JPS6040470B2 - Vinyl chloride resin composition - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a vinyl chloride resin composition that is an excellent flame retardant.

Among synthetic resins, vinyl chloride resin is one of the resins with excellent flame retardancy, but if a plasticizer is added to increase flexibility, the plasticizer is flammable, so vinyl chloride resin becomes easily flammable. As a result, the characteristic of key fire is lost.

As a method for improving the flame retardance of soft vinyl chloride resins to which plasticizers have been added, it is generally known to add, for example, various metal oxides or halogen-containing compounds.

However, these methods only slightly improve the flame retardance of the material itself, and in the case of sandwich structures with other combustible materials such as wall materials, coaxial cables, high-voltage electric wires, etc., or external coating structures, etc. Even if the vinyl chloride resin material coated on the outside has excellent flame retardancy, it is difficult to suppress the combustion of the combustible material inside. For example, in coaxial cables used for internal wiring in televisions, etc., polyethylene is used as an insulator, and a European vinyl chloride-based material is used as an outer covering material. Although the coaxial cable is coated with a vinyl chloride resin made flame-retardant by a known method using an inorganic flame retardant as a sheath material, even if the vinyl chloride resin has a high oxygen index of 0I
SK7201), it is not possible to suppress the combustibility of polyethylene, and when a UL standard flame retardancy test or vertical flame test is performed, the product will fail. The present inventors have discovered that this type of electric wire has flame retardant properties as an external sheath material, and also has the function of blocking internal flammable materials from flames even when exposed to flames. Knowing that it was essential to use a substance, we investigated various options and found that a graphite compound was the most suitable.

That is, the present invention provides a flame-retardant pinyl chloride resin composition, particularly a flame-retardant pinyl chloride resin composition suitable for coating polyethylene insulated wires. , a vinyl chloride resin composition comprising a plasticizer and a retardant, characterized in that a graphite compound is used as a retardant. To explain the present invention in more detail, the vinyl chloride resin used in the present invention is mainly composed of a vinyl chloride homopolymer, vinyl chloride, and comonomers copolymerizable with the vinyl chloride, such as ethylene and propylene. , copolymers with vinyl acetate, acrylic acid, acrylic acid esters, ptagene, etc., terpolymer copolymers, and mixtures of these polymers. Examples of plasticizers include aromatic carboxylic acids such as phthalic acid, terephthalic acid, isophthalic acid, trimellitic acid, and pyromellitic acid, or aliphatic carboxylic acids such as adipic acid, azelaic acid, and sebacic acid, and methanol, ethanol, butanol, heptanol, Examples include mono- or esters with alcohols such as isodecanol, tridecanol, nonanol, undecanol, etc. Specific examples include 2-ethylhexyl phthalate, 2-ethylhexyl adibate, 2-ethylhexyl trimellitate, normal ectyl trimellitate. etc. Other plasticizers that are generally known as plasticizers for vinyl chloride resins, such as diventaerythritol ester, adipic acid polyester, and phthalic acid polyester, can also be used. Of course, two or more of these plasticizers may be selected and used in combination. Therefore, the amount of plasticizer used varies depending on the use of the vinyl chloride resin composition of the present invention, but is generally 10 to 15 parts by weight, preferably 20 to 7 parts by weight, per 10 G parts by weight of the vinyl chloride resin. It is best used within a range. Graphite compounds, which are an essential part of the composition of the present invention, are compounds in which various anions, ions, or molecules are inserted between layers without causing any essential change to the network plane of graphite carbon atoms. And,
For example, oxidized graphite with oxygen atoms between each layer, hydrogen sulfate graphite with anions such as hydrogen sulfate, bromine, and fluorine between the eyebrows, graphite salts such as bromide graphite, fluorine graphite, potassium,
Alkaline salts of graphite containing enteric ions such as rubidium and cesium, graphite sulfate, graphite nitrate, graphite phosphate, graphite pyrophosphate, graphite selenate, graphite arsenate, and the like can be mentioned.

All of these graphite compounds can impart flame retardancy to the composition of the present invention, but among these, sulfuric acid, nitric acid,
When a graphite compound containing an inorganic acid such as perchloric acid or phosphoric acid is used, the effect of imparting flame retardance is remarkable. Therefore, the amount of the graphite compound added is not particularly limited, but it depends on the amount of the plasticizer added to the vinyl chloride resin composition of the present invention, and the type of known pyrotechnic agent used in combination as described below. It is preferable to change it appropriately depending on the base and the base. for example,
When no other key fuel is used in combination, and the amount of plasticizer added to 10 parts by weight of vinyl chloride resin is 2 parts by weight or less, the amount of graphite compound added may be about 4 parts by weight. When the amount of plasticizer added is 3 parts by weight, the amount of graphite compound added needs to be about 5 parts by weight. In general, considering the physical properties, moldability, appearance of molded products, etc. of the vinyl chloride resin composition 2, 5 to 1
Preferably, it is 0 parts by weight. The composition of the present invention can exhibit a synergistic flame retardant effect by using in addition to the graphite compound as a flame retardant, a compound known as a key flame retardant for various synthetic resins.

