JP2018184529A - Polyvinyl chloride resin composition, polyvinyl chloride resin composition sheet, insulated wire and cable - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a polyvinyl chloride resin composition which satisfies flame retardancy conforming a combustion test for railway vehicle, and is excellent in a balance among cold resistance, electric insulation property and oil resistance, and a sheet, an insulated wire and a cable using the same.SOLUTION: A polyvinyl chloride resin composition contains a polyvinyl chloride resin (A) having a K value of 69-79 and a partially crosslinked polyvinyl chloride resin (B), or the partially crosslinked polyvinyl chloride resin (B), diisononyl phthalate (C) and aluminum hydroxide (D) having an element mass concentration of sodium, calcium and potassium of 0.2 mass% or less, where an isononyl alcohol raw material having a specific composition is used in a raw material of the component (C), a mass ratio (A)/(B) of the component (A) to the component (B) is 0 to 60/40 to 100, the component (D) is 15-35 pts.mass with respect to 100 pts.mass of the sum of the component (A) and the component (B), and the total amount of the resin composition is 170-200 pts.mass.SELECTED DRAWING: Figure 1

Description

  The present invention relates to an environment-friendly polyvinyl chloride resin composition that does not contain an antimony compound, and a sheet, an insulated wire, and a cable that use the resin composition.

  The polyvinyl chloride resin can widely contain various additives. Therefore, the polyvinyl chloride resin composition can realize a wide range of mechanical characteristics and other characteristics.

  The polyvinyl chloride resin composition includes a hard polyvinyl chloride resin composition and a soft polyvinyl chloride resin composition. Rigid polyvinyl chloride resin compositions are used for molded articles such as exteriors of aircraft, vehicles and other transportation equipment, furniture, office goods, housing materials such as home appliances, and parts of semiconductor devices. The soft polyvinyl chloride resin composition contains a large amount of a plasticizer that imparts flexibility, and is used for insulating layers such as electric wires and cables that require flexibility.

  Among electric wires / cables, in the case of electric wires used for railway vehicle wiring, the insulating layer used is required to have high flame resistance (for example, classified as flame retardant in railway vehicle combustion tests). For this reason, various flame retardants are added and contained in the polyvinyl chloride resin composition constituting the insulating layer in order to impart flame retardancy.

  The applicant has already proposed a soft polyvinyl chloride resin composition to which a flame retardant is added (see, for example, Patent Document 1). According to Patent Document 1, as a flame retardant, zinc borate, metal hydroxide, and antimony trioxide are combined, and by adding a predetermined amount of flame retardant or plasticizer, flame retardancy, heat resistance, cold resistance, and It can be set as the polyvinyl chloride resin composition excellent in volume resistivity.

  However, antimony compounds used as flame retardants tend to be refrained from use in recent years due to concerns about adverse effects on the environment and the human body. For example, antimony trioxide has been designated as a deleterious substance because it is weakly irritating to the skin and mucous membranes. As its toxicity, the carcinogenicity of lung cancer has been pointed out by experiments administered to air for 55 weeks to rats. Due to this carcinogenicity, antimony compounds are classified into Group 2B (which may be carcinogenic to humans) by the International Cancer Research Organization (IARC) in terms of carcinogenicity for humans.

  In addition, antimony compounds as mineral resources are unevenly distributed, and supply and demand tend to be tight. For this reason, the use of antimony compounds has risks such as supply instability and price increase.

  For railcar electric wires, it is required that the classification shown in Table 1 below be certified as “Flame Retardant” or higher in a railcar combustion test defined by the Japan Railway Vehicle Machinery Association. For this purpose, it is necessary to reduce the amount of smoke generated during combustion as shown in Table 1 below. It is known that a polyvinyl chloride resin composition using antimony trioxide forms an oxyhalide compound during combustion and generates a heavy incombustible gas. It goes without saying that this gas generation is not suitable for the test standard.

注）１）炭化、変形の寸法は長径で表す。 ２）異常発炎するものは１級下げる。

Note) 1) The carbonization and deformation dimensions are represented by the major axis. 2) Lower the level of those that cause abnormal flames.

