JPH0359173A - Flame-retardant modacrylic fiber having excellent rust-proofing property - Google Patents

Abstract

PURPOSE:To obtain an excellent flame-retardant fiber while preventing the generation of rust in the course of the production of said fiber by applying a specific epoxy resin or an epoxy compound to the surface of a modacrylic fiber containing vinylidene chloride or vinyl chloride. CONSTITUTION:A modacrylic fiber made of a polymer composed of 45-70wt.% of acrylonirile, 30-55wt.% of vinylidene chloride or vinyl chloride, 0.5-3wt.% of a monomer containing sulfonic acid group and 0-55wt.% of an unsaturated monomer (e.g. acrylic acid) is immersed in a dispersion of a bisphenol A-type water-soluble epoxy resin or an epoxy compound of formula (a is 1.6; b is 4.4; R is alkyl) after the drawing and washing of the fiber in the spinning proc ess in an undried state to apply 1-1.5wt.% of the compound to the fiber. An excellent transparent and flame-retardant modacrylic fiber stable to light can be produced while preventing the rust generation during the production process and the spinning process of the fiber.

Description

DETAILED DESCRIPTION OF THE INVENTION <Industrial Application Field> The present invention relates to flame-retardant acrylic fibers with excellent rust prevention properties.

<Prior Art> Acrylic fibers have been used for a long time in a wide range of applications because of their excellent texture and dyeability. Particularly in recent years, as social demands have become more sophisticated, the demand for halogen-containing acrylic fibers, so-called modacrylic fibers, which have improved flammability, which is their biggest drawback, has increased.

However, when modacrylic fibers contain a chlorine component as a copolymer component, the fibers undergo a dechlorination reaction when exposed to light or heat, which causes rusting problems during the fiber manufacturing process and spinning process.

JP-A-57-82516, JP-A-57-8961
Publication No. 5 states that rust prevention is effective when used in combination with a glycidyl methacrylate polymer.

Sharing a glycidyl methacrylate polymer requires preparing the glycidyl methacrylate polymer in advance, which is difficult to call an industrially effective method, and the problem of rusting during the manufacturing process and spinning process is Despite this being a major problem with chlorine-containing flame-retardant modacrylic fibers, no effective means have yet been found.

<Problems to be Solved by the Invention> The present invention solves the problem of rusting in the manufacturing process and spinning process of the flame-retardant acrylic fiber containing vinylidene fii or vinyl chloride, and The purpose of the present invention is to provide a flammable acrylic fiber.

<Means for Solving Problem 1> The gist of the present invention is that acrylonitrile 45-
70 weight, vinylidene chloride case or vinyl chloride 30-5
A fiber consisting of a polymer of 5-[1 sulfonic acid group-containing monomer cLS to 3-weight polycarbonate and unsaturated monomer 0-55 monomer is, the Ni fiber coating surface being a bisphenol-type water-soluble epoxy resin. The flame-retardant acrylic fiber is characterized by having 1.0 to 1.5 weight of an epoxy compound represented by the following formula (1) adhered to the fiber, and has excellent rust prevention properties.

However, in the formula a = 16, t) -4,4, R-alkyl The polymer used to construct the fiber of the basic invention must be an acrylonitrile-based polymer copolymerized with a halogen-containing monomer. be.

A common method for incorporating halogen into acrylic fibers is to copolymerize acrylonitrile and a halogen-containing monomer, and the fibers obtained from the copolymer do not impair the performance of the acrylic fibers. most preferred.

Examples of the halogen-containing monomer include vinyl chloride, vinylidene chloride, vinyl bromide, etc., and vinylidene chloride and vinyl chloride are preferably used. In particular, vinylidene chloride has a slightly high boiling point, making it easy to handle in the polymerization process, and the characteristics of fibers made from vinylidene chloride copolymers are superior to general acrylic fibers in terms of their flame retardant performance. It can be used advantageously because it has excellent mechanical or thermal properties close to those of .

