JP5282163B1 - Flame-retardant resin composition and cable using the same - Google Patents

Abstract

The present invention provides a flame retardant resin composition and the like that can ensure excellent flame retardancy while ensuring excellent mechanical properties and terminal processability.
SOLUTION: The base resin, calcium carbonate particles blended at a ratio of 10 parts by mass or more and 120 parts by mass or less with respect to 100 parts by mass of the base resin, and 3 parts by mass greater than 1 part by mass with respect to 100 parts by mass of the base resin. An average particle diameter of calcium carbonate particles, including a silicone compound compounded at a ratio of less than or equal to parts and a fatty acid-containing compound compounded at a ratio of greater than 3 parts by mass and less than or equal to 20 parts by mass relative to 100 parts by mass of the base resin Is a flame retardant resin composition having a value greater than 1.8 μm and not greater than 5.0 μm.
[Selection figure] None

Description

  The present invention relates to a flame retardant resin composition and a cable using the same.

  So-called eco-materials are widely used for cable coverings, cable sheaths, tubes, tapes, packaging materials, building materials, and the like.

  As such an ecomaterial, for example, a composition obtained by adding calcium carbonate as a flame retardant to a polyolefin resin and adding a silicone compound such as silicone oil or magnesium stearate as a flame retardant aid is known. (See Patent Document 1 below).

JP-A-9-169918

  However, it has been difficult to say that the composition described in Patent Document 1 has sufficient flame retardancy. Here, if the amount of the flame retardant added is increased, the flame retardancy can be improved. However, in this case, the mechanical properties and terminal processability of the composition are lowered.

  For this reason, the flame-retardant resin composition which can also ensure the outstanding flame retardance, ensuring the outstanding mechanical characteristic and terminal processability was calculated | required.

  The present invention has been made in view of the above circumstances, and uses a flame retardant resin composition capable of ensuring excellent flame retardancy while ensuring excellent mechanical properties and terminal processability, and the same. The purpose is to provide a cable.

  In order to solve the above-mentioned problems, the present inventors have studied by paying particular attention to calcium carbonate which is a flame retardant. As a result, the present inventors set the average particle diameter of calcium carbonate within a specific range, and when the calcium carbonate particles, the silicone-based compound, and the fatty acid-containing compound are blended at a specific ratio with respect to the base resin, respectively. We found that the problem could be solved.

That is, the present invention comprises a base resin, calcium carbonate particles blended at a ratio of 10 parts by mass to 120 parts by mass with respect to 100 parts by mass of the base resin, and 1 part by mass with respect to 100 parts by mass of the base resin. Including a silicone compound compounded at a ratio of 3 parts by mass or less and a fatty acid-containing compound compounded at a ratio of greater than 3 parts by mass and 20 parts by mass or less with respect to 100 parts by mass of the base resin, Ri average particle size greater 5.0μm der less than 1.8μm particles, said base resin is a polyolefin compound der Ru flame retardant resin composition.

  According to the flame retardant resin composition of the present invention, it is possible to ensure excellent flame retardancy while securing excellent mechanical properties and terminal processability.

  In addition, the present inventors speculate as follows about the reason why more excellent flame retardancy is obtained in the flame retardant resin composition of the present invention.

  That is, a surface barrier layer is formed at the time of combustion by using calcium carbonate particles, a silicone compound, and a fatty acid-containing compound. At this time, if the surface barrier layer is dense and such a dense surface barrier layer is quickly formed, it is considered that the flame retardant effect is enhanced. In order for the dense surface barrier layer to be formed quickly, it is necessary to close the gaps between the particles of calcium carbonate or decomposition products constituting the surface barrier layer as quickly as possible. In this regard, as in the present invention, when the average particle diameter of the calcium carbonate particles is larger than 1.8 μm, the specific surface area decreases, so that the gaps between the calcium carbonate particles can be quickly closed. As a result, it is considered that the formation speed of the dense surface barrier layer is increased and the flame retardant effect is enhanced.

  Moreover, the present inventors infer the reason why excellent terminal processability is obtained in the flame retardant resin composition as follows.