  Under these circumstances, a soft flame-retardant polyvinyl chloride resin composition not containing an antimony compound is required as a resin composition constituting the insulating layer of the electric wire. For example, a resin composition using a combination of zinc stannate and zinc borate as an alternative to antimony trioxide has been proposed (see, for example, Patent Document 2). According to Patent Document 2, a soft flame-retardant polyvinyl chloride resin composition containing no antimony trioxide can be obtained by using zinc stannate and zinc borate together as a flame retardant.

  Zinc contained in zinc compounds such as zinc stannate and zinc borate acts as a catalyst for accelerating carbonization by eliminating hydrogen chloride in the polyvinyl chloride resin and contributing to the flame retardancy of the polyvinyl chloride resin. . The structure in which zinc contributes to the flame retardancy of the polyvinyl chloride resin will be described below.

  Polyvinyl chloride resin is decomposed by heating and ignited and then burns, but desorbs hydrogen chloride (dehydrochlorination reaction) upon heating. Zinc promotes the dehydrochlorination reaction and further promotes the dehydrochlorination reaction by reacting with the desorbed hydrogen chloride to produce zinc chloride. Due to the elimination of hydrogen chloride, the polyvinyl chloride resin deteriorates and finally becomes a carbonized layer. The carbonized layer has a heat insulating effect and can suppress ignition and combustion of the polyvinyl chloride resin. Thus, according to the zinc compound as a flame retardant, the dehydrochlorination reaction of the polyvinyl chloride resin is promoted to deteriorate the resin prior to the combustion of the resin (to make a carbonized layer). Can contribute to flammability.

  When the insulating layer composed of the resin composition of Patent Document 2 is heated in a combustion temperature range (generally 300 ° C. or higher), the dehydrochlorination reaction is accelerated by zinc and carbonizes quickly. And the surface of an insulating layer is coat | covered with the carbonization layer, and combustion will be suppressed.

  By the way, the polyvinyl chloride resin composition is heated at a predetermined temperature and molded into an insulating layer of an electric wire. The heating temperature (molding temperature range) during the molding process is 120 ° C to 190 ° C.

  In this regard, the polyvinyl chloride resin composition of Patent Document 2 has a problem in that it deteriorates due to heating during the molding process and the properties of the molded insulating layer and the like deteriorate. The polyvinyl chloride resin causes a dehydrochlorination reaction even in the molding temperature range, although it is smaller than the combustion temperature range. For this reason, in the polyvinyl chloride resin composition of patent document 2 containing a zinc compound, dehydrochlorination reaction is accelerated | stimulated and degradation of resin will advance.

  In other words, the zinc compound acts as a catalyst for promoting the dehydrochlorination reaction (although it contributes to the flame retardancy of the polyvinyl chloride resin by the catalytic action in the combustion temperature range), the zinc compound acts as a catalyst for the catalytic action in the molding temperature range. The deterioration of the vinyl chloride resin is promoted, and the stability (heat resistance) of the resin against the heat load is reduced.

  In addition, the polyvinyl chloride resin composition described in Patent Document 2 uses zinc stannate and zinc borate in combination as a flame retardant, resulting in an increase in the zinc content in the resin composition. The hydrogen chloride reaction is high and the heat resistance of the resin is further reduced.

  As described above, the polyvinyl chloride resin composition described in Patent Document 2 does not contain a harmful antimony compound, but uses zinc stannate and zinc borate, which are alternatives, and therefore at least flame retardancy and heat resistance. It was difficult to achieve both.

  Patent Document 3 is a prior art that solves these problems. Patent Document 3 discloses a polyvinyl chloride resin composition that does not contain antimony trioxide and has an excellent balance of flame retardancy, heat resistance, cold resistance, and electrical insulation.

JP 2009-126963 A Japanese Patent Laid-Open No. 11-80474 Patent No. 5716653

However, the flame retardant test performed on the polyvinyl chloride resin composition of Patent Document 3 is a UL-specified VW-1 test, in which case the flame retardant property passes, and the above-described railway vehicle It was found to be rejected when the combustion test was performed. This is because the resin composition at the time of combustion is deformed and inhibits the flame retardant effect.

  The present invention has been made in view of such problems, and an object of the present invention is to contain no antimony compound, satisfy a certification condition of “flame retardant” or higher in a railcar combustion test, and be resistant to cold. It is providing the polyvinyl chloride resin composition which is excellent in balance of property, electrical insulation, and oil resistance, and a sheet, an insulated wire, and a cable using the resin composition.

