JPH0730332B2 - Foamable fireproof composition and foamable fireproof sheet - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial field of application] The present invention uses a so-called foamable fire-prevention composition that produces a foaming coal fire when heated to a high temperature and exhibits a fireproofing function, and the composition. Foamable fireproof sheet.

[Prior art] From the experience of tragic fire accidents in factories and buildings, the development of disaster prevention equipment and fire prevention materials in our country has been truly remarkable recently, and the newly developed disaster prevention technology can be applied to various production facilities. Contributes to the realization of higher productivity under higher security against fire.

[Problems to be solved by the invention]

The present inventors have previously developed a foamable fireproofing composition, but the composition is somewhat inadequate for adaptability to equipment constantly operated at high temperature, for example, 60 to 100 degrees, and a foamed carbonized layer. There was also room for improvement in toughness. For this reason, usability at high temperatures and strengthening of the foamed carbonized layer have become problems.

[Means for solving problems]

This problem can be solved by using a fluorinated elastomer together with a chlorinated polyethylene, a nitrogen-containing polyphosphate compound, pentaerythritol, melamine and the like.

That is, the specific invention of the present invention is (a) chlorinated polyethylene,
(B) a nitrogen-containing polyphosphate compound, (c) pentaerythritol, (d) melamine, and (e) a fluorine-based elastomer, and (b) component (c) component per 100 parts by weight of (a) component, and The total amount of component (d) is 50-
400 parts by weight, component (e) is 5 to 50 parts by weight, and the component ratio of component (b), component (c) and component (d) is α point (10, 60, 30) on the triangular coordinate. , Β point (35, 60, 5), γ
Points (90, 5, 5), δ points (35, 5, 60), and ε points (1
(0, 30, 60) is located in a region surrounded by a straight line that sequentially connects points, and the second invention of the present invention is (a) chlorinated polyethylene, b) a nitrogen-containing polyphosphate compound, (c) pentaerythritol,
(D) Melamine and (e) Fluorine-based elastomer, and the total amount of (b) component (c) component and (d) component is 50 to 400 parts by weight per 100 parts by weight of (a) component, ( component (e) is 5 to 50 parts by weight, component (b),
The component ratios of the (c) component and the (d) component are α point (10, 60, 30), β point (35, 60, 5), γ point (90, 5, 5) on the triangular coordinate, δ points (35, 5, 60) and ε points (10,
(30, 60), which is composed of the composition within a region surrounded by a straight line connecting the respective points in sequence, and has been subjected to heat treatment, and is directed to a foamable fireproof sheet.

[Operation and Configuration of Invention]

INDUSTRIAL APPLICABILITY According to the present invention, a composition which is excellent in high temperature usability, has a strong foamed carbonized layer, maintains the shape of the foamed carbonized layer for a long time, and therefore does not deteriorate fire protection performance can be obtained. In addition, various physical properties such as self-fusion property are also improved.

As the component (a), commercially available chlorinated polyethylene is used, and those having a chlorine content of 20 to 50% by weight are particularly suitable.

As the component (b), for example, the general formula H _{(nm) +2} (N
H ₄ ) _m P _n O _{3n + 1} (where m / n is 0.7 to 1.1) and ammonium polyphosphate having an average degree of polymerization of 20 to 400, a general formula (NH ₄ ) _{n + 2} P _n O _{3n +} Ammonium polyphosphate, which is a linear condensate having an average degree of polymerization of 150 to 200 represented by ₁ , or polyphosphoric acid amides (for example, Sumitomo Chemical Co., Ltd., trade name Sumisafe P) is used.

As the component (c), various pentaerythritols such as mono-, di-, or tripentaerythritol are used.

The components (b), (c), and (d) are α points (10, 60, 30), β points (35, 60, 5), γ points (90, 5, 5) on the triangular coordinates. , Δ points (35, 5, 60) and ε points (10,
30 and 60) are used in the area where each point is connected by a straight line. Further, the total amount of the component (b), the component (c), and the component (d) is 50 per 100 parts of the component (a) (parts by weight, the same applies hereinafter).
~ 400 parts, preferably used in the range of 100-200 parts,
The component (e) is 5 to 50 parts, preferably 1 to 100 parts (a).
Used in the range of 0 to 30 parts.

The effect of the fluorine-based elastomer as the component (e) is that the composition promotes foaming and carbonization when it comes into contact with a fire, strengthens the foamed and carbonized layer, and maintains the shape retention of the carbonized layer for a long time.
Performs a function that does not deteriorate fire protection performance for a long time.

As the component (e), any commercially available fluorine-based elastomer can be effectively used. For example, vinylidene fluoride-6-fluorinated propylene copolymer rubber (Viton A manufactured by DuPont, manufactured by Daikin)
G755 etc.), vinylidene fluoride-6-propylene propylene-4
Fluorinated ethylene terpolymer rubber (Viton B manufactured by DuPont, G901, G902 manufactured by Daikin), vinylidene fluoride-5 propylene fluorinated copolymer (Technoflon SL, T manufactured by Monte Edison) Etc.

When the amount of the component (e) used is less than 5 parts per 100 parts of the component (a), the strength of the foamed carbonized layer is weak and the shape cannot be retained for a long time. On the other hand, when it is more than 50 parts, the processability of the composition is poor.

