JPH10279759A - Flame resistant vinyl chloride-based resin composition, and flame resistant wire and cable - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain the subject composition having excellent strength, thermal stability, oil resistance and electric insulating properties while keeping an excellent flame resistance, and suitable for insulator, etc., for a wire and cable by using a specific halogenated epoxy-based flame retardant. SOLUTION: This flame resistant vinyl chloride-based resin composition comprises (A) 100 pts.wt. vinyl chloride-based resin, (B) 20-60 pts.wt. plasticizer, (C) 2-40 pts.wt. halogenated epoxy-based flame retardant of formula I [R1 and R2 are each a group of formula II, etc.; R3 is a group of formula III, etc.; X is bromine or chlorine; (i) is 1-4; (n) is 0-20] having 50-150 deg.C softening point, and preferably (D) 1-10 pts.wt. antimony trioxide based on 100 pts.wt. component A. Further, the component C is preferably the halogenated epoxy compound having two or more halogen atoms in a molecule, e.g. a diglycidyl ether obtained by carrying out a condensation reaction of tetrabromobisphenol A and an epihalohydrin.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a flame-retardant vinyl chloride resin composition, and more particularly to a flame-retardant vinyl chloride resin composition suitably used in the field of electric wires requiring high safety. The present invention relates to electric wires and cables coated with the composition.

[0002]

2. Description of the Related Art Vinyl chloride resins have heat resistance, weather resistance,
It has excellent electrical properties and is counted as one of the domestically produced resins. Homopolymers of vinyl chloride are rigid and have poor workability, so some of them are used as rigid vinyl chloride resin copolymerized with vinyl acetate; for stationery, hard plastics such as records, floor materials, synthetic fibers, paints, etc. However, most of them are used as soft vinyl chloride resin containing a plasticizer in electric wires, cable coatings, films, sheets, flooring materials, vinyl foams, fibers and the like. When a plasticizer is used, the excellent flame retardant effect of the vinyl chloride resin alone decreases and becomes insufficient, so that it is common to add a flame retardant to process. At present, the intended flame retardancy is achieved by using a halogen-based flame retardant as the flame retardant. However, as the uses of vinyl chloride resins are further expanded and diversified in the future, and higher physical properties are required, the physical properties of conventional vinyl chloride resins using flame retardants are not at a satisfactory level. It is. That is, the addition of the flame retardant causes a high level of physical property deterioration of the polyvinyl chloride itself, which causes a problem that, for example, the mechanical strength, thermal stability, electric insulation and the like become insufficient. These physical properties can be satisfied to some extent by suppressing the amount of the flame retardant added, but on the contrary, there is a problem that the flame retardancy is reduced. In particular, in the future, demand for safety and durability is expected to increase from the viewpoint of environmental resources, and a resin composition having excellent strength, heat stability, oil resistance, and electrical insulation while having higher flame retardancy has been developed. Is desired.

[0003]

DISCLOSURE OF THE INVENTION The present invention solves the above-mentioned problems of the prior art and is a flame-retardant vinyl chloride resin composition which has excellent strength and heat stability while maintaining high flame retardancy. It is an object of the present invention to provide a composition having water resistance, oil resistance and electric insulation.

[0004]

In view of such circumstances, the present inventors have been keen to obtain a resin composition which is excellent in strength, heat stability, oil resistance and electrical insulation while maintaining high flame retardancy. As a result of the study, it has been found that the problem can be solved by using a specific halogenated epoxy-based flame retardant for the flame retardation of a vinyl chloride resin, and the present invention has been achieved. That is, the present invention provides: “1. 100 parts by weight of a vinyl chloride resin,
A flame retardant vinyl chloride composition comprising 60 parts by weight and 2 to 40 parts by weight of a halogenated epoxy flame retardant having a softening point represented by the following general formula (I) of 50 to 150 ° C. General formula (I)

[0005]

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[Wherein R ₁ and R ₂ are

[0007]

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[0008]

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The same or different groups selected from (Y is bromine or chlorine, j is an integer of 0 to 5), and R ₃ is

