor containing copper are bundled, the electric wire being made of a halogen-free resin material containing no halogen element or having a halogen element content at least lower than that of vinyl chloride resin. With an adhesive that is used by coating a wire bundle consisting of a halogen-free insulated wire covered with a conductor or a part thereof around a wire bundle formed by replacing a PVC insulated wire covered with the electric conductor with a vinyl chloride resin material A wire harness protective material in a tape shape, a tube shape, or a sheet shape, wherein the adhesive tape-shaped material, the tube-shaped material, and the sheet-shaped material contain a copper damage inhibitor. Harness protection material. 2. The wire harness protective material according to claim 1, wherein the base material of the tape-shaped material with adhesive, the tube-shaped material, and the sheet-shaped material is made of a vinyl chloride resin material. 3. The base material of the tape-shaped material, the tube-shaped material, and the sheet-shaped material with an adhesive is made of a halogen-free resin material containing no halogen element or containing halogen element at least lower than vinyl chloride resin. The wire harness protection material according to claim 1, wherein 4. The content of the copper damage inhibitor contained in the pressure-sensitive adhesive-attached tape-shaped material, tube-shaped material or sheet-shaped material is 0.00 with respect to 100 parts by weight of the base polymer of the base material.
The wire harness protective material according to claim 2 or 3, wherein the amount is in the range of 1 to 5 parts by weight. 5. The wire harness protective material according to claim 4, wherein the tape-shaped material, the tube-shaped material, or the sheet-shaped material with the adhesive contains an antioxidant. 6. The content of the anti-aging agent contained in the tape-shaped material, the tube-shaped material or the sheet-shaped material with the adhesive, the ratio of the anti-aging agent of the base material is the ratio of the anti-aging agent of the electric wire. The wire harness protection material according to claim 5, wherein the wire harness protection material is substantially equal to the quantity. 7. An electric wire bundle in which electric wires covering an electric conductor containing copper are bundled, the electric wire being made of a halogen-free resin material containing no halogen element or having a halogen element content at least lower than that of vinyl chloride resin. Wire harness protection used by covering a wire bundle consisting of a halogen-free insulated wire covered with a conductor or a part thereof around a wire bundle formed by replacing the PVC insulated wire covered with the electric conductor with a vinyl chloride resin material The tape-shaped material with a pressure-sensitive adhesive comprises a base material and / or a pressure-sensitive adhesive containing a copper damage inhibitor, the content of each of which is 0. A wire harness protective material, characterized in that the amount is in the range of 001 parts by weight to 5 parts by weight. 8. The tape-shaped product with an adhesive contains an anti-aging agent in its base material and / or an adhesive, and the content of each of the anti-aging agent in the base material is the amount of the anti-aging agent of the electric wire. The wire harness protection material according to claim 7, wherein the proportion of the inhibitor is substantially equal to the proportion of the inhibitor. 9. An electric wire bundle in which electric wires covering an electric conductor containing copper are bundled, the electric wire being made of a halogen-free resin material containing no halogen element or containing halogen element at least lower than vinyl chloride resin. A wire bundle consisting of a halogen-free insulated wire covered with a conductor or a part of a wire bundle formed by replacing a part thereof with a PVC insulated wire covered with the electric conductor with a vinyl chloride resin material.
A wire harness which is covered with the wire harness protective material according to any one of items 1 to 8. 10. The wire covering material of each wire of the wire bundle made of the halogen-free insulated wire or a part of the wire bundle in which the PVC insulated wire is replaced with a copper damage inhibitor and / or an antioxidant. 10. The method according to claim 9, wherein
Wire harness described in.