JPS60151314A - Production of aromatic polyamide fiber - Google Patents

Abstract

PURPOSE:An undrawn yarn of a specific aromatic polyamide is coated with a fine powder of another aromatic polyamide melting at a temperature higher than the drawing temperature of the yarn, then subjected to flow drawing at elevated temperature to give the titled fiber which can be used in reinforcement, because of its good flexibility and high adhesion to rubber, without trouble in filament fusing. CONSTITUTION:An undrawn or semi-drawn yarn of the aromatic polyamide in which more than 80mol% of the recurring units is formula I (Ar1, Ar2 are aromatic residue of formulas II and III, which may be substituted with halogen and lower alkyl) is coated with a fine powder of an aromatic polyamide with a melting point higher than the yarn drawing temperature, then subjected to flow- drawing at >=300 deg.C to give the objective fiber.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to the TiA method for producing aromatic polyamide 1JIi navy blue. More specifically, an aromatic polyamide undrawn yarn or semi-drawn yarn consisting of one set of polymer repeating units is flow-stretched to a high magnification to produce a high-strength, high-modulus aromatic polyamide yarn. The present invention relates to improvements in methods for producing polyamide fibers.

[L Good 1] In recent years, the requirements for synthetic fibers have become more sophisticated, especially high strength,
In response to the demand for Hatake mosicolase, various new fiber layers have been developed. Among them, aromatic 1M polynoamide fiber,! 411ff, a substantially para-oriented aromatic copolyamide containing ether bonds in some of the polyamide repeating units, as described in British Patent No. 1501948, exhibits its performance. In order to avoid this, the undrawn yarn □ is drawn at a high temperature of 300°C or higher at a draw ratio of ´C.
The "J method" in which the yarn is stretched to a high magnification of 6 times or more is employed. In this case, the undrawn yarn is gradually stretched without passing through the neck, taking the form of so-called 1-1-stretching.

However, when this J: sea urchin is flow-stretched at a high temperature, the yarn is stretched to 11, becomes extremely soft, and the M! A phenomenon occurs. '1. Furthermore, as the number of filaments in the yarn increases, the fusion rate increases, which not only reduces drawability but also results in extremely low flexibility of the resulting drawn yarn. .

Therefore, a method has been proposed in which a water-soluble or hydrated gel-forming inorganic compound is added to the undrawn yarn (for example, 1:j Kaimei No. 53-147811, Japanese Patent Application Laid-Open No. 58-54021). Publications, etc.).

This 7'j? According to A, fusion is reduced, drawability is improved, and the drawn yarn becomes considerably flexible. However, its ability to prevent fusion is insufficient, and the inorganic compounds remaining in the thread impair its adhesion to rubber and resin.

OBJECTS OF THE INVENTION As mentioned above, the main purpose of the present invention is to prevent the fusion between single fibers that occurs when flow-drawing the aromatic Borif 7-mid fibers at high temperatures, and to improve the drawability by -1. In addition, it increases the flexibility of the drawn yarn and improves its adhesion to rubber and resin.
In particular, these shrines are
The purpose of the present invention is to produce aromatic hX polyamide fibers.

According to the present invention, an undrawn yarn or semi-drawn yarn of a fiber made of a specific aromatic polyamide (1) is subjected to an 811 point higher than the drawing temperature of the undrawn yarn or semi-drawn yarn. This is achieved by applying a fine powder of another aromatic polyamide (II) as described above and drawing the undrawn yarn at a drawing temperature of 300 DEG C. or higher.

In the present invention, "the fiber shoulder 1 made of a polyamide (I)" means that 80 mol% or more -LNlf or 90 mol% or more of the repeating units constituting the polyamide are -N +
-1-1 Δr+ N H, CO-Arz Co- As for small polyamides or aromatic coborias, see, for example, British Patent No. 1,501,948, U.S. 14th Edition, No. 3 z-'t 30 a It is described in the April specification, Japanese Unexamined Patent Publication No. 100322/1984, etc.

In the present invention, on the back side of the aromatic polyamide (i), 51 of the An, Arz and 80 mo) Li% U.

Above is the following aromatic IN residue, group (A), ([3>(A)
Aromatic boria/midos that are ~40% are preferred.