[0010]

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[0011]

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[0012]

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[0013]

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X is bromine or chlorine, i is an integer of 1 to 4 and n is a natural number of 0 to 20. ] 2. 2. The flame-retardant vinyl chloride resin composition according to item 1, wherein the halogenated epoxy flame retardant represented by the general formula (I) is a halogenated epoxy compound having two or more halogen atoms in a molecule. 3. Further, 1 part by weight of vinyl chloride resin
3. The flame-retardant vinyl chloride resin composition according to item 1 or 2, comprising from 10 to 10 parts by weight of antimony trioxide. 4. A flame-retardant electric wire and cable coated with the flame-retardant vinyl chloride resin composition according to any one of items 1 to 3. About.

[0015]

DESCRIPTION OF THE PREFERRED EMBODIMENTS The halogenated epoxy flame retardant used in the present invention must have a softening point of 50 to 150 ° C. The softening point is not particularly limited as long as it is within the above range, and can be appropriately selected so that optimum physical properties can be obtained depending on the resin to be mixed.
A halogenated epoxy-based flame retardant at about 120 ° C. is particularly preferably used. With a halogenated epoxy flame retardant having a softening point of 50 ° C. or lower, heat resistance and thermal stability are significantly reduced. When a halogenated epoxy resin having a softening point of 150 ° C. or higher is used, mechanical strength such as tensile strength and impact resistance are reduced. The softening point must be limited within the above range, since the drawbacks such as a decrease in the target strength, poor flowability and difficulty in molding are caused.
The softening point is measured by the ring and ball method according to Japanese Industrial Standard JIS K 7234.

The halogenated epoxy flame retardant represented by the general formula (I) used in the present invention has at least two halogen atoms in a molecule. If it is less than 2, the flame retardant effect is not sufficient. As the halogen, bromine or chlorine is preferable from the viewpoint of the flame retardant effect and the miscibility with the vinyl chloride resin. N in the general formula (I) is a natural number of 0 to 20. If it is 20 or more, the miscibility with the vinyl chloride resin becomes poor, and the mechanical properties of the composition decrease.

In the present invention, antimony trioxide, a conventionally used flame retardant, can be used in an amount of 1 to 10 parts by weight based on 100 parts by weight of a vinyl chloride resin. If the amount is less than 1 part by weight, the flame-retardant effect due to its use is poor, and if it is added more than 10 parts by weight, the mechanical properties of the composition deteriorate, which is not preferable.

The halogenated epoxy flame retardant is used in an amount of 2 to 40 parts by weight based on 100 parts by weight of the vinyl chloride resin. If the amount is less than 2 parts by weight, the flame-retardant effect cannot be obtained, and if the amount is more than 40 parts by weight, the mechanical properties of the composition deteriorate.
Examples of the halogenated epoxy flame retardant used in the present invention include tetrabromobisphenol A, tetrachlorobisphenol A, dibromobisphenol A, dichlorobisphenol A, tetrabromobisphenol S,
Examples include diglycidyl ethers obtained by condensation polymerization of epichlorohydrin with tetrachlorobisphenol S, dibromophenol novolak, and the like. Addition polymerization products of these with halogenated bisphenols, and one of these epoxy groups Part or all of which are blocked with halogenated phenols are also included. Here, specific examples of the halogenated phenol used for blocking include 2,4,6-
Examples include tribromophenol, dibromophenol, monobromophenol, 2,4,6-trichlorophenol, dichlorophenol, monochlorophenol and the like. Particularly preferred as the halogenated epoxy flame retardant is diglycidyl ether obtained by a condensation polymerization reaction of tetrabromobisphenol A and epichlorohydrin, an addition polymer thereof and tetrabromobisphenol A, and part or all of epoxy groups thereof. Is blocked with tribromophenol.

