JPS63315685A - Heat and flame resistant rope - Google Patents

Abstract

(57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.

Description

[Detailed description of the invention] [Field of application of the invention] The present invention relates to robes, particularly heat-resistant and flame-resistant ropes.

Heat-resistant and flame-resistant ropes are useful as ttl robes, ladders, nets, etc. (hereinafter abbreviated as evacuation equipment) using the robes for evacuation, lifesaving, etc. in the event of a fire.

[Conventional technology]

Traditionally, robes have been made using natural, chemical, and synthetic fibers. Robes made of natural fibers or chemical fibers have the drawbacks of low strength and poor durability, so in recent years robes made of synthetic fibers have become mainstream. However, although robes made of synthetic fibers have vastly improved strength and durability compared to ropes made of natural fibers, in order to be used as evacuation equipment in the event of a fire, they require heat resistance and flame resistance. was inferior.

For example, if a fire spreads while you are evacuating using evacuation gear, i! There was a risk that the difficult tools themselves would burn out prematurely and become unusable.

Asbestos and glass fiber are fiber materials with excellent heat resistance and flame resistance, but the use of asbestos has been decreasing drastically in recent years due to problems with carcinogenicity, and it is also difficult to use as a residual material. Furthermore, although glass fiber has high yarn strength, its strength utilization rate is extremely low, and it cannot be used as a rope at all.

There are methods to make fibers flame retardant by post-processing natural fibers to give them resistance to flames, or by mixing so-called flame retardants into chemical or synthetic fibers, or by post-processing flame retardants. Even if ropes were used, if flames came into direct contact with the ropes, they would burn and break, and since the melting point of flame-retardant fibers did not rise, they would also melt and break at the same time, so they were rarely a solution to the problem.

'In addition, the meta-based wholly aromatic polyamide fibers that have been commercialized in recent years (for example, DuPont's Nomex, Teijin's Cornex) are mainly composed of polymetaphenylene inphthalamide, but this fiber has not been used in the past. Although it has higher heat and flame resistance than other flame-retardant fibers, when the fibers are exposed to high temperatures near their melting point, they undergo large thermal contractions and melt, resulting in poor heat resistance when exposed to flame. was rarely adequate.

[Problem that the invention seeks to solve]

The present invention aims to improve the above-mentioned drawbacks of conventional evacuation equipment and to create safer evacuation equipment. That is, the object is to provide evacuation gear that has excellent heat resistance and flame resistance, has a very slow burning rate, and can be used for a long time even when exposed to flames.

[Means for solving problems]

That is, the present invention provides Tm2350°C, Tm-Tex≧3
0”C.

Xc≧10cm, DE≧10%, Dsr (Tm)≦15cm, by using heat-resistant and flame-resistant rope made of amide fiber as evacuation gear, it is extremely effective compared to conventional evacuation gear. We have discovered that it is possible to obtain evacuation gear with high flame resistance.

Note that the characteristic values and physical property values of the aromatic polyamide fiber in the present invention represent values obtained using the measuring equipment and measuring conditions described below, respectively.

TrrB Melting point (°C); DS manufactured by PerkinElmer
Approximately 10 samples were placed in a sample dish made by A/C-20, and a 080 curve was obtained from room temperature to a predetermined temperature at 10°C per minute in a nitrogen gas flow (30ml/wig), and the endothermic peak temperature was determined as Tm. shall be.

Tex: Exotherm onset temperature (°C); PerkinElmer ■
Place a sample of approximately 10 mp in an At sample dish using DSC-2C (manufactured by Miyazaki) and draw a 080 curve from room temperature to a specified temperature at 10°C per minute in an air stream (30 FI// tone), and let the temperature at which the heat starts to heat up to be Tex. .

Crystallinity:
.

Using a diffraction angle of 2θ = 5° to 35' while rotating the sample in a plane perpendicular to the X-ray beam.
Obtain the line diffraction intensity curve, then convert the diffraction curve to the crystalline region (Ac)
and an amorphous region (Aa), and the value Xc calculated from the following equation is defined as crystal (t, fff).

Ac DE: Fiber elongation (%); using an Instron tensile tester, sample length 10 cn1, tensile speed 5α/min, initial load io
, 05r/d.

Dsr: Dry heat shrinkage rate (%); 0.1/d for fiber material
After measuring the thickness length tO by applying a load of The dry heat shrinkage rate DSR was determined by the formula.

D S R = -X 100% t.

Dsr (Tm) is the dry heat shrinkage rate at the melting point, and Ds
r(Tm+55'C) is the dry heat shrinkage rate at the melting point +55°C. □ The aromatic polyamide fiber used in the present invention needs to have the above characteristic values and physical property values. This will be explained.