  In order to achieve the above object, the present invention provides the following polyvinyl chloride resin composition, and a sheet, an insulated wire, and a cable using the resin composition.

[1] Polyvinyl chloride resin (A) and partially crosslinked polyvinyl chloride resin (B), or partially crosslinked polyvinyl chloride resin (B), diisononyl phthalate (C), and polyhydride containing aluminum hydroxide (D) In the vinyl chloride resin composition, the K value of the component (A) is 69 or more and 79 or less, and the isononyl alcohol composition of the raw material of the component (C) is 25 parts by mass or more of dimethyl heptanol with 100 parts by mass of the whole raw material. , 20 parts by mass or more of monomethyl octanol, 15 parts by mass or less of n-nonalol, and 30 parts by mass or less of the element (D), and the element mass concentration of sodium, calcium and potassium of the component (D) is 0.2% by mass or less, The mass ratio (A) / (B) = 0 to 60 / 40-100 of the component (A) and the component (B), and the sum of the component (A) and the component (B) To 00 parts by weight, the component (D) is not more than 35 parts by mass or more 15 parts by weight, polyvinyl chloride resin composition is 200 parts by weight from the total amount of 170 parts by weight of the resin composition.
[2] The polyvinyl chloride resin composition according to [1], further including a stabilizer, a filler, and other additives in addition to the components (A), (B), (C), and (D).
[3] A polyvinyl chloride resin composition sheet having a thickness of 0.1 mm or more using the polyvinyl chloride resin composition according to [1] or [2].
[4] An insulated wire comprising a conductor and an insulating layer made of the polyvinyl chloride resin composition according to [1] or [2], which is coated on an outer periphery of the conductor.
[5] A cable including a sheath made of the polyvinyl chloride resin composition according to [1] or [2].

  According to the present invention, a polyvinyl chloride resin composition that does not contain an antimony compound, satisfies a certification condition of “flame retardant” or higher in a railway vehicle combustion test, and has an excellent balance of cold resistance, electrical insulation, and oil resistance. And a sheet, an insulated wire, and a cable using the resin composition can be provided.

It is a cross-sectional view which shows an example of the insulated wire which concerns on embodiment of this invention. It is a cross-sectional view showing an example of a cable according to an embodiment of the present invention.

  As described above, predetermined flame retardancy, oil resistance, electrical characteristics, and cold resistance are required for the resin composition used for the insulating layer of the vehicle electric wire. For example, in the case of a resin composition used for an insulating layer of a 60 ° C. rated WV electric wire (Wheel Vinyl electric wire), the combustion characteristics are required to satisfy the “flame retardant” or higher certification condition in the rail vehicle combustion test. Is done. Moreover, also in electrical characteristics, oil resistance, and cold resistance, it is necessary to satisfy the standard value of JISK6723 type 1 specification.

  However, a polyvinyl chloride resin composition containing a zinc compound such as zinc stannate as an alternative to an antimony compound does not exhibit an effect with a low addition, and it is difficult to satisfy electrical characteristics when a high addition is made. It was.

  Accordingly, the present inventors have made use of a high molecular weight PVC resin, a plasticizer structure to be plasticized, and aluminum hydroxide used as a flame retardant as a method for satisfying the above-described combustion characteristics without deteriorating electrical characteristics. A new formulation was studied from the viewpoint of composition.

  As a result, the present inventors added a raw material isononyl to a polyvinyl chloride resin (A) having a K value of 69 or more and 79 or less and a partially crosslinked polyvinyl chloride resin (B) (or only component (B)). A polyvinyl chloride resin composition containing diisononyl phthalate (C) having an alcohol composition of 25% by mass or more of dimethylheptanol, 20% by mass or more of monomethyloctanol, 15% by mass or less of n-nonalol, and 30% by mass or less of other. It has been found that a large amount of aluminum hydroxide that can be dehydrated and foamed during molding can be added. In addition, it was found that the specified electrical characteristics can be obtained by selecting an aluminum hydroxide (D) to be added having an element mass concentration of sodium, calcium, or potassium of 0.2% by mass or less. Furthermore, regarding the content of additives, it was found that cold resistance and oil resistance can be achieved by controlling the total amount of the polyvinyl chloride resin composition from 170 parts by weight to 200 parts by weight with respect to 100 parts by weight of the resin component.

  Below, the polyvinyl chloride resin composition which concerns on one Embodiment of this invention is demonstrated.