The plasticizer used in the present invention is a commonly used plasticizer and need not be limited. Specific examples of the plasticizer include phthalic acid esters such as dibutyl phthalate, dioctyl phthalate, diisodecyl phthalate, phosphate esters such as tricresyl phosphate and trioctyl phosphate, fatty acid esters such as dioctyl adipate and dioctyl sebacate, and the like. Chlorinated paraffins, polyesters and the like can be mentioned, and dioctyl phthalate is often used in general. Plasticizer is vinyl chloride resin 100
20 to 60 parts by weight based on parts by weight is preferred. If the amount is less than 20 parts by weight, a sufficient plasticizing effect cannot be obtained, and if it is more than 60 parts by weight, sufficient mechanical strength of the composition cannot be obtained.

In the present invention, a stabilizer, an impact resistance imparting agent, a flame retardant aid, a colorant, a filler, a lubricant, etc. may be used as additives, and the additives may be limited as long as the object of the present invention is not impaired. No need to be done. For example, generally with respect to 100 parts by weight of a vinyl chloride resin, 20 to 60 parts by weight of a plasticizer, 2 to 40 parts by weight of a flame retardant, 1 to 10 parts by weight of a stabilizer, 0.2 to 3 parts by weight of a lubricant,
0 to 5 parts by weight of a coloring agent and 3 to 50 parts by weight of a filler are examples. Examples of the stabilizer include tribasic lead sulfate, inorganic salts such as dibasic lead phosphite, dibasic lead stearate, metal soaps such as lead stearate, dialkyltin dilaurate, dialkyltin malate and the like. Organic tin compounds, other alkyl phenols, phosphites, and the like are used, and it is particularly preferable to use two or more kinds in combination. As the colorant, inorganic pigments, organic pigments and dyes are used, and the dyes are more preferably used because the weather resistance is poor. As the filler, calcium carbonate, titanium white, clay, asbestos and the like are used. As the lubricant, a metal stearate compound, stearic acid esters, low molecular weight polystyrene, liquid paraffin, and the like are used. Processing of the flame-retardant vinyl chloride-based resin composition in the present invention can be easily processed by conventional equipment and methods generally used in general, specifically, calendering, extrusion, lamination, Slash molding, dipping and the like can be mentioned. Ease of processing
Calendaring and extrusion are more preferred methods. Since the flame-retardant vinyl chloride resin composition of the present invention is excellent in oil resistance and electrical insulation, an insulated wire in which a conductor is coated with this composition has a higher difficulty than a conventional vinyl chloride resin-coated insulated wire. It is flammable and has an excellent safety effect in case of fire. Also, when used for a cable sheath, a cable having excellent flame retardancy, thermal stability, oil resistance, etc. can be obtained.

[0021]

EXAMPLES Hereinafter, the present invention will be described in more detail with reference to Examples and Comparative Examples, but the present invention is not limited thereto. The evaluation methods used in the examples and comparative examples are shown below. 1. Oxygen index (O.I.): JIS K 7201 2. Tensile strength, tensile strength after heating: JIS K672
3 100 ° C for 5 days 3. Oil resistance: JIS K 6723 4H 4. Embrittlement temperature: JIS K 6723 5. Thermal stability: JIS K 6723 6. Heat deformation rate: JIS K 6723 100 ℃ ・
1H 7. Volume resistivity: JIS K 6723 30 ° C Table 1 shows the flame retardants used in Examples and Comparative Examples.

[0022]

[Table 1]

(Note) In the table, O to U are groups represented by the following chemical formulas. Structural formula O

[0024]

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Structural formula P

[0026]

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Structural formula Q

[0028]

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Structural formula R

[0030]

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Structural formula S

[0032]

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Structural formula T

[0034]

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Structural formula U

[0036]

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Example 1 3000 g of polyvinyl chloride resin (Denka Vinyl SS-130 manufactured by Denki Kagaku Kogyo Co., Ltd., degree of polymerization: 1300), 1500 g of dioctyl phthalate (diasizer DOP manufactured by Mitsubishi Chemical Corporation), tribasic sulfate (Mizusawa) A resin (A1) shown in Table 1 as a flame retardant was added to 150 g of Stabinex TC (manufactured by Chemical Industry Co., Ltd.) and 1200 g of calcium carbonate (Epicoat 5 manufactured by Yuka Shell Epoxy Co., Ltd.).
050) and mixed by a ribbon blender for 10 minutes, and then melt-extruded with an extruder at a melting temperature of 150 ° C. and a screw rotation of 80 rpm to obtain a pellet-shaped flame-retardant resin composition. The composition obtained by the above method was molded into test pieces by an injection molding machine set at 180 degrees, and the results of measuring the properties of each were shown in Table 2.