  That is, the terminal processability is considered to depend on the elongation of the base resin. The smaller the elongation of the base resin, the easier it is to perform terminal processing, that is, mechanically remove the flame retardant resin composition. The elongation of the base resin becomes smaller as the average particle size of the calcium carbonate particles is larger and the blending amount of the silicone compound is smaller. For this reason, when the average particle diameter of the calcium carbonate particles is larger than 1.8 μm and not larger than 5.0 μm, and the compounding amount of the silicone compound is larger than 1 part by mass and not larger than 3 parts by mass, the terminal processability is further improved. The present inventors speculate that this may be improved.

  Moreover, in the said flame-retardant resin composition, it is preferable that the said fatty acid containing compound is mix | blended in the ratio of 10 mass parts or less with respect to 100 mass parts of said base resins.

  In this case, superior mechanical properties can be obtained as compared with the case where the proportion of the fatty acid-containing compound is larger than 10 parts by mass.

  In the flame retardant resin composition, the calcium carbonate particles are, for example, heavy calcium carbonate or light calcium carbonate.

  In the flame retardant resin composition, the silicone compound is preferably a silicone gum.

  In this case, bloom is less likely to occur.

  In the flame retardant resin composition, the fatty acid-containing compound is preferably magnesium stearate. In this case, more excellent flame retardancy can be obtained as compared with the case where the fatty acid-containing compound is not magnesium stearate.

  In the flame retardant resin composition, the fatty acid-containing compound may be stearic acid.

  Moreover, this invention is equipped with the insulated wire which has a conductor and the insulating layer which coat | covers the said conductor, and the said insulating layer is a cable comprised with the flame-retardant resin composition mentioned above.

  The present invention further includes a conductor, an insulated wire having an insulating layer covering the conductor, and a sheath covering the insulating layer, wherein at least one of the insulating layer and the sheath is the above-described flame-retardant resin. A cable composed of the composition.

In the present invention, the “average particle size” means that the area S of the two-dimensional image when a plurality of calcium carbonate particles are observed with an SEM is obtained, and these areas S are considered to be equal to the area of a circle, respectively. From these areas, the following formula:
R = 2 × (S / π) ^1/2
The average value of R calculated based on

  ADVANTAGE OF THE INVENTION According to this invention, the flame retardant resin composition which can ensure the outstanding flame retardance while ensuring the outstanding mechanical characteristic and terminal workability, and a cable using the same are provided.

It is a partial side view which shows one Embodiment of the cable of this invention. It is sectional drawing along the II-II line of FIG.

  Hereinafter, embodiments of the present invention will be described in detail with reference to FIGS. 1 and 2.

[cable]
FIG. 1 is a partial side view showing an embodiment of a cable according to the present invention, and shows a flat cable. FIG. 2 is a cross-sectional view taken along the line II-II in FIG. As shown in FIGS. 1 and 2, the flat cable 10 includes two insulated wires 4 and a sheath 3 that covers the two insulated wires 4. The insulated wire 4 includes an inner conductor 1 and an insulating layer 2 that covers the inner conductor 1.

  Here, the insulating layer 2 and the sheath 3 are made of a flame retardant resin composition, and the flame retardant resin composition is 10 parts by mass or more and 120 parts by mass with respect to 100 parts by mass of the base resin and the base resin. Calcium carbonate particles blended in the following proportion, silicone compound blended in a proportion of greater than 1 part by weight and less than or equal to 3 parts by weight with respect to 100 parts by weight of the base resin, and 3 parts by weight with respect to 100 parts by weight of the base resin And a fatty acid-containing compound blended at a ratio of 20 parts by mass or less. Here, the average particle diameter of the calcium carbonate particles is larger than 1.8 μm and not larger than 5.0 μm, and the base resin is a polyolefin compound.

  The insulating layer 2 and the sheath 3 composed of the flame retardant resin composition can ensure excellent flame retardancy while ensuring excellent mechanical properties and terminal processability.

[Cable manufacturing method]
Next, the manufacturing method of the flat cable 10 mentioned above is demonstrated.

(Inner conductor)
First, the inner conductor 1 is prepared. The inner conductor 1 may be composed of only one strand, or may be configured by bundling a plurality of strands. Further, the inner conductor 1 is not particularly limited with respect to the conductor diameter, the material of the conductor, and the like, and can be appropriately determined according to the application.

