JPS58109624A - Acrylonitrile fiber - Google Patents

Abstract

PURPOSE:To prepare the titled fibers, having improved flameproofness, flame retardancy, operability and processability, and easily crimpable, and useful as flameproofing clothing, etc., by applying a specific amount of a specified water- soluble basic aluminum complex salt to fibers. CONSTITUTION:Acrylonitrile fibers are passed through a 1% aqueous solution of water-soluble basic aluminum complex salt expressed by formulaI{(A), (B) and (C) are mutually different acid residues; (l) and (q) are integers or decimals; (m), (n) and (p) are integers or decimals and are not 0 at the same time, formula II[(Em), (En) and (Ep) are the valences of (A), (B) and (C)]or formula III}, and then dried under heating to give the aimed fibers (a) for flameproofing containing 0.01-5.0wt%, based on the weight of the fibers, applied aluminum. The flameproofing time of the resultant fibers (a) indicates a higher flameproofing efficiency than fibers (b) without the applied aluminum, and the flameproofing time can be reduced.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to acrylonitrile fibers for flame resistance, and more particularly to raw material acrylonitrile fibers that can be used for flame resistance and produce flame resistant fibers with excellent physical properties in a short time.

As is well known, flame-resistant fibers are obtained by oxidizing acrylonitrile fibers, and by making use of their flame-retardant and flame-retardant properties, they can be used for flame-resistant clothing, flame-resistant curtains, backing materials, etc. It is also used as a raw material for fibrous activated carbon and carbon fiber.

When flame-resistant fibers are used for the above-mentioned purposes, they must be processed into yarn, fabric, felt, etc. However, flame-resistant fibers are inherently difficult to crimp, so they are prone to breakage when made into threads. There were many problems in processing, such as a lot of fluffing, which significantly reduced work efficiency, and a lot of falling cotton when making felt, which led to lower yields and poor workability.

As a result of studying these problems, the present inventors found that
If an aqueous solution of a specific basic aluminum composite salt is attached to acrylonitrile fiber in advance and then subjected to flame-retardant treatment, the flame-resistant fiber obtained will not have the above-mentioned processing difficulties, and in this case, flame-retardant It was found that the process progressed rapidly.

The present invention was completed based on the above findings, and the water-soluble basic aluminum composite salt represented by the following general formula is used in an amount of 0.01 to 100% of the weight of the fiber as aluminum.
This is a flame-resistant acrylonitrile fiber that is brazed and attached.

AQx (OH)Q (A)I (B)n (C
)D(Cj2)Q However, ■, A, B, C: mutually different acid residues ■, j2
．． q: All are integers or decimals ■, ", n1D: All are O or integers or decimals (except when all three are 0 at the same time) ■, Q+m -Es +n -En +p -E
El+Q≦6 (EP, E's Ep is the valence of each A%B, C) ■, 0.4≦−−−−−−−≦0.9470a +
n + p + q When the acrylonitrile fiber of the present invention subjected to such adhesion treatment is used to make it flame resistant, the oxidation treatment temperature can be lowered by 10°C or more compared to the case without treatment, and the oxidation treatment time can be reduced by 1. /2 or less.

Moreover, the obtained flame-resistant fiber has excellent crimp properties and good processability.

In the present invention, the acrylonitrile fiber that is the base material is a III fiber obtained from a polymer or copolymer containing 85% by weight or more of acrylonitrile, or a fiber obtained from a mixture of a polymer and a copolymer. be. In this case, comonomers include (1), acrylic acid, methacrylic acid, (2), their salts, esters, acid chlorides, acid amides, n-substituted derivatives of vinylamide, (3), chlorinated Examples include vinyl, vinylidene chloride, α-chloroacrylonitrile, vinylpyridines (4), vinylsulfonic acid, allylsulfonic acid, vinylbenzenesulfonic acid, alkali metal salts and alkaline earth metal salts thereof.

The fineness of the acrylonitrile fiber of the present invention is not particularly limited, but is 0.5 to 15, particularly 1.0 to 5 denier (d).
Preferably. If it is thinner than 0.5 d, the fiber strength will be low and fiber breakage will easily occur.On the other hand, if it is thicker than 15 d, the oxidation rate will be slow, and when it is made into fibrous activated carbon, the strength and elasticity will decrease and the activation yield will be low.

The water-soluble basic aluminum complex salt in the present invention is represented by the following general formula and has α.

AQx (OH)Q (A)II (B)n (C
H1)(CQ)q In the formula, A, B, and C each refer to different types of acid residues, and the acid residues include acid residues such as nitric acid, sulfuric acid, and phosphoric acid.