(Polyvinyl chloride resin)
Examples of the polyvinyl chloride resin (PVC) include homopolymers of vinyl chloride, that is, polyvinyl chloride, copolymers of vinyl chloride and other copolymerizable monomers, and blends thereof. The polyvinyl chloride resin is a blend of a polyvinyl chloride resin (A) having a K value of 69 or more and 79 or less and a partially crosslinked polyvinyl chloride resin (B). The K value is a value indicating the specific viscosity of the polyvinyl chloride resin and correlates with the degree of polymerization. The K value is a value obtained by a test method of JIS K7367-2 or ISO 1628-2.

As the partially crosslinked polyvinyl chloride resin (B), it is preferable to use a partially crosslinked polyvinyl chloride resin (B) having a K value of 69 to 79 and a THF insoluble content of 10% to 30%.
By setting the THF-insoluble content to 10% or more, it is possible to maintain the matting effect on the surface of the resin composition, suppress the conspicuousness of the crosslinked PVC particles, and improve the surface particle appearance.
The method for measuring the insoluble content (THF insoluble content) of polyvinyl chloride resin in THF (tetrahydrofuran) is as follows.
Take 1.0 g of PVC sample into a 100 mL colorimetric tube and add THF. This is kept at 75 ° C. for 1 hour while being vibrated, and then allowed to cool to room temperature. THF is added so that the solution becomes 100 mL, and the mixture is allowed to stand for a whole day and night. Then, 10 mL of the supernatant is collected, and the amount of residual resin after evaporation to dryness is precisely weighed. The formula for calculating the THF-insoluble content is as follows.
THF-insoluble content [%] = 100-residual resin amount [g] × 10 × 100
The K value of the partially crosslinked polyvinyl chloride resin (B) is a value obtained by measuring the THF-soluble content by the method described above.

  As a blend ratio, the sum of (A) and (B) is 100 parts by mass, and the mass ratio of (A) and (B) is (A) / (B) = 0-60 / 40-100. . When the ratio of (A) is 60 parts by mass or less, since the softening of the polyvinyl chloride resin sheet can be suppressed and combustion can be suppressed during the railway vehicle combustion test, flame retardancy is improved. Moreover, deterioration of the external appearance of the electric wire can be suppressed. The proportion of (A) is preferably adjusted in the range of 0 to 60 parts by mass. When extrudability is facilitated and the cost is taken into consideration, it is better that the addition ratio is larger, and when importance is placed on electrical characteristics and cold resistance, it is better.

(Plasticizer)
The plasticizer is an additive for imparting flexibility to the polyvinyl chloride resin and facilitating processing. In this embodiment, diisononyl phthalate is used as a plasticizer. As diisononyl phthalate, the raw material isononyl alcohol composition preferably comprises the following (a) to (d). (A) 25 parts by mass or more of dimethylheptanol, (b) 20 parts by mass or more of monomethyloctanol, (c) 15 parts by mass or less of n-nonalol, (d) 30 parts by mass or less of other alcohols. The diisononyl phthalate of the present invention is produced by ester synthesis of alcohol (100 parts by mass in total) having a ratio of (a) to (d) and phthalic anhydride.

The above-mentioned (a) and (b) are 25 parts by mass and 20 parts by mass or more, respectively, and unless (c) is 15 parts by mass or less, the electrical characteristics mentioned as the object of the present invention are not exhibited.
Further, (c) is preferably adjusted to 4 parts by mass or more from the viewpoint of imparting cold resistance. If (d) is an alcohol having 7 to 12 carbon atoms, the structure may be either a straight chain type or a side chain type, or a mixture.

(Aluminum hydroxide)
Aluminum hydroxide is an additive for imparting flame retardancy. In the present embodiment, an element having a mass concentration of sodium, calcium, or potassium of 0.2% by mass or less is selected. This is because if it exceeds 0.2% by mass, the cost becomes low, but the electric characteristics are not satisfied. The addition amount of aluminum hydroxide is preferably 15 parts by mass or more and 35 parts by mass or less. If the amount is 15 parts by mass or more, the flame retardancy is good, and if it is 35 parts by mass or less, the electrical characteristics have a high likelihood, and cold resistance and oil resistance are improved.

  The average particle diameter of aluminum hydroxide is preferably 0.5 to 5 μm from the viewpoint of the extrusion appearance. You may use what is surface-treated with a stearic acid, a silane compound, and a titanium compound if needed.