(Flame retardant resin composition)
On the other hand, the flame retardant resin composition is prepared. As described above, the flame retardant resin composition includes the base resin, calcium carbonate particles blended at a ratio of 10 parts by mass to 120 parts by mass with respect to 100 parts by mass of the base resin, and 100 parts by mass of the base resin. On the other hand, a silicone compound compounded at a ratio of more than 1 part by mass and 3 parts by mass or less and a fatty acid-containing compound compounded at a ratio of more than 3 parts by mass and 20 parts by mass or less with respect to 100 parts by mass of the base resin. Contains.

(Base resin)
Although base resin will not be restrict | limited especially if it is resin, As such resin, polyolefin compounds, such as polyethylene and a polypropylene, ethylene ethyl acrylate copolymer (EEA), ethylene methyl acrylate copolymer (EMA) ) And styrene butylene rubber (SBR).

(Calcium carbonate particles)
The calcium carbonate particles may be either heavy calcium carbonate or light calcium carbonate. Among them, heavy calcium carbonate is preferable because it is easily available and is inexpensive.

  The average particle diameter of the calcium carbonate particles is larger than 1.8 μm and not larger than 5.0 μm. When the average particle diameter of the calcium carbonate particles is within the above range, more excellent terminal processability can be obtained. That is, compared to the case where the average particle diameter is 1.8 μm or less, when the insulating layer 2 is peeled off using a stripper, the insulating layer 2 is less likely to be stretched, and the average particle diameter exceeds 5.0 μm. The inner conductor 1 and the coating itself are less likely to be damaged.

  The calcium carbonate particles are blended at a ratio of 10 parts by mass or more and 120 parts by mass or less with respect to 100 parts by mass of the base resin. In this case, more excellent flame retardancy can be obtained as compared with the case where the proportion of the calcium carbonate particles is less than 10 parts by mass with respect to 100 parts by mass of the base resin.

  Further, when the blending ratio of the calcium carbonate particles with respect to 100 parts by mass of the base resin is within the above range, the flame retardant resin composition is compared with the case where the blending ratio of the calcium carbonate particles with respect to 100 parts by mass of the base resin is larger than 120 parts by mass. The mechanical properties of the object can be further improved.

  The calcium carbonate particles are preferably blended at a ratio of 80 parts by weight or less, more preferably blended at a ratio of 50 parts by weight or less, and further preferably blended at a ratio of 40 parts by weight or less. It is still more preferable to mix | blend in the ratio of 30 mass parts or less, and it is especially preferable to mix | blend in the ratio of 20 mass parts or less. When calcium carbonate particles are blended in the above range, compared with the case where the blending ratio exceeds the upper limit of each of the above ranges, the mechanical properties are further improved while sufficiently ensuring the flame retardancy of the flame retardant resin composition. It can be improved sufficiently.

(Silicone compound)
The silicone-based compound functions as a flame retardant aid, and examples thereof include polyorganosiloxane. Here, the polyorganosiloxane has a siloxane bond as a main chain and an organic group in a side chain. Examples of the organic group include a methyl group, a vinyl group, an ethyl group, a propyl group, and a phenyl group. Specific examples of the polyorganosiloxane include dimethylpolysiloxane, methylethylpolysiloxane, methyloctylpolysiloxane, methylvinylpolysiloxane, methylphenylpolysiloxane, and methyl (3,3,3-trifluoropropyl) polysiloxane. Is mentioned. Examples of the polyorganosiloxane include silicone powder, silicone gum, and silicone resin. Among these, silicone gum is preferable. In this case, bloom is less likely to occur.

  As described above, the silicone-based compound is blended in a proportion of greater than 1 part by mass and less than or equal to 3 parts by mass with respect to 100 parts by mass of the base resin. In this case, more excellent flame retardancy can be obtained as compared with the case where the ratio of the silicone compound is 1 part by mass or less.

  Moreover, when the compounding ratio of the silicone compound relative to 100 parts by mass of the base resin is within the above range, superior terminal processability can be obtained as compared with the case where the compounding ratio of the silicone compound is larger than 3 parts by mass.