Both g and q represent integers or decimals, and Q > O, q
>0. -, n, and p all represent 0, an integer, or a decimal number, and cases in which the combination champions are 0 at the same time are excluded.

And this complex salt is the following Q+s -El +n #En +p -Ep
+(1≦6(Em, En% Ep is each A, B,
valence of C).

Furthermore, the composite salt must also satisfy 0.4≦□≦0.9 g + n + p + q, and if it is less than 0.4, it is preferably 0.01 to 5.0 as aluminum to fiber weight in water. 0.05 to 3.5% by weight (aluminum weight%) is deposited.

In the present invention, it is essential to use the above-mentioned specific water-soluble basic aluminum complex salt, and even if the same amount of aluminum is deposited using aluminum hydroxide, aluminum sulfate, aluminum phosphate, etc. instead, the desired amount of aluminum can be achieved. No purine imparting effect can be obtained. In the present invention, if the amount of aluminum attached to the fiber exceeds 5% by weight, the strength of the flame-resistant fiber will decrease, and if it is less than 0.01% by weight, the effect of imparting crimp properties to the fiber cannot be expected, and the flame-retardant treatment time will be shortened. You can't expect much either.

Attachment to acrylonitrile fibers can be carried out by a conventional method such as preparing an aqueous solution of the composite salt and immersing the fibers in this solution or spraying this solution onto the fibers.

The composite salt-adhered fiber of the present invention is limited to use for flame resistance. Flameproofing treatment is usually carried out in several ways. 200 to 400°C in an oxidizing atmosphere, such as air, oxygen, hydrogen chloride, sulfur dioxide, a single gas or a mixture of these gases, or a mixture of these gases with a temperature-proofing gas.
Oxidize for 0.3-20 hours.

In this case, the oxidation is performed when the specific gravity of the fiber is approximately 1.37 to 1.470/
Do this until you reach CC. If the oxidation is kept below L37a/cc, the resulting flame-resistant fibers will undergo fiber breakage in the subsequent fibrous activated carbon manufacturing process, and the activation yield will also decrease. On the other hand, if oxidation is carried out to a value of 1.47 MCC or more, the strength of the flame-resistant fiber will decrease and fiber breakage will occur frequently in the crimp imparting step. The tension applied during the flameproofing treatment time is preferably adjusted to approximately 70 to 90% of the free shrinkage rate at that temperature, and the corresponding value is 0.
．． 01~0.3a/d. If a strong tension is applied so that the free contraction rate is less than 70%, the cord bundle becomes disordered and tends to be cut, and if it is more than 90%, the tension will break, which is inappropriate.

When the 7crylonitrile-based l111 of the present invention is used for flame resistance, flame-resistant fibers having excellent crimpability and good strength can be efficiently obtained in a short time.

This is clear from the results shown in Table 1 below.

In Table 1, the acrylonitrile fibers to be adhered include 93% by weight of acrylonitrile and 5% by weight of methyl acrylate.
A fiber bundle (tow) of a copolymer consisting of 5% by weight and 1.5li% of acrylamide with a single fiber fineness of 2d and a number of constituent fibers (tow) of 270,000 fibers, to which a composite salt of the following formula % (%) is prepared. The above-mentioned composite salt (5) is applied as an aqueous solution. In addition, the flame treatment conditions are as follows:
For each experiment, the upper limit temperature at which flame resistance can be stably achieved in air was adopted, the treatment time was selected so that the specific gravity of the fiber was 1.42 to 1.45 g/cc, and the free shrinkage rate at each concentration was 75%.
The tension was adjusted in %.

Then, crisps were applied to the flame-resistant fiber using a stuffing box as a crimper under conditions of a feed rate of 100 s/hr, a stuffing pressure of 1 Kg/C11, and a nip pressure of 2 KO/Cm''.

According to Table 1, when the fibers of the present invention are used, the strength of the resulting resistant fibers is greater, and the number of crimps and The crimp rate is large.

In addition, when #A cord of the present invention is used for flame resistance, adhesion 11
Compared to the case of 0, the treatment temperature for flame resistance can be made higher, and therefore the treatment time can be shortened. This can also be seen from Figure 1. Figure 1 shows the results of the flame-retardant condition at 230°C, when the present invention fiber with an adhesion amount of 2.02% by weight was used for flame-retardant (curve ■) and when IlO adhesion was used (curve O). The relationship between the specific gravity and the flame resistance time is shown, and as is clear from this, when the fibers of the present invention are used, the specific gravity of the fiber can be further increased with the same flame resistance time, and the flame resistance can be further progressed. is possible,
Therefore, the flame resistance time can be shortened.