(Stabilizer, filler and other additives)
As the stabilizer, a known composite stabilizer such as calcium-zinc-based or barium-zinc-based can be used. As the composite stabilizer, those other than those containing lead, which have a negative effect on the environment and the human body, are preferred, and examples thereof include those containing hydrotalcite as a main component. Hydrotalcite can supplement hydrogen chloride generated during heat load such as during molding of the resin composition by ion exchange.

As the filler, known fillers such as calcined clay, calcium carbonate, talc and silica can be used. Among these, application of fired clay is preferable from the viewpoint of improving electrical characteristics.
Other additives include antioxidants, colorants, UV absorbers, copper damage inhibitors, processing aids, etc. In addition to these, polymers, plasticizers and flame retardants other than those specified above are added. be able to.

The stabilizer, filler and other additives may be added in such a manner that the total amount of the polyvinyl chloride resin composition is 170 parts by mass to 200 parts by mass with respect to 100 parts by mass of the polyvinyl chloride resin component. From the viewpoint of oil resistance.
According to the above-described polyvinyl chloride resin composition according to one embodiment of the present invention, it does not contain an antimony compound and satisfies a certification condition of “flammability” or higher in a railcar combustion test even with a wall thickness of 1 mm or less. And it can be set as the polyvinyl chloride resin composition excellent in the balance of cold resistance, electrical insulation, and oil resistance.

(Electrical wire)
FIG. 1 is a cross-sectional view showing an example of an insulated wire according to an embodiment of the present invention.
As shown in FIG. 1, the insulated wire 10 according to the present embodiment includes a conductor 1 and an insulating layer 2 covered on the outer periphery of the conductor 1. As the conductor 1 to be coated, for example, a conductor formed of a metal material such as copper or a copper alloy having an outer diameter of about 0.15 to 7 mmφ can be used. The conductor etc. which twisted the tin plating annealed copper wire can be used conveniently. The conductor 1 is not limited to a single conductor as shown in FIG. 1, and may be a plurality of conductors. The conductor diameter and material are not particularly limited, and an optimal conductor can be appropriately selected according to the application. . Further, the thickness of the insulating layer is not particularly limited, and an optimum thickness is selected according to specifications.

Next, the manufacturing method of an insulated wire is demonstrated.
First, a predetermined amount of a plasticizer and a flame retardant are added to a polyvinyl chloride resin and uniformly kneaded to form a polyvinyl chloride resin composition. The kneading method may be any method in which the components of the resin composition are substantially uniformly dispersed, mixed, and kneaded. For example, a Banbury mixer, a kneader, a same-direction twin screw extruder, a different-direction twin screw extruder, and the like. It can be kneaded with a roll kneader, a batch kneader or the like. Subsequently, a polyvinyl chloride resin composition is extrusion coated on the outer periphery of the conductor using a known wire coating extruder to produce an electric wire.

(cable)
The cable according to the embodiment of the present invention is characterized in that the polyvinyl chloride resin composition according to the embodiment of the present invention is used as a coating material (sheath or insulating layer and sheath).

FIG. 2 is a cross-sectional view showing an example of a cable according to the embodiment of the present invention.
As shown in FIG. 2, the cable 30 according to the present embodiment includes a three-core stranded wire obtained by twisting three insulated wires 10 with a conductor 1 covered with an insulating layer 2 together with an interposition 4 such as paper, and the like. A presser wound tape 5 is provided on the outer periphery of the stranded wire, and a sheath 3 is coated on the outer periphery by extrusion coating. Not only a three-core stranded wire but also one insulated wire (single core) or a multi-core stranded wire other than a three-core stranded wire may be used.

  The sheath 3 is comprised from said polyvinyl chloride resin composition which concerns on embodiment of this invention. The insulating layer 2 may also be comprised from said polyvinyl chloride resin composition. A cable can be obtained by coating as an insulating layer or a sheath layer by a molding means such as extrusion coating.

  In the present embodiment, the sheath may be composed of a single layer or a multilayer structure. Furthermore, you may give a separator, a braiding, etc. as needed.

The outer diameter of the insulated wire or cable according to the embodiment of the present invention is, for example, 0.4 to 11 mmφ.
The insulated wire and cable which concern on embodiment of this invention can be used conveniently for the electric wire and cable for railway vehicles.