Specific examples of this J:Una aromatic copolyamide include copolyamides composed of the following three seven-piece units.

Further, an aromatic copolyamitom having 30 mol% or more of the above Δn, Ar2, or the following aromatic residues (A), (B'), and the structural unit (B) in a mol% of 10 to 40%. suitable.

Specific examples of such 'Al7M copolyamides include:
The following copolyamides are composed of 414 units:

The fibers made of the above-mentioned aromatic polyamide (I), especially the fibers made of the aromatic copolyamide (1) containing an ether bond in a part of the polymer, are undrawn yarns or semi-drawn yarns:
(To obtain a drawn yarn with high tenacity and high modulus by drawing it to a ratio of 8, the undrawn yarn or semi-drawn yarn should be heated at 300°C or higher, preferably from 350 to 550°C. Maro ni IJ11
However, pull it out gradually to avoid creating a neck! J [
)L”-stretching”. This is because the yarn is i! '! It is necessary to lengthen the heating zone so that the heating period until the end of stretching is 0.2 seconds or more.

At this time, since the yarn is drawn at a high quality, the single fibers become soft and the drawability deteriorates considerably, and the quality of the drawn yarn also deteriorates. Therefore, a method has been proposed in which a water-soluble or hydrated gel-forming inorganic compound is applied to the semi-drawn yarn (Japanese Patent Application Laid-open No. 54021/1983), but the number of song titles is reduced. Therefore, there was a drawback that the adhesion force with the resin and the coating was reduced when applying 1hf.

In the present invention, in order to solve this problem, the undrawn yarn or semi-drawn yarn is coated with fine powder made of an aromatic polyamide (■) whose melting point is higher than the drawing temperature.
C, followed by C, the undrawn yarn or semi-drawn yarn at 300°C or higher.
Preferably, at a stretching temperature of 350 to θoo'c,
Extend.

Aromatic polyamide (n
) Due to the coating of fine powder in 1), the distance between the single fibers is greater than before.
Not only is it possible to significantly reduce the number of 141 coats, but also the adhesion of the drawn yarn to rubber or resin is improved.

The aromatic polyamide (II) used in the present invention is an undrawn or semi-drawn yarn made of aromatic polyamide (it'), which has a melting point higher than that of a stretched yarn.

Here, "undrawn yarn or semi-drawn yarn" refers to the
Fibers made of χ polyamide (1) that have undergone the final drawing and have insufficient molecular orientation.For example, the strength of the drawn yarn is 259/de, the X7 rate is 900 g/lie In this case, the strength of the [undrawn yarn or semi-drawn yarn] is 15 J/dO or less, and the Young's modulus is 5007.
There is a smaller amount of C than /de. A yarn with such physical properties is either a yarn that has not been drawn at all or a yarn that has been drawn to an intermediate stage in multi-stage drawing.

Furthermore, in the present invention, the "stretching temperature of undrawn yarn or semi-drawn yarn made of 6-aromatic polyamide (I)" refers to the temperature reached during stretching of undrawn yarn or semi-drawn yarn made of yJ aromatic polyamide (i). This means the highest yarn temperature (1max). The yarn temperature (1-max) is lower than the temperature of the gas in a non-contact furnace or the hot plate surface of a contact drawing hot plate per item.
1a I stand C.

In the present invention, C, y';
) When using aromatic polyamide powder with a melting point lower than the yarn temperature (Tmax) of
The effects of the present invention cannot be compared to the monofilament comrades. However, the aromatic polyamides 1 to (II
The fine powder of It also shows a clear melting +: a and includes decomposition J.-1
-From max to 11"f,il! A fine powder of aromatic polyamide <II) with a point I1 is applied to an undrawn yarn or a semi-drawn yarn and stretched. 4) The drawn yarn with strong force is drawn once.

A preferred polyilamide (11) of the present invention is one in which 80% or more of the aromatic residues in the polymer are composed of bacinoJ-lene groups. , 1, ′j is polyparaphenylene terephthalamide,
Polyparabenzamide is preferred.

No clear melting point is observed for Boribara Funyren J-Renotarami 1- and Boribashi Benzami 1~, but it is clear that A11! is below 500°C! There are no points.