  The silicone compound may be attached in advance to the surface of the calcium carbonate particles. In this case, it is preferable that the entire calcium carbonate particles contained in the flame retardant resin composition are coated with a silicone compound. In this case, since the calcium carbonate particles can be easily dispersed in the base resin, the uniformity of characteristics in the flame retardant resin composition is further improved.

  As a method for adhering a silicone compound to the surface of calcium carbonate, for example, a silicone compound is added to and mixed with calcium carbonate particles to obtain a mixture, and then the mixture is dried at 40 to 75 ° C. for 10 to 40 minutes. The dried mixture can be obtained by pulverizing with a Henschel mixer, an atomizer or the like.

(Fatty acid-containing compound)
The fatty acid-containing compound functions as a flame retardant aid. The fatty acid-containing compound refers to a compound containing a fatty acid or a metal salt thereof. Here, as the fatty acid, for example, a fatty acid having 12 to 28 carbon atoms is used. Examples of such fatty acids include lauric acid, myristic acid, palmitic acid, stearic acid, tuberculostearic acid, oleic acid, linoleic acid, arachidonic acid, behenic acid and montanic acid. Among these, as the fatty acid, stearic acid or tuberculostearic acid is preferable, and stearic acid is particularly preferable. In this case, more excellent flame retardancy can be obtained as compared with the case of using a fatty acid other than stearic acid or tuberculostearic acid.

  Examples of the metal constituting the fatty acid metal salt include magnesium, calcium, zinc and lead. As the fatty acid metal salt, magnesium stearate is preferred. In this case, more excellent flame retardancy can be obtained as compared with the case of using a fatty acid metal salt other than magnesium stearate.

  As described above, the fatty acid-containing compound is blended at a ratio of more than 3 parts by mass and 20 parts by mass or less with respect to 100 parts by mass of the base resin. In this case, more excellent flame retardancy can be obtained as compared with the case where the proportion of the fatty acid-containing compound is 3 parts by mass or less.

  Further, when the blending ratio of the fatty acid-containing compound with respect to 100 parts by mass of the base resin is within the above range, the terminal processing is more excellent than when the blending ratio of the fatty acid-containing compound with respect to 100 parts by mass of the base resin is larger than 20 parts by mass. Sex is obtained.

  It is preferable that a fatty acid containing compound is mix | blended in the ratio of 10 mass parts or less. In this case, superior mechanical properties can be obtained as compared with the case where the proportion of the fatty acid-containing compound is larger than 10 parts by mass.

  The flame retardant resin composition may further contain a filler such as an antioxidant, an ultraviolet deterioration inhibitor, a processing aid, a color pigment, a lubricant, and carbon black as necessary.

  The flame retardant resin composition can be obtained by kneading a base resin, calcium carbonate, a silicone-based compound, a fatty acid-containing compound, and the like. The kneading can be performed with a kneading machine such as a Banbury mixer, a tumbler, a pressure kneader, a kneading extruder, a twin screw extruder, a mixing roll, and the like. At this time, from the viewpoint of improving the dispersibility of the silicone compound, a part of the base resin and the silicone compound are kneaded, and the obtained master batch (MB) is mixed with the remaining base resin, calcium carbonate particles and fatty acid. You may knead | mix with a containing compound etc.

  Next, the inner conductor 1 is covered with the flame retardant resin composition. Specifically, the flame retardant resin composition is melt kneaded using an extruder to form a tubular extrudate. Then, the tubular extrudate is continuously coated on the inner conductor 1. Thus, the insulated wire 4 is obtained.

(sheath)
Finally, two insulated wires 4 obtained as described above are prepared, and these insulated wires 4 are covered with a sheath 3 produced using the above-mentioned flame-retardant resin composition. The sheath 3 protects the insulating layer 2 from physical or chemical damage.

  The flat cable 10 is obtained as described above.

  The present invention is not limited to the above embodiment. For example, although the flat cable 10 has two insulated wires 4 in the above embodiment, the cable of the present invention is not limited to the flat cable, and only one insulated wire 4 is provided inside the sheath 3. You may have, and you may have three or more. A resin portion made of polypropylene or the like may be provided between the sheath 3 and the insulated wire 4. Furthermore, the cable of the present invention may further include an outer conductor between the sheath 3 and the insulated wire 4 like a coaxial cable.

