JP3174809B2 - Flameproof sheet - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

TECHNICAL FIELD The present invention relates to a flameproof sheet,
More specifically, the present invention relates to a flameproof sheet in which a bromine-based flame retardant and an antimony-based flame retardant are blended into a sheet structure, and the flame resistance is improved by improving the fluidity of the sheet structure.

[0002]

2. Description of the Related Art A woven or knitted fabric or sheet made of a polyolefin resin is used in many industrial fields due to its properties such as moldability, mechanical strength, and economic efficiency. Due to its flammability, its use is limited by the flame-retardant laws and regulations in some applications. Here, as a general method for imparting flameproofing performance to a polyolefin-based resin, a method of blending a predetermined amount of a flame retardant into a polyolefin-based resin is employed. Flameproofing treatment by blending a bromine-based flame retardant which is highly economical and easy to handle is widely performed. However, when a large amount of a flame retardant is blended in order to improve the flame prevention effect, there are various problems depending on the use form as follows. First, when producing a drawn yarn from a polyolefin resin blended with a flame retardant, if the drawing ratio is increased in order to improve the drawing effect, yarn breakage or the like occurs, so that the drawing ratio cannot be increased so much. It is difficult to obtain the expected strength. Also, due to the effect of the flame retardant exposed on the surface of the filament,
Unsatisfactory spinnability and subsequent weaving efficiency. Or,
When a polyolefin-based resin layer containing a large amount of a flame retardant is laminated on a woven or knitted fabric made of a drawn yarn, the adhesiveness and the moldability of the resin layer are poor, which is not preferable. Furthermore, using a large amount of flame retardant is not preferable in terms of economy.

[0003]

SUMMARY OF THE INVENTION In order to solve the above-mentioned problems, the present invention is to mix a specific amount of a bromine-based flame retardant and an antimony-based flame-retardant additive into a constituent and improve the fluidity of the constituent. An object of the present invention is to provide a flameproof sheet having improved flameproofness.

[0004]

SUMMARY OF THE INVENTION The present invention provides a woven or knitted fabric comprising a polyolefin-based resin thread or a sheet-like material comprising a laminate in which at least one surface of the woven or knitted fabric is covered with a polyolefin-based resin layer. 3-10% by weight of brominated flame retardant,
A composition containing 1 to 5% by weight of an antimony-based flame retardant aid, wherein the melt flow rate of the composition is 6 g / 10 m
in. or more.

[0005]

DETAILED DESCRIPTION OF THE INVENTION The polyolefin resin used in the present invention is polypropylene, high density polyethylene, medium density polyethylene, low density polyethylene, linear low density polyethylene, ethylene-propylene copolymer, ethylene-propylene copolymer.
It is a resin such as a vinyl acetate copolymer and an ethylene-acrylate copolymer alone or in combination of two or more. The melt flow rate (hereinafter abbreviated as MFR) of the polyolefin resin is preferably 1 to 20 g / 1.
0 min., More preferably 5 to 10 g / 10 min.

[0006] The yarn spun from the polyolefin resin is not particularly limited in its shape, and may be, for example, a monofilament, a multifilament, a split yarn, a flat yarn or the like, and may be a combination of the same or different polyolefin resins. , A core-sheath type or a side-by-side composite yarn. Next, the above-described yarn body is woven and knitted using warp yarns to form a woven knitted fabric and used as a sheet-like material. The weaving and knitting structure is not particularly limited, and examples of the woven fabric include various woven fabrics such as plain weave, woven weave, leno weave, and the like. Is a tricot,
The Miranese edition and the Russell edition are listed. Further, it can be used as a sheet-like material comprising a laminate in which at least one surface of the woven or knitted fabric is covered with a polyolefin-based resin layer.

The brominated flame retardants used in the present invention include tetrabromobisphenol A, decabromodiphenyl oxide, octabromodiphenyl oxide, bis (2,3-dibromopropyl ether) tetrabromobisphenol A, bis (2,3- Aromatic bromine flame retardants such as dibromopropyl ether) tetrabromobisphenol sulfone; alicyclic bromine flame retardants such as hexabromocyclododecane, dibromoethyldibromocyclohexane, and tris (dibromopropyl) isocyanurate;
And liquid bromine-based flame retardants such as pentabromodiphenyl oxide and tetrabromodiphenyl oxide. These may be used alone or as a mixture of two or more.

A flame retardant aid is used in combination with the brominated flame retardant for the purpose of improving the flame retardant effect.
Specific examples of the flame retardant aid include antimony-based flame retardant aids such as antimony trioxide and antimony trichloride. It is preferable that the compounding ratio of bromine-based flame retardant / antimony-based flame retardant aid be in the range of 2/1 to 3/1.

The amount of the bromine-based flame retardant and the antimony-based flame-retardant aid is determined by the amount of the brominated flame-retardant in the sheet.
10 to 10% by weight, 1 to 5% by weight of an antimony-based flame retardant, preferably 5 to 8% by weight of a bromine-based flame retardant, and 2 to 4% by weight of an antimony-based flame retardant. If the amount of the brominated flame retardant and the amount of the antimony-based flame retardant are less than 3% by weight of the bromine-based flame retardant and less than 1% by weight of the antimony-based flame retardant, the flame retardant effect is not sufficient, and the amount of the brominated flame retardant is 10%. % Or more than 5% by weight of the antimony-based flame-retardant auxiliary, the strength of the thread is undesirably reduced.

As a method of blending a bromine-based flame retardant and an antimony-based flame retardant auxiliary, a bromine-based flame retardant and an antimony flame-retardant auxiliary may be mixed with a polyolefin resin and supplied directly to an extruder; A masterbatch containing a high concentration of a bromine-based flame retardant and an antimony flame-retardant auxiliary in a polyolefin-based resin may be manufactured in advance and supplied as this masterbatch.