The fine powder made from the aromatic polyamide (lt) of the present invention has an average particle size of 20 microns or less, 10 microns or less per Zj, and is suitable for uniformly spreading on the surface of single fibers. -(I'm ashamed.

Here, the average particle size (r) is the average particle size of fine powder particles V
From the following formula (・Sub-main.

The polymerization of the aromatic hX small lismid (if)
An interfacial method using diamine and hIS group acid diacid dichloride trimer and using conventionally known polymerization media such as C-1-RAH-Furan, N,N'-dimethylaretamide, N-MeJ-R, etc. A solution using pyrrolidone or the like as a polymerization medium is easily carried out. The aromatic 15-group polyamide (I
In order to obtain 1 quart of the fine powder of I), crush the polymer mass that has precipitated after polymerization using a high-speed hutter, etc., and add a precipitant to the polymer that has been polymerized and dissolved. The polymer is crushed while adding, preferably 0% to the polymer.
Using a certain polymerization medium as solvent-C, polymerization was carried out under rapid stirring at a rate of -(l':'+l) and the polymer was simultaneously imitated.
In this case, the degree of polymerization of the polyurethane is low, but the lower the degree of polymerization, the less bulky the fine powder becomes.
It is rather suitable for the purposes of the present invention.

For example, polyparaphenylene terephthalamide and polypara I
＼In order to remove the heavy content, use a polymerization medium with increased dissolving power, 1 and 4 samedelphos small amide/N-methylpyrrolidone/lithium chloride. system, N-methylpyrrolidone/calcium chloride, chloride system, N,N'-dimethyl 71cetamide/J
Mated layer lucium lithium chloride system, N, N', N''
, N''-Te1~lamedel urea/calcium chloride, lithium chloride systems, etc. are used, but in the present invention (゛ is a hand compound with low dissolving power, iJ /, f straw hexylmethyl small sphoramide, N-methyl Pyrrolidone, N,N'-dimedylarethamide, N,N.

Nl, NN, NILL-I, il-solvents such as lamedel urea are preferred.

Polymerization took 103 sec-' or more! /v If) I-speed IQ stirring C is performed, for example, when using a screw type stirring blade, 100 r 11111
A higher rotational speed is preferred.

The aromatic hk polyamide (11) containing melon (LC<T
In order to reduce the aroma, one of the diamine and the aromatic acid dichloride is added in excess.

Precipitation of the polymer fine powder1. :! f! The finishing system may be washed with water and the fine powder may be used in a wet state, or it may be used after drying.

The method of applying the fine powder to undrawn yarn or semi-drawn yarn of 'r';It/A polyamide (I) is as follows:
It is preferable to disperse the fine powder in water, soak the undrawn yarn or semi-drawn yarn in 1iif; 1- Apply to the thread through the snow II 'J ru l) Nno, r
b J, I 1゜The dispersion liquid is prepared by adding water to the fine particles in the above-mentioned wet state, or by adding water to the dried fine particles to adjust the concentration to usually 0.5 to 3%. . It is also possible to use a surfactant to improve the dispersibility of the fine powder, or to mix an antistatic agent to improve the cohesiveness of the yarn. Mix inorganic fine powder within a range that does not damage '+1'L.

The amount of J shield for the undrawn yarn of the fine powder is
(!- Based on the standard, 3% to C001 is suitable. (
= If the amount of J is too small, the effect of the present invention will be reduced, and if it is too large, the fibers will be contaminated with fine powder, and the subsequent process C-
It can also cause tofu.

The undrawn yarn or semi-drawn yarn coated with the fine powder is 4+
Stretching temperature C is flow stretched at 0℃ or higher, but the horn type is contact) (, non-contact type is 4:) J, for example, hot plate, medium Y tube, gas blowing (=J, The stretching atmosphere is air-free, but the stretching temperature is in the range where polymer oxidation and cross-linking reactions occur, nitrogen, water, air, etc. An inert gas is preferred.

The temperature of zone () is adjusted to the specified stretching temperature (
It is preferable to adjust the temperature to a temperature higher than 100° C. from 100° C. to 20° C.

The heating atmosphere varies depending on the type of fiber being drawn, the fiber size, etc., but in order to increase the drawing ratio to the maximum,
The fiber being drawn must be heated for at least 0.2 seconds.