In the present invention, if necessary, a known inorganic flame retardant,
Organic flame retardant, for example, Sb ₂ O ₃ , hydrated alumina, decapromodiphenyl oxide in an amount of 1 to 1 per 100 parts of the component (a).
About 00 parts may be used together, and various agents, stabilizers, pigments, plasticizers such as rubber and plastic compounding agents, such as tricresyl phosphate, tris (monochloropropyl) phosphate, tris (1,3 dichloropropyl). A flame retardant plasticizer such as phosphate may be added in a usual amount.

The composition of the present invention can be formed into various shapes, for example, pipes, rods, sheets (including tapes) by ordinary means such as extrusion processing and roll processing, and fire protection equipment. When applied to the above-mentioned products, the above-mentioned various forms have an effect of being used after being molded.

The composition of the present invention is manufactured by a usual kneading method, and then molded into a desired shape, for example, a sheet, and then subjected to a mild heat treatment to improve the physical properties at a higher temperature, particularly the stress crack resistance. The above heat treatment is 60 ℃ -120 ℃, especially 80-100 ℃
It is preferable to carry out the treatment at 60 ° C for 2-3 times, at 80 ° C for 10-40 hours, and at 100 ° C for 5-2.
It may be 0 hour, 120 ° C. for 0.5 to 2 hours. The tape-shaped heat-treated sheet may be manufactured by heat-treating a wide sheet and then chopping it.

〔Example〕

Hereinafter, the present invention will be described in more detail with reference to Examples and Comparative Examples.

[Examples 1 to 9 and Comparative Examples 1 to 12] The compositions of Examples 1 to 9 and Comparative Examples 1 to 12 shown in Table 1 were mixed and kneaded by a two-roll mill, and then an 8-inch inverted L-shaped calender roll. After rolling to a thickness of 0.7 mm, a tape was cut into a width of about 40 mm, and a predetermined heat treatment was applied. (However, Examples 8 and 9 are not heat-treated.) In Table 1, the blending amount of each component is shown in parts by weight.

A tape produced from each composition was manually wound twice on a 600V 3 × 3.5 mm ² CV cable with a 1/2 wrap, and the tape was wound and coated to a thickness of about 2 mm according to the test method and evaluation criteria described below. Foam fire resistance and thermal stress cracking resistance in hot water immersion at 60 ℃ were evaluated.

Separately, the flame resistance and self-fusing property of the tapes produced from each composition were evaluated.

(Foaming fireproof performance evaluation test method)

Approximately 2 mm of tape on a 600 V 3 x 3.5 mm ² CV cable (approximately 30 cm long)
The sample of wire covered with winding until it becomes thick is heated to flame temperature 11
It burns with a Bunsen gas burner whose temperature is adjusted to 00-1200 ℃. Immediately after the sample comes into contact with the flame, measure the time until a short circuit is generated by applying a voltage of AC600V between the lines. The test results were ranked in three levels according to the criteria described below. That is, those with fire protection performance that does not crack or collapse in the carbonized layer in 40 minutes or more short-circuit time under AC600V energization, ◎, those with no crack in the carbonized layer in 20 minutes or more 〇, short-circuit time
The case where a large crack or collapse occurred in the carbonized layer within 10 minutes was judged as x.

Normal 600V 3x3.5mm without tape wrapped
The short circuit time of the ² CV cable was 2-3 minutes.

[Thermal stress crackability evaluation test method]

A sample electric wire with a length of about 70 cm is immersed in a water tank at 60 ° C with both ends exposed above the water surface, and the presence or absence of tape cracks is observed during the immersion.
Left for days.

In the evaluation, those in which the tape cracks were generated were evaluated as bad, and those in which the tape cracks were not generated were evaluated as good.

[Flame retardancy evaluation test method]

The oxygen index was measured in accordance with JIS K 7201, and those with 55 or more were rated as A, those with 30 or more and less than 55 were rated as B, and those with less than 30 were rated as C.

[Self-fusion property]

Adhesive strength is measured according to JIS C 2107. A with an adhesive strength of 2 kg or more is A, B with 1 kg or more and less than 2 kg, 1
Those having less than kg were evaluated as C.

[Brief description of drawings]

The attached figure is a triangular coordinate showing the component ratio of the component (b), the component (c) and the component (d) used in the present invention.

Claims (2)

[Claims] 1. A chlorinated polyethylene, (b) a nitrogen-containing polyphosphate compound, (c) pentaerythritol,
(D) Melamine, and (e) Fluorine-based elastomer, and (b) component per 100 parts by weight of (a) component,
The total amount of the components (c) and (d) is 50 to 400 parts by weight,
(E) component is 5 to 50 parts by weight, (b) component, (c)
The component ratio of the component and the component (d) is α on the triangular coordinate.
Points (10, 60, 30), β points (35, 60, 5), γ points (90,
5, 5), δ point (35, 5, 60), and ε point (10, 30, 6)
(0) A foamable fire protection composition, which is in a region surrounded by a straight line connecting each point in sequence. 2. (a) Chlorinated polyethylene, (b) Nitrogen-containing polyphosphate compound, (c) Pentaerythritol,
(D) Melamine and (e) Fluorine-based elastomer, and the total amount of (b) component (c) component and (d) component is 50 to 400 parts by weight per 100 parts by weight of (a) component, ( component (e) is 5 to 50 parts by weight, component (b),
The component ratios of the (c) component and the (d) component are α point (10, 60, 30), β point (35, 60, 5), γ point (90, 5, 5) on the triangular coordinate, δ points (35, 5, 60) and ε points (10,
(30, 60) is a foamable fireproof sheet characterized by comprising a composition within a region surrounded by a straight line connecting each point in sequence and heat-treated.