Tm (melting point) is 350°C or more, and Tex (exothermic onset temperature) is 30°C or more lower than Tm (Xc (
When the crystallinity (crystallinity) is 10% or more, the fiber has excellent shape stability even when exposed to high temperatures above the melting point.

In other words, even when Tm2350℃ and Xc≧10%, Tm-Tex is 30℃ or more and Tm
- When comparing fibers with a Tex of less than 30°C, the former, that is, the Tex (thermal decomposition onset temperature) is 930° lower than the Trn (melting point).
The one lower than 3 is the latter, that is, Tex is Tm at 30°C.
It is said that the shape stability at high temperatures above the Tm (melting point) of the fiber is better than those below. This may seem absurd, but surprisingly, it actually turns out to be T.
The lower the ex, the better the shape stability.

I don't know the exact reason for this, but Tm23
50℃, Xc≧10% means 6.Tax For aromatic polyamide fibers that are 30℃ or more lower than KaTm, thermal decomposition starts from a relatively low Tex, so it occurs slowly and mainly in the amorphous region. At that time, since the microcrystals exist without melting in the crystalline region, the microcrystals act as restraint points for the molecular chains against thermal contraction that occurs as the orientation of the oriented molecular chains in the amorphous region is relaxed due to heat. It is thought that the morphological stability is improved even above the melting point because a kind of cross-linking occurs between the molecular chains as the thermal decomposition reaction progresses at the same time, and a three-dimensional structure is formed.

On the other hand, even if Tm is 350°C and Xc≧10, if Tex is lower than Tm by only 30°C, thermal melting will occur before a three-dimensional structure is formed due to sufficient intermolecular crosslinking. It is thought that heat shrinkage and fusion between fibers increased, resulting in poor shape stability.

In addition, the range of Tm-Tex is Tm-Tax≧30℃
−t”, preferably Tm−Tm+55′
C More preferably, Tm - Tex≧70゛c.

In addition, at temperatures above Tm, the tR fibrous property of the pond decreases to some extent, so in order to make a heat-resistant fiber that can be used at temperatures 200'C or more higher than general synthetic fibers, Tm23
50°C, preferably Tm≧400°C or more, more preferably Tm≧420”C.

That's all.

In addition, even if Tm2350℃ and Tm-Tex≧30℃, if the crystallinity is small (XC<10%), there is almost no restraining effect on molecular chain movement by microcrystals, so T
From the glass transition point, which is much lower than m, the thermal shrinkage increases rapidly and the shape stability becomes poor.

For these reasons, it is necessary that Xc≧10%,
Preferably Xc≧15%.

Furthermore, in order for the fiber to be used in the same way as existing organic synthetic fibers in applications such as clothing and industrial materials, good flexibility and processability as well as dyeability are essential conditions. For this purpose, it is important to have a sufficient balance between strength and elongation, especially elongation, and DE (fiber elongation) ≧1.
Must be 0chi. Preferably DE>15%, more preferably DE>20. Furthermore, fibers must be added to further enhance the morphological stability at high temperatures.

When Dsr (Tm) exceeds 15%, dry heat shrinkage is already large at the melting point, and the shape stability cannot be said to be good. Even if Dsr(Tm)≦15, thermal shrinkage increases rapidly, which is not preferable for the purpose of the present invention. Therefore, it is important that thermal contraction is sufficiently small even at temperatures considerably higher than the melting point.

Aromatic polyamide fibers having such specific physical properties include, for example, a lower alkyl group having 1 to 4 carbon atoms, or an amine group at the nitrogen atom of the amide bond and/or the ortho position of the phenylene group directly connected to the carbon atom. , a functional group selected from a sulfone group, a carboxyl group, a hydroxyl group, etc.
Or aromatic polyamide with halogen atoms)
! ! It is the fiber that was left behind. The substituent present at the ortho-position of the 7-ale group of the aromatic polyamide may be any substituent as long as it satisfies the physical properties of the fiber, but the above-mentioned substituents are preferred. More preferred are lower alkyl groups having 1 to 4 carbon atoms.