Stretching can be done in one stage with zero, but it is also difficult to stretch it in two or more stages. Further, after pre-stretching at a low temperature of 300'CJ, the stretching of the present invention can be carried out.

When the stretching ratio is set such that the total stretching ratio is at least Gfs, preferably at least 8 times, fibers with high strength and high modulus can be produced.

Functions and Effects of the Invention The above-mentioned aromatic poly)nomide fiber is a yarn.
The performance of C1 is first revealed by U-stretching it to iI (i: J S4+!) at high temperatures above the softening temperature, such as when the degree of hardness is about 30°C (1'C or more), and it has high strength and high modulus. Sen 11 (screams. However, 5 yen E
Since the single fibers of the Z polyamide fiber do not fuse together in this softened state, the undrawn yarn has no water solubility or hydrated gel forming property (method 1: applying a back-stroke and drawing it);
? However, in order to reduce melting, increasing the amount of coating reduces the adhesive strength of rubber and resin.

However, according to the present invention, the undrawn yarn of the aromatic polyamide fiber is injected with another aroma that has the points (J, H', and M1) to the right of the drawing temperature of the undrawn yarn or semi-drawn yarn. family bolino′
The surface of the C1 single fiber is coated with the Group 6 polytsunomide fine powder CB, which suppresses the occurrence of song names in a single meter length and stretches it, resulting in a high-quality sheet with less fusion. Since high-quality yarn is obtained, and the fiber surface is covered with organic matter, adhesion to rubber and resin is greatly improved.Also, the strength and stiffness are high, so it is not suitable for rubber or resin. It can be widely used for a variety of purposes, including reinforcing materials.

11, the method of the present invention will be explained in detail by way of examples. In addition, in the following example, the main characteristic vessel C is measured as follows. .

(1) Intrinsic repulsion of polymer (1, V,) A strode! l"Ji' + common tube, the flow time of only the solvent is t
o (seconds), the flow time of the dilute polymer co-solution is 1 (seconds),
When the polymer concentration in the dilute a9 solution is C<w/dρ), it is expressed as lV=[1(t/lo)/c.

Unless otherwise noted by Qir, solvent was 97.5% sulfuric acid, C=
0.59/d Measured at 30°C in summer.

(2) Lean sill the fused and stretched A7-line to a length slightly longer than 100 cm, and hold the 9i: with a clip so that it does not hang vertically.

Set the measurement range to 1 (10 cm), insert a bottle of approximately 1 putΦ between any fibers in the center, move it up and down so that the pin moves without resistance (measure the distance it pulls, and find the distance. .

If there is not enough 1u for the pin to stop within the measurement range on one side, the bottle will move if!'I measure the distance within the specified range.

Take 20 pieces of wood, find the average value, and fuse it (
L) Dokanaf.

(3) Peeling Adhesive Strength 5 cords were buried near the surface layer of the rubber sheet and vulcanized for 130 minutes at 150'C under pressure, and then the 5 cords were peeled off from the rubber sheet 1 at a speed of 200 mIn1 min. The force required for isolation is defined as the peel adhesion force.

(4) Pulling Adhesive Strength A =1-tall with a length of 10 mm was embedded in 10 packs of uncombed rubber and vulcanized under pressure for 150"C for 130 minutes, and then the cord was pulled from the rubber block at a speed of 200 m/min. In step 1, the force (resistance) required for pulling out is defined as the pulling adhesive force.

Example 1 Preparation of aromatic hχ polyamide fine powder (river; '4 inhibitor) 1 (1-speed deflection J'l'&! -Methyl-
Add 2-pyrrolidone (NMP) 850 yen to 21.34
Dissolve diamine in No. 49 baraf. While stirring the solution at 30°C at high speed (1000 r++m ), 37,715 y of terenothalic acid dichloride powder was added all at once to proceed with polymerization, and after about 20 seconds, fine powder of polyparaphenylene terephthalamide (PPTA) was precipitated. What happened to the dispersed slurry?

4. Filter this slurry, wash it with water, and leave it in a wet state.
3. Add Q of water to make 151k of anti-fusing agent dispersion with a concentration of 1% or more.