The above bromine-based flame retardant and antimony flame retardant auxiliary are mixed in the form of a laminated or core-sheath type composite yarn. Alternatively, it is preferable to mix only the sheath layer so as not to lower the strength of the core layer having a stretching effect by orientation. Even in the case where the yarn is a parallel type composite yarn, it is preferable that the bromine-based flame retardant and the antimony flame-retardant auxiliary be blended only in the surface layer so as not to lower the strength of the intermediate layer having a stretching effect by orientation. . Further, in a sheet-like material comprising a laminate in which a polyolefin-based resin layer is laminated on at least one side of a woven or knitted fabric, by blending a bromine-based flame retardant and an antimony flame-retardant auxiliary only in the laminated polyolefin-based resin layer, It is preferable not to reduce the strength of the woven or knitted fabric. .

[0012] The melt flow rate of the sheet-like material composed of the polyolefin resin containing the brominated flame retardant and the antimony flame retardant aid as described above may be at least 6 g / 10 min., Preferably at least 8 g / 10 min. It is important. The melt flow rate of the sheet is 6 g / 1
If it is less than 0 min., Since the sheet-like material exposed to the flame does not flow from within the flame, the sheet-like material is continuously exposed to the flame, causing a problem that it is carbonized and ignited and does not self-extinguish. The sheet-like material exposed to the flame is in a molten state first, and the polyolefin heated by the flame is decomposed and burns as hydrogen and carbon monoxide, and then the remaining carbon is ignited and becomes difficult to self-extinguish. However, at the time when the molten state is first obtained, the fluidity is good, so that it is washed away from the flame, and can be avoided from being further decomposed into a combustion or carbonized state. In this way, the molten material dropped from the flame early in the molten state is relatively lower than the ignition temperature of ordinary combustibles, so even if the ignition temperature is not lower than the melting temperature, even if it contacts the combustibles It does not propagate the flame.

[0013] The sheet-like material thus obtained preferably has a performance that meets the flameproof standard specified in Japanese Industrial Standard JIS-L1091.

The polyolefin resin used in the present invention includes an antioxidant, an ultraviolet absorber, a light stabilizer, a lubricant, an antistatic agent, a pigment, an inorganic filler, a flame retardant, without departing from the spirit of the present invention. And additives such as a crosslinking agent, a foaming agent and a nucleating agent.

[0015]

EXAMPLES The test method and evaluation method of the present invention were based on the following methods. Test method 1. Melt flow rate of sheet material: JIS K675
8 2. Flame retardancy: based on JIS L1091-D method. 3. Ignition property by drop: conforms to UL94VTM.

Example 1 It was difficult to mix a brominated flame retardant bis (2,3-dibromopropyl ether) tetrabromobisphenolsulfone and antimony trioxide at a ratio of 2: 1 with polypropylene (MFR = 5 g / 10 min.). A fuel master batch was blended, melt-spun using an extruder having a diameter of 65 mm, and drawn at a draw ratio of 7 to obtain a monofilament having a fineness of 400 denier (hereinafter abbreviated as d). Using this monofilament, a plain-woven fabric was formed at a driving density of 30 wefts / inch.

Example 2 A high-density polyethylene (MFR = 5 g / 10 min.) Was melt-film-formed, slit to a width of 20 mm, and stretched at a stretch ratio of 7 to obtain a flat yarn having a fineness of 950 d. Using this flat yarn, a plain woven fabric was formed at a weft density of 14 yarns / inch, and then a bromide flame retardant decabrom diphenyl oxide and antimony trioxide were applied on the front and back surfaces of the woven fabric at a ratio of 2: 1. The flame retardant masterbatch mixed in the ratio was blended with low density polyethylene (MFR = 8) and laminated by extrusion lamination to a thickness of 50 μm to form a laminate sheet.

Example 3 A high-density polyethylene (MFR = 3 g / 10 min.) Was mixed with a flame retardant masterbatch obtained by mixing a brominated flame retardant decabromodiphenyl oxide and antimony trioxide at a ratio of 2: 1. Was melt-spun using an extruder having a diameter of 65 mm, and stretched at a draw ratio of 7 to obtain monofilaments having finenesses of 500d and 850d. Of these monofilaments, a plain weave fabric was formed at a driving density of 26 filaments / inch through a 500d monofilament and 16 filaments / inch by a 850d monofilament.

Comparative Examples 1 to 3 Comparative Example 1 was performed in the same manner as in Example 1 except that polypropylene (MFR = 1 g / 10 min.) Was used.
Comparative Example 2 was performed in the same manner as in Example 2 except that high-density polyethylene (MFR = 1 g / 10 min.) Was used. High density polyethylene (MFR = 1g / 10mi
Comparative Example 3 was performed in the same manner as in Example 3 except that n.) was used.

Table 1 summarizes the measurement results of these Examples and Comparative Examples.

[0021]

[Table 1]

[0022]

As described above, the present invention is intended to improve the fluidity of a resin composition by blending a bromine-based flame retardant and an antimony-based flame retardant aid in a resin composition serving as a flameproof sheet. The flameproof performance can be improved, and it is effective as various flameproof sheets.

──────────────────────────────────────────────────続 き Continued on front page (51) Int.Cl. ⁷ Identification code FI C08L 23/02 C08L 23/02

Claims (1)

(57) [Claims] 1. A woven or knitted fabric comprising a polyolefin-based resin thread or a sheet comprising a laminate in which at least one surface of the woven or knitted fabric is covered with a polyolefin-based resin layer, 3 to 10% by weight of a bromine-based flame retardant. %, Antimony flame retardant aid 1
A flameproof sheet comprising 5% by weight and having a melt flow rate of 6 g / 10 min. Or more.