Example 2 The flame retardant resin (A1) used in Example 1 was replaced with the resin (A2)
(Epicoat 5051 manufactured by Yuka Shell Epoxy Co., Ltd.)
A test piece was prepared and physical properties were measured in the same manner as in Example 1 except that the test was performed in place of the above.

Example 3 The flame retardant resin (A1) used in Example 1 was replaced with the resin (A3)
(Epicoat 5051 manufactured by Yuka Shell Epoxy Co., Ltd.)
A test piece was prepared and physical properties were measured in the same manner as in Example 1 except that the test was performed in place of H).

Example 4 The flame retardant resin (A1) used in Example 1 was replaced with a resin (A4)
(Epicoat 5201 manufactured by Yuka Shell Epoxy Co., Ltd.)
A test piece was prepared and physical properties were measured in the same manner as in Example 1 except that the test was performed in place of the above.

Example 5 The flame retardant resin (A1) used in Example 1 was replaced with the resin (A5)
(Epicoat 5354 manufactured by Yuka Shell Epoxy Co., Ltd.)
A test piece was prepared and physical properties were measured in the same manner as in Example 1 except that the test was performed in place of the above.

Comparative Example 1 The flame retardant resin (A1) used in Example 1 was replaced with the resin (B1).
A test piece was prepared and physical properties were measured in the same manner as in Example 1 except that the test was performed in place of (FG3000 manufactured by Teijin Chemicals Limited).

Comparative Example 2 The flame retardant resin (A1) used in Example 1 was replaced with the resin (B2)
A test piece was prepared and physical properties were measured in the same manner as in Example 1, except that the test was performed in place of (FG3100 manufactured by Teijin Chemicals Limited). Table 2 shows the test results.

[0044]

[Table 2]

From the results shown in Table 2, it is clear that the resin composition according to the present invention is excellent in mechanical strength, heat stability, oil resistance and electrical insulation while maintaining high flame retardancy.

[0046]

According to the present invention, the flame-retardant vinyl chloride resin composition having a halogenated epoxy resin as a flame retardant has superior strength and heat stability as compared with the conventional flame retardant other than epoxy resin. It is possible to provide a highly safe resin that can maintain a high level of flame retardancy while having properties, oil resistance and electrical insulation. In particular, the composition of the present invention is suitable for application to insulators and sheaths of electric wires and cables, judging from its properties.

Claims (4)

[Claims] 1. A halogenated epoxy flame retardant having a vinyl chloride resin 100 parts by weight, a plasticizer 20 to 60 parts by weight, and a softening point represented by the following general formula (I) of 50 to 150 ° C. A flame-retardant vinyl chloride resin composition comprising parts by weight. General formula (I) Wherein R ₁ and R ₂ are Embedded image (Y is bromine or chlorine, and j is an integer of 0 to 5.)
R ₃ is the same or different group selected from Embedded image Embedded image Embedded image X is bromine or chlorine,
i is an integer of 1 to 4, and n is a natural number of 0 to 20. ] 2. The flame-retardant chloride according to claim 1, wherein the halogenated epoxy flame retardant represented by the general formula (I) is a halogenated epoxy compound having two or more halogen atoms in a molecule. Vinyl-based resin composition. 3. The flame-retardant vinyl chloride resin composition according to claim 1, further comprising 1 to 10 parts by weight of antimony trioxide based on 100 parts by weight of the vinyl chloride resin. 4. A flame-retardant electric wire and cable coated with the flame-retardant vinyl chloride resin composition according to claim 1.