The production of such aromatic polyamides and fibers thereof is
Although not particularly limited, for example, according to the method disclosed in Japanese Patent Application No. 60-31490 separately filed by the present inventors, -N,N'- Using dimethylethylene urea as a solvent and an alkali metal compound as a catalyst, heating polycondensation is carried out at a temperature of 100°C or higher to obtain 1,1 (4-methyl-1,3-
) Unicine terephthalamide) is obtained. This polymerization solution is used as it is or, if necessary, concentrated and used as a spinning dope. The fiber manufacturing method includes, for example, using the above-mentioned spinning solution at a temperature of 20 to 150°C, preferably 40 to 150°C.
Hold at 100°C and add metal salts such as CaCA2, Z
10 to 50 wt% of nCA2, LiC42, LiBr, etc.
contained temperature 30 to boiling point temperature, preferably 50 to 100
℃ wet spinning in an aqueous solution, then 1.1 to 5 times wet heat stretching in an aqueous solution bath with almost the same composition as the coagulation bath, and then thorough water washing in 50 to 100 ℃ hot water. After drying with hot air at 100-200℃, then drying at 300℃
1.1-5 in air or inert gas bath at ~450°C
Manufactured by double dry heat stretching heat treatment.

The heat-resistant and flame-resistant rope according to the present invention has the above-mentioned Tm≧350°C.
, Tm-Tax≧30°C, Xc≧10%, DE≧Dsr
(Tm) It is of course possible to use a fiber made of 100% aromatic polyamide fiber, or to mix it with other fibers (blending, twisting, blending) as necessary.

Next, aspects of the present invention will be specifically explained with examples, but the present invention is not limited by these examples.

Example 1 Production of aromatic polyamide Terephthalic acid 166.0 f (0,9991 mol) and monopotassium terephthalate m2 were placed in a 3-capacity separable flask equipped with a stirrer, thermometer, condenser, dropping funnel, and nitrogen introduction tube. .038F, anhydrous N2, N'-dimethylethylene urea (1600 m/) is charged under a nitrogen atmosphere and heated to 200°C with stirring on an oil bath. Tolylene-2,4-diisocyanate 174.0f (0,9991 mol) was added to anhydrous N while maintaining the contents at 200°C.
, N'-dimethylethylene urea 160d was added dropwise from the dropping funnel over a period of 4 hours, and after the reaction was continued for an additional hour, heating was stopped and the mixture was cooled to room temperature. A portion of the reaction solution was poured into strongly stirred water to precipitate a white polymer, and after further washing with a large amount of water,
The logarithmic viscosity (9
5ch H2SO40.1%, 30°C) was 2.2.

The polymer concentration of the polymerization solution is still about 11.0 fi-[%,
The viscosity of this solution is 420 boise (BW viscometer; 50°C)
Met. The obtained polymer also has an IR spectrum, N
It was confirmed by MR spectrum that it was poly(4-methyl-1,3-)unicine terephthalamide).

The above polymerization solution is degassed under reduced pressure at 50° C. to prepare a spinning dope that does not contain air bubbles. Then, while maintaining the temperature at 50°C, the pore diameter Q and l1
54.w, from a nozzle with 600 holes (6 holes are circular) into an aqueous coagulation bath containing 4240% CaC maintained at 80°C.
Discharge at 4M/min. The filament discharged from the nozzle passes through a coagulation bath and is then subjected to moist heat stretching for approximately 1 hour in a bath having the same composition as the coagulation bath.
．． 6 times, and then thoroughly washed with water in a washing bath of 80°C warm water, followed by applying an oil agent and drying in a hot oven at 150°C to obtain a moist heat drawn spun yarn.

The spinning yarn has an oval cross section but is homogeneous and has a diameter of 2900
It was a denier/600 filament.

Next, this spun yarn was subjected to hot drawing at a draw ratio of about 2.4 times using a nitrogen flow hollow dry heat drawing machine maintained at 430"C, thereby producing the poly(4-methyl-1,3) of the present invention.
-) unilente terephthalamide) fiber was produced.

The physical properties of the obtained fiber were as follows: single yarn denier = 2, strength = 5.
897 dr, elongation ji=25.4%, Young's modulus=88f
/d, Tm=425℃, Tex=330℃, Tm
-Tex=95℃, XC=24%, Dsr(Tm)
= I) sr (425°C) = 11%, Dsr (Tm) Dsr (425°C) 13%, which numerically shows good general fiber physical properties and excellent morphological stability at high temperatures above the melting point. I understand.

Using this fiber (2 dr x 51 m), a spun yarn with a cotton count of 10''/1 was spun by a normal staple spinning method.

The strength of the obtained spun yarn is 1.5 to 4! , the elongation was 16%. Using this yarn, 12 φ three strokes 50-pu (10
1s/10X3X11X3) was created. Rope performance is shown in Table 1.

The heat-resistant and flame-resistant dest shown in Table 1 is one in which a rope is stretched horizontally and flame is blown from a propane gas burner from 505 m below the rope.