The content of vinylidene chloride or vinyl chloride is flame retardant M!
In order to maintain effective flame retardant performance as a fiber, it is necessary to have a weight of over 30% by weight. Furthermore, if 5511Ef4 is added, it can be used in most products in current practical applications, and when combined with flame retardant additives, this fiber can be used in all applications. be.

The thus obtained chlorine-containing acrylonitrile polymer is spun by a conventional acrylic fiber spinning method. 1
However, from the viewpoint of productivity and low heat history, it is preferable to use a wet spinning method to form fibers.

However, when a chlorine-containing acrylonitrile polymer is shaped into fibers by a wet spinning method, it has a drawback that voids are easily generated due to its coagulation properties. Although these voids are once burned out in the drying process, they occur again in the moist heat relaxation process or the dyeing process, causing the fibers to devitrify and impairing the clarity of the dyeing.

In order to solve such problems, an effective method is to copolymerize a sulfone e group-containing monomer such as sodium methacrylsulfonate to introduce a sulfonic acid group into the polymer.
The content of the sulfonic acid group-containing monomer is rumored to be 1.0 to 50% by weight, and 1.0 to 50% by weight.

Other unsaturated monomers as copolymerization components are known, but these are monomers that can be introduced to improve the properties of fibers, such as acrylic acid, methacrylic acid,
Examples include vinyl acetate, methacrylamide, and esters thereof. However, the amount of copolymerization should be limited to at most 5.5% by weight; introduction of more than this will significantly reduce the heat resistance properties of the fibers.

The rust prevention property of the IRm of the present invention is 1.0 to 1.51 when the bisphenol type water-soluble epoxy resin or the epoxy compound shown in the formula (1) is applied to the fibers! Quantity M! Obtained by adhering to rough surfaces.

It is generally known that epoxy compounds have the effect of inactivating hydrochloric acid produced by a dehydrochlorination reaction through a chemical reaction. However, in the process of manufacturing the m-miscellaneous material of the present invention, it is necessary to dry the fibers and subject them to moist heat relaxation treatment, and in the process of imparting thermal history to the fibers, the highly reactive epoxy compounds are easily decomposed. In addition to being unable to achieve the original purpose, it also had the disadvantage of causing the fibers to turn pink.The present invention solves these disadvantages of epoxy compounds by using the above-mentioned specific epoxy compounds. It can also impart rust prevention properties to the fibers.

The epoxy compound used in the present invention is a bisphenol type water-soluble epoxy resin or an epoxy compound shown in the above formula (1). 1.0 of these compounds to fiber
The object of the present invention can be achieved by attaching a ~t5 weight layer to the fiber surface. If the amount of adhesion is less than 1.0% by weight, it will not be possible to provide sufficient rust prevention;
．． When the number of layers exceeds 5, gum-up phenomenon occurs on the drying roll during the drying process of N&fiber, which causes a decrease in operability.

The method for attaching an epoxy compound to the fiber surface is as follows:
Methods include immersing the undried or dried fibers after stretching and washing in a dispersion of an epoxy compound and then drying and fixing them, but the former method of immersing the undried fibers is preferable in terms of the manufacturing process. The temperature at which the epoxy compound is fixed onto the fibers is effectively carried out within the range of 130 to 130°C.

Further, the amount of the epoxy compound attached to the fiber surface can be set by adjusting the amount continuously added to the dispersion of the epoxy compound.

In general, acrylic fibers used for spinning are coated with a rust-preventing oil agent on the surface of the fibers to ensure processability. The epoxy compound used in the present invention may be attached to the fibers as a mixed dispersion with these spinning oils, or may be attached to the casing or *S as a separate dispersion without impairing the rust-preventing effect. do not have. However, epoxy compounds other than those used in the present invention react with the cationic oil, which is an antistatic component in the spinning oil, and lose their antirust effect.

Preferable examples of the solvent capable of dissolving the acrylonitrile polymer used in the present invention include organic solvents such as dimethylacetamide, dimethylformamide, and dimethylsulfoxide.