Hereinafter, the present invention will be described in more detail based on Examples, Comparative Examples, and Reference Examples, but the present invention is not limited thereto.
A polyvinyl chloride resin composition and an insulated wire 10 having the structure shown in FIG. 1 were produced and evaluated by the following methods.

(1) Preparation of polyvinyl chloride resin composition The materials shown in Tables 2 to 3 were blended in the stated proportions, kneaded with a 6-inch mixing roll set at 170 ° C for 5 minutes, and then formed into a sheet. The ingredients of the compounding agents used are as shown in Table 4.

(2) Preparation of Evaluation Sheet Each resin mixture formed into a sheet is preheated at 170 ° C. for 3 minutes with a hot press, and then kept at a pressure of 100 kgf / cm ² for 2 minutes and kept at room temperature for 5 minutes. 5 types (0.3 mm, 0.6 mm, 0.8 mm, 1 mm, 2 mm) of each evaluation sheet with different thicknesses were manufactured.

(3) Production of insulated wires Each resin mixture formed into a sheet was cut into 2 mm square pellets. Each of the cut pellets was extrusion coated onto a conductor with a 40 mm extruder set at a cylinder temperature of 180 ° C., a head temperature of 185 ° C., and a linear speed of 200 m / min, to produce the electric wires shown in FIG. Each of the extrusion operations was continuously performed for 2 hours. The conductor used was a tin-plated copper wire with an outer diameter of 0.94 mm (26 strands of strands with an outer diameter of 0.16 mm), the coating thickness was 0.6 mm, and the outer diameter after coating was 2.16 mm.

(4) Evaluation method About each produced evaluation sheet | seat, it evaluated oil oil, cold resistance, electrical insulation, and the "flammability" certification | regulation condition in the combustion test for rail vehicles. Moreover, the extrusion moldability (appearance) was evaluated about each produced insulated wire. Each evaluation method will be described below.

(Oil resistance)
Oil resistance was carried out using an evaluation sheet (thickness 1 mm) according to JIS K 6723. The material classification of the mixture was Type 1 No. 1 (general insulator), and the tensile strength residual rate and elongation residual rate after immersion in Type 1 No. 2 insulating oil at 70 ° C. for 4 hours were determined. A tensile strength residual ratio of 85% or more satisfying the standard and an elongation residual ratio of 80% or more were evaluated as ◯, and those not satisfying the standard were evaluated as x.

(Cold resistance)
Cold resistance was carried out using an evaluation sheet (thickness 2 mm) in accordance with JIS K 6723. The material classification of the admixture was Class 1 No. 1 (general insulator), cold resistance satisfying the standard −15 ° C. or less was rated as “◯”, and those not meeting the standard were marked as “X”.

(Electrical insulation)
Electrical insulation is 30 ° C. according to JIS K 6723 (6.8.1 measuring instrument and electrode in volume resistivity test of 6.8, measurement of thickness of 6.8.2 test piece and test piece). The volume resistivity was measured, and 5 × 10 ¹³ Ω · cm or more satisfying the standard was evaluated as ◯, and the one not satisfying the standard was evaluated as ×.

(Extrudability)
Each insulated wire was evaluated as “O” when there was no surface roughness, surface grain, burnt (discoloration), bump detection error due to foaming, and a spark tester error, and no whitening occurred even when the coated surface of the insulated wire was rubbed with a nail. The case where any one of surface roughness, surface grain, burn (discoloration), bump detection error, spark tester error, and abrasion whitening occurred was evaluated as x.

(Flame retardance)
Three types of evaluation sheets (thickness 0.3 mm, 0.6 mm, and 0.8 mm) were used as test pieces in accordance with the combustion test (non-metallic material for railway vehicles) prescribed by the Japan Railway Vehicle Machinery Technology Association. ). A test piece is formed in a B5 size (182 mm × 257 mm), the test piece is held at a 45 ° inclination, and the center of the bottom of the fuel container is 25.4 mm (1) vertically below the center of the lower surface (combustion surface) of the test piece. It is a test method in which it is placed on a base made of a material having low thermal conductivity such as cork, 0.5 cc of pure ethyl alcohol is ignited and left to stand until the fuel is burned out.