The present invention will be explained below by way of examples. Percentages and parts are by weight unless otherwise stated.

Example 1゜Methyl acrylate 8.4%, sodium allylsulfonate 1
%, acrylonitrile fiber bundle with a copolymerization composition consisting of the remainder of acrylonitrile (single fiber 3d, total denier 5
40,000, strength 3.81; l/d 1 elongation 25%) was passed through a 1% aqueous solution of a complex salt represented by the following formula %.
0.1 as aluminum for bone-dry fibers dried at ℃
A fiber bundle with % adhesion was obtained.

This product was heated in air at 250°C for 1 hour, and then at 270°C.
The flameproofing treatment was continued for 1.3 hours.

The tension during flame resistance is 70 to 9 of the free shrinkage rate at each temperature.
This corresponds to a tension of 0%. , oa g/d was adopted. The fiber bundle obtained in this way is applied to a crimper at a nip pressure of 2Ko/(,w"1stuffing pressure iKo 10r
, at a feed rate of 95 m/hr to obtain crimped flame-resistant fibers.

This flame-resistant fiber has a crimp number of 15.0 and a crimp rate of 8.
1% tensile strength 26.5KO/Peng 2, elongation 18.4%,
It had a specific gravity of 1.45 o/cc, and had excellent crimp characteristics and good fiber performance. When this material was applied to a cotton spinning machine and made into yarn, most of the yarns broke and a yarn with a count of 40 was produced.

Example 2゜Methyl acrylate 5.0%, acrylamide 1.0%,
Acrylonitrile fiber bundle with a copolymer composition consisting of 1.2% sodium allylsulfonate and the balance acrylonitrile (single fiber 2d, total denier 540,000, strong I 3.9o)
/d, elongation 129%) 125
0.2 as aluminum for bone-dry fibers dried at ℃
% to obtain a fiber bundle.

This was heated in air at 245°C for 30 minutes and then at 275°C.
, 2 hours, and 280° C. for 10 minutes. The tension at the time of flameproofing corresponds to a tension that is 10 to 90% of the free shrinkage rate at each temperature. ,os
g/d was adopted.

The obtained flame-resistant fibers were continuously applied to a crimper under the conditions of a nip pressure of 2 KQ/Gf, a stuffing pressure of 1 KO 10 l'', and a feed rate of 95-/hr.

The obtained flame-resistant fiber had a crimp number of 7.8 and a crimp rate of 1.
8%, tensile strength 29.4! 11/-12, elongation 20
．． 1%, specific gravity 1.44 g/Co, and had excellent crimp properties and good fiber performance.

This flame-resistant fiber was treated in a nitrogen gas atmosphere at 1000° C. under tension o, ooso/d for 1 minute to obtain carbon fiber. This material had crimps with a number of crimps of 4 and a crimp rate of 5%, and when it was passed through a card machine for cotton spinning, it was possible to obtain a good sliver with almost no dropped cotton.

[Brief explanation of the drawing]

Figure 1 shows the relationship between flame resistance and specific gravity of the fiber at 230°C.
The curve for I is flame resistant, and the curve for O is for the case where the coating amount is 0. Patent applicant Higashi Lugesshi: / Shinshiki company representative patent attorney
Doi 3-Part Procedural Amendment (Method) May 13, 1981 1. Indication of the case 1982 Patent Application No. 214088 2. Name of the invention Acrylonitrile-based Ill fiber 3. Person making the amendment 〒103. Related Patent Applicant Residence Address: 9 Nihon Nara 3-chome, Chuo-ku, Tokyo 9 @ name
Name: Toho Bethlon Co., Ltd. Representative: Seiya Yuasa 4, Agent: 105 Address: 1-1018-5 Nishi-Shinbashi, Minato-ku, Tokyo Date of amendment order: April 9, 1980 (Date of dispatch: April 1980) 27th)
6. Subject of amendment Application and specification

Claims (1)

[Claims] The following general formula % formula % ()) However, ■, A, B, C: mutually different acid residues ■, (2
, a: All are integers or decimals ■, "5nSp: All are 0 or integers or decimals (except when all three are 0 at the same time) ■, J2+l-E+n-En+p-Ep+Q≦6 (Em, En, El) is the valence of each A, BSC) ■ 0.4≦-111111111≦0.9
The water-soluble basic aluminum composite salt represented by j7+s+n+p10q is added to the fiber amount
Acrylonitrile fiber for flame resistance, which has 0.01 to 5.0 weight percent of aluminum attached to the flame resistant acrylonitrile fiber.