On the other hand, a small amount of polymer was taken out from this dispersion, dried, and the melting point was measured using a differential heating mat (DSC).
Dispersion started at 500°C and no clear melting point was shown. There was clearly no melting point below 500°C.

On the other hand, polymer 1. V is 0. f3, and the average particle size was 3 μm c.

Grave 1 row 11 The upper unit below is an I, V, -3,1 aromatic copolyamide composed of N-methyl-2-pyL:l lydone ( A polymer solution prepared by dissolving 6% by weight in NMP) was prepared using a pore diameter of 0, 3 mm, and a pore number of 2.
It was extruded from a 50 spinneret at a rate of 937/min.

After traveling approximately 10 mm in the air, it was coagulated in a coagulation bath of NMP/water (30/70 ω%) at 50°C for 15 years.
After taking it out at a speed of t/' min and washing it in a water bath at 50°C, the PPTA adjusted by the h method of the previous method was used. The sample was immersed in a dispersion of an inhibitor (circulated and stirred for uniform dispersion) for 1 second, then pulled up, squeezed between a rubber 1'' roller and a metal roller, and then dried.

The yarn was then flow-stretched at a l'C1 draw ratio of 11 times by touching a hot plate with a surface temperature of 500° C. and an effective length of 11 nm, and then wound up. The drawing condition was good, and the melting length of the obtained yarn was aecm, fiber (da)/strength (SJ/de
)/Naka 1 Sorrow (%)/'+yng rate (J/+Jc) Ha37
3/27.1/ 4.2/ G4b"ea Uk Iko.

Comparative Example 1゜Fuchipox 1% was added to the same polymer as in Example 1 using the same lj method.
A hydrated aluminum silicate (trade name [A-SUS Nj]) prepared in Japanese Patent Application Laid-Open No. 58-540218 (trade name: A-SUS-Nj) was given and dried for 11 days.

Then, the C1 yarn was subjected to the same stretching as in Example 2.

Although the stretching condition was good, the length of the song obtained was as low as 24 cm, and the fineness (clen/strong (h/
da) / elongation (%) / A7 rate (g/de) is 370
/25.7/ 4.1/ G35 (d6 Igo.

Reference example Evaluation example 1 of code type 11 and ratio example 1C Two drawn yarns (
370/2>, number of twists aox 40T/' 10r:
After forming a code of M, it was immersed in the first bath adhesive shown in Table 1, 100°C (2 minutes, 0.5% tension drying and 240°C).
The natural rubber Table 2 shows the results of embedding and peeling adhesion and pultrusion into a rubber with a small [d] composition of /SBR rubber = 8/2. Extraction? ,'+i+'l'1dll'("There is no clear difference, but the exfoliation fossil property is I) I"I' A powder is cloudier by 1.

Table-'11 Heavy agent composition First bath enclosing agent N to I<010Δ1) 5.0'Jliii
part dioctyl 5ulfa 5ucci++at
e 0.5 parts by weight N 1po12518F 32) (
40wt%) 5.0 small fa parts water 89.5 heavy parts 2nd bath enunciator rcsorci++c 1.5 ffl parts realmal
inc (37w1%) 1.7ffl Rakube electric sorter aqueous solution (10wt%) 0.6 reprint part N 1DOI2!1
18F S (40wt%") 40.0ffl 1 part water 56.2 weight part 1) Nagase rff, work (body 2) 1 piece 12A (body making table-2 adhesion 11 evaluation results example 2 1. notation) An aromatic copolyamide of 1, V, = 4.0 made of 41-1 in one unit is mixed with 6 in N-methyl-2-pyrrolone (NMP) containing calcium chloride (CaC10).
The polymer solution dissolved in weight% was added to the pore size of 0.31M1.
It was extruded from a spinneret with 250 holes at a discharge rate of 'J3j/'. After running about 10M in air, it was coagulated in a coagulation bath of NMP/water (30/70Φlli%) at 50°C and dried at a rate of 15 FIL/min, followed by a water bath at 50°C. (・Cleaned, Example 1 (adjusted l”
PTA fine powder molecules were soaked in the solution for 1 second, squeezed between a rubber roller and a metal roller, and dried.Then, the thread was dried using a hollow vibrator with a diameter of 160 cm. However, in this case, superheated steam was blown into the hollow pipe, and the atmosphere temperature was 460°C for one serving. The rubber adhesion properties created and evaluated are shown in the table below.