  Combustion judgment is divided into alcohol combustion and after combustion. During combustion, the test piece is observed for ignition, ignition, smoke generation, flame condition, etc. After combustion, afterflame, residue, carbonization The state of deformation is investigated and certified. All three test specimens were certified as “flame retardant”, and those certified as “slowly flammable” or “flammable” were marked as x.

(5) Evaluation results (Examples 1 to 7)
Table 2 shows the evaluation contents of Examples 1 to 7 of the present invention. Examples 1-7 are the examples which adjusted the total amount of the polyvinyl chloride resin mixture to 170 mass parts-200 mass parts using polyvinyl chloride resin, diisononyl phthalate, and aluminum hydroxide as shown in Table 2. is there. Of course, antimony trioxide is not used.

  As shown in Table 2, each of the characteristics (oil resistance, cold resistance, electrical insulation, flame retardancy) and extrusion moldability of Examples 1 to 7 was evaluated as “good”.

(Comparative Examples 1-6, Reference Example 1)
Table 3 shows the evaluation contents of Comparative Examples 1 to 6 and Reference Example 1.
Comparative Example 1 is an example using aluminum hydroxide in which the total amount of sodium, potassium and calcium is 0.3% by mass. The electrical insulation could not satisfy the standard value.

  Comparative Example 2 is an example in which only the polyvinyl chloride resin of Comparative Example 1 is A (polyvinyl chloride resin having a K value of 72). In addition to electrical insulation, flame retardancy was also x.

  Comparative Example 3 is an example in which the total amount (A + B + C + D + E) of the polyvinyl chloride resin composition with respect to 100 parts by mass of the resin component was 167 parts by mass and out of the range of the present invention (small amount). Flame retardance was x.

  Comparative Example 4 is an example in which the grade of the polyvinyl chloride resin is out of the scope of the present invention. Sparking occurred due to foaming during extrusion, and the extrusion moldability was x. Moreover, the electrical insulation was also x.

  Comparative Example 5 is an example using diisononyl phthalate (plasticizer DINP3) having a composition outside the scope of the present invention. The electrical insulation, flame retardancy, and cold resistance were x.

  Comparative Example 6 is an example in which the total amount (A + B + C + D + E) of the polyvinyl chloride resin composition with respect to 100 parts by mass of the resin component was 204 parts by mass, out of the range of the present invention (a large amount). The cold resistance, oil resistance, and electrical insulation properties were out of the standard and rated as x.

  Reference Example 1 is an example using antimony trioxide. Due to the effect of antimony oxyhalide gas generated during combustion, it was judged that the amount of smoke was large, and the flame retardancy was x. Moreover, since the degree of crosslinking of the partially crosslinked polyvinyl chloride resin (B) is high, the extrusion moldability was also x.

1: Conductor 2: Insulating layer 3: Sheath 4: Intervening 5: Presser winding tape 10: Insulated wire 30: Cable

Claims (5)

A polyvinyl chloride resin (A) and a partially crosslinked polyvinyl chloride resin (B), or a partially crosslinked polyvinyl chloride resin (B);
Diisononyl phthalate (C),
In the polyvinyl chloride resin composition containing aluminum hydroxide (D),
K value of the said component (A) is 69-79,
Isononyl alcohol composition of the raw material of the component (C) is 25 parts by mass or more of dimethylheptanol, 20 parts by mass or more of monomethyloctanol, 15 parts by mass or less of n-nonalol, and 30 parts by mass or less of other parts. ,
The element mass concentration of sodium, calcium, potassium of the component (D) is 0.2% by mass or less,
It consists of the mass ratio (A) / (B) = 0-60 / 40-100 of the said component (A) and the said component (B), with respect to the sum 100 mass part of the said component (A) and the said component (B). The polyvinyl chloride resin composition wherein the component (D) is 15 parts by mass or more and 35 parts by mass or less, and the total amount of the resin composition is 170 parts by mass to 200 parts by mass.   The polyvinyl chloride resin composition according to claim 1, further comprising a stabilizer, a filler, and other additives in addition to the components (A), (B), (C), and (D).   A polyvinyl chloride resin composition sheet having a thickness of 0.1 mm or more using the polyvinyl chloride resin composition according to claim 1.   An insulated wire comprising a conductor and an insulating layer made of the polyvinyl chloride resin composition according to claim 1 or 2, which is coated on an outer periphery of the conductor.   A cable comprising a sheath made of the polyvinyl chloride resin composition according to claim 1 or 2.

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