At this time, one end of the rope was fixed, and a load of 60 positive was applied to the other end via a pulley.

Comparative Example 1 Production of poly(metaphenylene isophthalamide) Into a 2 t jacketed separable flask equipped with a stirrer, a thermometer, and a jacketed dropping funnel, 600 d of anhydrous tetrahydrofuran containing 250.2 F (1,232 mol)% of diinphthalic acid chloride was introduced. The contents were cooled to 20° C. by passing a refrigerant through the jacket. While stirring vigorously, add 11% of metaphenylenediamine to 400% of anhydrous tetrahydrofuran.
Approximately 20% of the solution containing 33.7f (1,237 mol)
It was dripped in minutes. The obtained white emulsion was quickly poured into water (water-cooled) containing 2.464 mol of anhydrous carbonate under strong stirring. Immediately, the slurry temperature rose to near room temperature. Subsequently, the slurry was prepared with caustic soda to a concentration of 11, and the resulting cake was thoroughly washed with a large amount of water and dried overnight under reduced pressure at 150°C. The logarithmic viscosity of the polymer was 1.4.

Preparation of poly(meta-phenylene isophthalamide) fibers The poly(meta-phenylene isophthalamide) or P
MIA polymer powder was mixed with N-methyl-2-pyrrolidone (N
MP) and NMP were dissolved in a solvent containing 2 parts of LiC1 with a 22% heavy-duty tile, and defoamed under reduced pressure at 80°C to prepare a spinning dope free of air bubbles. Then, while maintaining the temperature at 80°C, it was discharged from a nozzle with a hole diameter of 0.08 mm and 100 holes (6 holes are circular) into an aqueous coagulation bath containing 240% CaCt maintained at 80°C for 5.297 minutes at 10 m/min. After passing through a rotating roller and an 80°C hot water bath, rinse thoroughly with water.
Subsequently, wet heat stretching was performed in hot water at 98°C using rollers at a magnification of 2.88 times, and after applying an oil agent,
The yarn was dried by passing it through a hot air bath at ℃ to obtain a spun yarn that had been subjected to wet heat stretching. The spun yarn had a homogeneous cocoon-shaped cross section and was laid with 358 denier/100 filaments.

Next, this spun yarn was dry-heat-stretched by 1.88 times on a plate at 310°C to form poly(metaphenylene inphthalamide) hawk fiber (8 strands).

The physical properties of the obtained fibers were as follows: single yarn denier = 2, strength = 4.
9 P/d, time variation = 28.5%, Young's modulus = 80f/d
%Tm=425℃, Tex=405℃, Tm-Tex
=20°C, Xc = 2 s%, Dsr(Tm) =
Dsr (425"C) = 16%, and although this PMIA fiber exhibits good general fiber properties, it is clearly inferior to Example 1 in terms of shape stability at high temperatures above the melting point. became.

Using this fiber (2dr x 51+m), a spun yarn with a cotton count of 101 s/l was spun by ordinary staple spinning.

The resulting spun yarn had a tenacity of 1.3 and an elongation of 20%. Using this yarn, use a 12fiφ triple rope (10
18/10X3X11X3) was created. Rope performance is shown in Table 1.

Comparative Example 2 Commercially available vinylon 12■φ triple rope (s 1315
Table 1 shows the result of performance measurement of X3X11X3).

Chapter 1 Table Patent applicant RiRashi Co., Ltd. Same Mitsui Toatsu Chemical Co., Ltd.

Claims (1)

[Claims] 1. Heat-resistant and flame-resistant rope made of aromatic polyamide fiber having characteristics satisfying the following formula: Tm≧350°C Tm-Tex≧30°C Xc≧10% DE≧10% Dsr (Tm)≦ 15% [Dsr(Tm+55°C)]/Dsr(Tm)≦3 (where Tm is the melting point (°C), Tex is the exothermic start temperature (°C),
Xc is crystallinity (%), DE is elongation (%), Dsr (T
m) is the dry heat shrinkage rate (%) at the melting point Tm, Dsr(T
m + 55℃) is the dry heat shrinkage rate (%) at the melting point + 55℃
represents. ) 2. The aromatic polyamide fiber has a lower alkyl group having 1 to 4 carbon atoms, or an amino group, a sulfone group, a carboxyl group, or a hydroxyl group in the ortho position of the phenylene group directly connected to the nitrogen atom and/or carbon atom of the amide bond. The heat-resistant and flame-resistant rope according to claim 1, which is manufactured from an aromatic polyamide having a selected functional group or a halogen atom.