  Moreover, in the said embodiment, although the insulating layer 2 and the sheath 3 of the insulated wire 4 are comprised with said flame-retardant resin composition, the insulating layer 2 is comprised with normal insulating resin, and only the sheath 3 is insulated. The layer 2 may be composed of a flame retardant resin composition.

  Furthermore, in the said embodiment, although the cable has a sheath, the cable does not need to have a sheath. That is, the cable may be composed of only insulated wires.

  Furthermore, in the above embodiment, the flame retardant resin composition of the present invention is used as a material constituting the insulating layer and the sheath of the cable. However, the flame retardant resin composition of the present invention is a tube, tape, or packaging. It can also be used for materials and building materials.

  Hereinafter, the content of the present invention will be described more specifically with reference to examples and comparative examples, but the present invention is not limited to the following examples.

(Examples 1-16 and Comparative Examples 1-7)
Polyethylene (PE), silicone masterbatch (silicone MB), fatty acid-containing compound and calcium carbonate particles are blended in the blending amounts shown in Tables 1 to 5, and kneaded at 160 ° C. for 15 minutes with a Banbury mixer, flame retardant resin A composition was obtained. In Tables 1 to 5, the unit of the blending amount of each blending component is part by mass. Moreover, in Tables 1-5, the compounding quantity of the column of "PE" is not 100 mass parts. However, PE is also contained in the silicone MB, and if the blending amount in the “PE” column and the blending amount of PE in the silicone MB are summed, the total amount is 100 parts by mass.

Specific examples of the polyethylene, silicone MB, calcium carbonate particles, fatty acid-containing compound, and n-octadecane as hydrocarbons were as follows.
(1) Polyethylene (PE)
Excellen GMH GH030 (trade name, manufactured by Sumitomo Chemical Co., Ltd.)
(2) Silicone MB
X-22-2125H (trade name, manufactured by Shin-Etsu Chemical Co., Ltd.)
Contains 50% silicone gum and 50% PE by weight (3) Calcium carbonate particles A) Calcium carbonate particles (average particle size 1.8 μm)
Softon 1200 (trade name, manufactured by Shiraishi Calcium)
B) Calcium carbonate particles (average particle size 2.2 μm)
Softon 1000 (trade name, manufactured by Shiraishi Calcium)
C) Calcium carbonate particles (average particle size 3.6 μm)
BF100 (trade name, manufactured by Shiraishi Calcium Co., Ltd.)
D) Calcium carbonate particles (average particle size 5.0 μm)
BF200 (trade name, manufactured by Shiraishi Calcium)
E) Calcium carbonate particles (average particle size 8.0 μm)
BF300 (trade name, manufactured by Shiraishi Calcium)
(4) Fatty acid-containing compound A) Mg stearate
Fcochem MGS (trade name, manufactured by ADEKA)
B) Stearic acid sakura (trade name, manufactured by NOF Corporation)
C) Lauric acid NAA-122 (trade name, manufactured by NOF Corporation)
D) Behenic acid NAA-222S (trade name, manufactured by NOF Corporation)
E) Montanic acid lycowax S (trade name, manufactured by Clariant Japan)
(5) n-octadecane octadecane (trade name, manufactured by Pure Chemical Industries)

Subsequently, the flame retardant resin composition obtained as described above was kneaded at 160 ° C. for 15 minutes by a Banbury mixer. Thereafter, the flame retardant resin composition is put into a single screw extruder (L / D = 20, screw shape: full flight screw, manufactured by Mars Seiki Co., Ltd.), and a tubular extrudate is extruded from the extruder. A conductor (number of strands / cross-sectional area of 2 mm ² ) was coated to a thickness of 0.7 mm. Thus, an insulated wire was obtained.

  About the insulated wire of Examples 1-16 obtained as mentioned above and Comparative Examples 1-7, a flame retardance, a mechanical characteristic, and terminal workability were evaluated as follows.