A7-n fiber 35OLIO Strong melon (g/da) 24.3 Elongation 4.2% Fli1! Wear length (cm) 71 (PPTAf”Jt7
1it O, 7%) Cord adhesive 11 pieces 5i (%) 7.2 Peeling adhesive force (lτ9) 4.5 Pull-out bond i (A!?) 12.0 Comparative example 2 Actual/l-Example 1 Which comparison Therefore, I) P 1 of Example 1
``A zero-order speculative powder was used instead of the A fine powder for comparison.

These are talc with an average particle size of 2 μm rL, and an average particle size of 10 μm.
yet's hydrated j'lumium silicate, average particle size 0.005
There are μl of ultrafine particle silica C, each of which is dispersed in 1% of +11 ml and used as C1, and the fusion length and adhesion of "-" are evaluated by h'1'/C8 and the results are shown in Table 3. Shown in J.

Table-3 Melting 1 state and touching 1 drawing result Example 3 Same as Example 1 41 method Solvent -N,N'-dimethylaretononoshi 1-) (Rose) 7mino Ankyu Anzu Combine chloride hydrochloride, C,1,V, = 0.4, average grain 1'l
2 tlIIL (7)la 15) end bo',) v
−(P r) B△) i! ,1/,:.

This was used in place of the PTA dispersion in Example 1 (1), which was dispersed in water. The 1q drawn thread melts! i5cmc ah Iko1. Yo1. : The peel adhesion strength of the cord prepared and evaluated in the same manner as in the reference example was 3.91 (#t at 7j a Comparative Example 3 1 to 1 to 1 furan to methanoenylene di)min, isonotaric acid cycloly I-4 Insert it and hit it at high speed 1jχ to 1
, V, == 0. ．． 11. Polystaph 1 nylene isonotalamide (PIVIIA) with an average particle size of 7μ711
The powder is 1!1.

The melting temperature of this $5) powder was measured by DSC in a nitrogen atmosphere, and the Ic value was 430°0.

Disperse the fine powder in water with a concentration of 19 (+ (7)
P P T /\molecule fil! of Example 1 ! Used instead of 1, between Example 1 and U-jo I! 1. Stretching system III
child. The name of the drawn yarn was 9 cm C. From this, if a powder with a melting point lower than 500'C is used,
It can be seen that the effect of preventing items from getting stuck is low.

Claims (1)

[Scope of Claims] 1. Undrawn yarn or semi-drawn yarn of Katayama/1χ Borino'mil' (I) consisting of 80 mol% or more of Borin-repetition medium or 11°L of repetition 5) Apply a fine powder of aromatic/rk polyamide (n) having one gland point 11) higher than the drawing temperature of the undrawn yarn or semi-drawn yarn. The yarn should be flow stretched at a stretching temperature of 300℃ or higher! A method for producing an aromatic polyamide braid with R+ characteristics. 2. J5 Riru △r+, Ar on aromatic polyamide (di)
80 mol % or more of 2 is the following aromatic residue, %. 1) Production of the aromatic polytunomide fiber cord according to 1) old method. 3. △r1. in aromatic polyj1mide. Ar2 no 8
0 'E) Lr % or more, L Ka, F f5 m /
'4-' with IX remaining JJ and C, and the IM component (+3') has a % of 10 to 40%! r Hinoki Claims No. 1
Aromatic bolinomid fibers described in Section 1.1) Fragrance method. 4. Aromatic polytunomide (II) fine powder aroma XI
The fragrance according to claim 1, 2, or 3, wherein 80 sill% or more of the remaining base of X is composed of Baraf]-Nyrene Hakko, and the average particle size of the fine powder is 20 microns or less. A method for producing group polyamide fibers. 5. The fine powder of aromatic polyamide (11) is made of polyparaphenylene terephthalamide or polybalabenzamide, and has an average particle size of 20 μm or less.
A process for producing an aromatic 1M poly(l)mid fiber according to claim 1, 2, 3 or 4.