These key fuels include, for example, antimony trioxide,
Zinc shelf acid, aluminum hydroxide, zinc oxide, zirconium oxide, hexap. Mubenzene, Tetrabromobisphenol A, Trisdichloropropylphosphate, IJ
Chlorinated polymers containing carbon and chlorinated paraffin are preferably used, and among these, antimony trioxide, zinc oxide, zinc oxide, etc. are preferably used in combination.The range of usage of these flame retardants is usually within the range of graphite compounds. Although the addition amount may be within a range, the absolute amount of the total amount of the elutriation agent can be reduced in order to obtain the same flame retardant effect by using it in combination with a graphite compound.
Therefore, when other scale flame retardants are used together, the amount of the graphite compound added may be about 1 part by weight per part by weight of the vinyl chloride resin 10, and sufficient flame retardancy can be imparted. Furthermore, various additives such as stabilizers for vinyl chloride resins, thickeners, colorants, fillers, etc. can be added to the vinyl chloride resin composition of the present invention.

The pinyl chloride resin composition of the present invention has excellent flame retardancy in itself, and has extremely high utility value in fields that require flame retardancy and fire resistance, such as fin lines and wall materials.

Furthermore, when the composition of the present invention is used as an external covering material for combustible materials, when the composition is exposed to flame, the graphite compound greatly expands, and the effect of shielding internal combustible materials from the flame is large. , suitable as a sheath material for electric wires. Furthermore, by using a graphite compound and a scale softening agent other than the graphite compound together as a scale softening agent in the composition of the present invention, the burning effect can be significantly improved due to the synergistic action of both the softening agents.

EXAMPLES The present invention will be described in more detail below with reference to Examples, but the present invention is not limited to the following Examples unless it exceeds the gist thereof.

In addition, "parts" in the examples means "parts by weight."

Examples 1 to 6 100 parts of vinyl chloride resin with an average degree of polymerization of 1300, 10 parts of lead-based stabilizer, 1.5 parts of lubricant, adipic acid-based polyester plasticizer, graphite sulfate, antimony trioxide, and zinc esterate as elutriation agents. Adding it in the proportions listed in Table 1 to produce an elutriation-resistant vinyl chloride resin composition.

The physical properties of the composition were measured, and the following flame retardant tests were conducted on the covered wires, which are also listed in Table 1. The outer surface of a polyethylene-coated electric wire with a diameter of 2.4 mm and a core wire of 0.5 mm diameter is coated with a copper wire sewing material, and the above composition of the present invention is extruded and coated on the outer surface of the wire. A coated electric wire with a diameter of 4.5/m was manufactured.

Table 1 (Note 1) Physical property test methods Tensile strength and elongation According to JIS K 6723.

Limit oxygen index Based on JISK7202. (Note 2) Flame retardancy test according to UL standard items 492 and 758.

The covered electric wire K was lit using the vertical flame test method, and those that continued to burn for 60 seconds or more after the flame was removed after the fifth ignition were judged to have passed.

Comparative Examples 1 to 4 Compositions were prepared in the same manner as in Example 1 without using graphite compounds, and the same tests as in Example 1 were conducted, and the results are shown in Table 2.

Table 2 Examples 7 to 11 In addition to 100 parts of vinyl chloride resin used in Example 1, 5 parts of plasticizer, 15 parts of graphite compound, 1 part of antimony trioxide, and 35 parts of the compounds shown in Table 3. Using the obtained composition, the number of times the flame retardant test was carried out was measured in the same manner as in Example 1.

Table 3 Examples 12 to 13 10 parts of vinyl chloride resin, 10 parts of graphite compound, 1 part of antimony trioxide, 3 parts of zinc shelf acid were kept constant, and 6 parts of plasticizer
The number of times until landing in the flame retardancy test of Example 1 was measured for compositions with different amounts of plasticizer (Example 12) and 7 parts of plasticizer (Example 13). Ta.

Examples 14 to 16 10 parts of pinyl chloride resin used in Example 1, 6 parts of plasticizer, 1 part of antimony trioxide, 3 parts of zinc oxide, and 10 parts of lead-based stabilizer, and 0.5 parts of graphite compound, respectively. Flame retardancy tests were conducted on the compositions containing 1 part, 1 part and 3 parts in the same manner as in Example 1 and are listed in Table 4.

Table 4 Examples 17 to 19 100 parts of a vinyl chloride terpolymer containing 5 parts by weight, 25 parts by weight, and 25 parts by weight of pinyl chloride, ethylene, and vinyl acetate, respectively, and 1 part by weight of antimony trioxide. A vinyl chloride resin composition in which 0.5 parts, 1 part, and 3 parts of a graphite compound were added to Edo, 3 parts of zinc oxide, and 1 part of chain stabilizer, respectively, was prepared in the same manner as in Example 1. A flame retardant test was conducted.

The results are shown in Table 5. As is clear from the results in Tables 4 and 5, when other flame additives are used in combination, even 1 part of graphite compound shows good elutriation properties, and even the addition of 0.5 part meets the UL standard. I have passed the exam.

Claims (1)

[Scope of Claims] 1. A vinyl chloride resin composition comprising a vinyl chloride resin, a plasticizer, and a flame retardant, characterized in that a graphite compound is used as the flame retardant. 2. The vinyl chloride resin composition according to claim 1, which uses a graphite compound and a twist retardant other than the graphite compound as a flame retardant. 3. The vinyl chloride resin composition according to claim 2, wherein the twist retardant agent other than the graphite compound is antimony trioxide, zinc borate, or zinc oxide.