<Flame retardance>
(60 degree inclined combustion test)
About the insulated wire of Examples 1-16 and Comparative Examples 1-7, the 60 degree inclination combustion test of JISC3005 was done and the flame retardance was evaluated. The results are shown in Tables 1-5. In Tables 1 to 5, for each example and comparative example, 10 insulated wires are prepared and a flame retardancy test is performed, and the average value of the fire extinguishing time (unit: seconds) of 10 insulated wires is measured. did. Here, the fire extinguishing time is the time from self-extinguishing immediately after the end of flame contact (immediately after releasing the burner flame from the electric wire), and the shorter the fire extinguishing time, the higher the flame retardancy. At this time, the flame contact was performed until ignition of the electric wire occurred within 30 seconds. The results are shown in Tables 1-5. In Tables 1 to 5, the unit of the average value of the fire extinguishing time is seconds, and the acceptance criteria for the average value of the fire extinguishing time are as follows. In Table 5, “Completion” was displayed for the comparative example that did not self-extinguish.

60 seconds or less: Pass over 60 seconds: Fail

<Mechanical properties>
The mechanical properties were evaluated based on the measured tensile strength of the insulated wires of Examples 1 to 16 and Comparative Examples 1 to 7, which were subjected to a tensile test according to JIS C3005. The results are shown in Tables 1-5. In Tables 1 to 5, the unit of tensile strength was MPa, and the pass / fail criteria for tensile strength was as follows. In the tensile test, the tensile speed was 200 mm / min, and the distance between the marked lines was 20 mm.

10 MPa or more: pass less than 10 MPa: fail

<Terminal processability>
The terminal processability was evaluated according to the following criteria by stripping the insulated wire coatings of Examples 1 to 16 and Comparative Examples 1 to 7 using a stripper. The results are shown in Tables 1-5. Regarding the pass / fail criteria for terminal processability, ◎ and ○ were accepted and x was rejected.

◎: The coating could be stripped without causing any elongation of the coating or damage to the conductor. ○: Although the coating was slightly stretched, the coating on the conductor or the gripped part was not damaged, and the skinning was performed. ×: The extension of the coating or the coating of the conductor or the gripped part was damaged, and the skinning process could not be performed.

  From the results shown in Tables 1 to 5, the insulated wires of Examples 1 to 16 reached the acceptance criteria for all of flame retardancy, mechanical properties, and terminal processability. On the other hand, the insulated wires of Comparative Examples 1 to 7 did not reach the acceptance criteria for one of flame retardancy, mechanical properties, and terminal processability.

  From this, it was confirmed that according to the flame retardant resin composition of the present invention, excellent flame retardancy can be secured while securing excellent mechanical properties and terminal processability.

DESCRIPTION OF SYMBOLS 1 ... Inner conductor 2 ... Insulating layer 3 ... Sheath 4 ... Insulated electric wire 10 ... Flat cable

Claims (8)

A base resin;
Calcium carbonate particles blended at a ratio of 10 parts by mass or more and 120 parts by mass or less with respect to 100 parts by mass of the base resin;
A silicone compound blended in a proportion of greater than 1 part by weight and less than or equal to 3 parts by weight with respect to 100 parts by weight of the base resin;
A fatty acid-containing compound that is blended at a ratio of greater than 3 parts by weight and less than or equal to 20 parts by weight with respect to 100 parts by weight of the base resin,
Ri average particle size greater 5.0μm der less than 1.8μm of the calcium carbonate particles,
Wherein the base resin is a polyolefin compound der Ru flame retardant resin composition.   The flame-retardant resin composition according to claim 1, wherein the fatty acid-containing compound is blended at a ratio of 10 parts by mass or less with respect to 100 parts by mass of the base resin.   The flame retardant resin composition according to claim 1 or 2, wherein the calcium carbonate particles are heavy calcium carbonate or light calcium carbonate. The flame retardant resin composition according to any one of claims 1 to 3 , wherein the silicone compound is silicone gum. The flame retardant resin composition according to any one of claims 1 to 4 , wherein the fatty acid-containing compound is magnesium stearate. The flame retardant resin composition according to any one of claims 1 to 4 , wherein the fatty acid-containing compound is stearic acid. Conductors,
An insulated wire having an insulating layer covering the conductor;
The cable in which the said insulating layer is comprised with the flame-retardant resin composition as described in any one of Claims 1-6 . An insulated wire having a conductor and an insulating layer covering the conductor;
A sheath covering the insulating layer;
A cable in which at least one of the insulating layer and the sheath is composed of the flame-retardant resin composition according to any one of claims 1 to 6 .

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