Note that S-free salts, strong acid salts, acetone, etc. can also be used as solvents, but each condition must be considered individually.

To prepare the spinning stock solution, the concentration of the acrylonitrile polymer is set at 15 to 30 parts by weight in order to ensure process passability, and the solution is dissolved at a low temperature of 30 DEG C. or lower to avoid coloring due to heat. In order to improve the light resistance, heat resistance, and flame retardance of the fiber of the present invention, various compounds can be added to the spinning dope.
Any method is possible as long as it does not impair the effects of the present invention.

The spinning stock solution prepared in this manner is discharged from a nozzle into a coagulation bath consisting of a mixed solution of a solvent and water, and is shaped into an undrawn yarn.

The obtained undrawn yarn is drawn while washing away the solvent in the washing-drawing process, but it is preferable to set the drawing ratio in hot water as high as possible in order to spin the devitrification in the dyeing process. Stretching is carried out in hot water at a normal maximum stretching ratio of 30 scratches, and after immersion treatment in an oil agent and an aqueous dispersion of the epoxy compound used in the present invention, drying and densification and attachment of the epoxy compound are performed. If necessary, it is also possible to perform stretching again by dry heat after drying.

After stretching and drying, the fibers are subjected to a relaxation treatment under moist heat to form MM with well-balanced strength and elongation, and then cut into required lengths to obtain raw cotton for spinning. The thus obtained m-fibers are flame-retardant acrylic fibers that have superior rust prevention properties compared to conventionally cut chlorine-containing acrylic fibers.

<Example> Hereinafter, the present invention will be explained in more detail with reference to Examples. The evaluation method in the examples is as follows. Flame retardancy was evaluated based on the oxygen index method (No. K720-1a1 from J). The polymer specific viscosity was measured in α5 dimethylformamide solution at 25°C. The transparency of the fibers was evaluated using the light transmission weight shown below.

The fibers treated with fresh water for 1 hour were cut into 30 lengths of sea bream, and 5 pieces were collected, 100cm wide x 200cm wide, 1cm thick.
The felt is created using the needle punch method.

A 10 m x 20 m felt piece weighing soq was taken and placed in a 10 m thick glass cell containing 5 m of benzyl alcohol.
Measured at a wavelength of 915 nm.

According to this method, determination can be made with high accuracy even with a small amount of sample. Although the absolute value of the numerical value displayed as the transmittance value is small, if the transmittance of the clean water-treated fiber is 40 or more, the transparency of the fiber is extremely good, and the devitrification prevention property is judged to be sufficient.

Rust prevention was evaluated using the method shown below.

Fully opened fiber 11? Pour into a 200 cc beaker and cover with a lid. This is treated under dry heat at 140° C. for 40 minutes. Insert 10 spun steel bottles into the treated fibers to obtain 634RH.

Leave it for 24 hours under constant temperature and humidity at 25°C. The spun steel bottles were taken out after being left unused, and the rusting status of each bottle was checked, and points were given according to the degree of rust. The maximum score is 30, with 30 points being no rust and 0 points being all rust, and the higher the point, the better the rust prevention.

The amount of epoxy compound attached to the fiber surface was measured by the following method.

Thoroughly opened raw cotton is treated with ethanol to extract the epoxy compounds attached to the fiber surface.

The amount of ebony in this extract is determined by the Vt-boric acid-dioxane method (W eq /f-fiber). This value is calculated as the epoxy equivalent (E f/eq) of each epoxy compound.
The amount of epoxy compound attached to the fiber surface was quantified by dividing by .

Amount of epoxy compound attached to fiber surface (vrtlg)
= -X 10 G Example 1 A polymer (specific viscosity 1.10) consisting of acrylonitrile 5a 5 weight range, vinylidan chloride 0 weight range, and sodium methacryl sulfonate 1.5 weight range was dissolved in dimethylacetamide at 40°C. A spinning dope having a polymer concentration of 25% by weight was obtained. This spinning dope was spun into a dimethylacetamide-water mixture (30°C) with a pore size of 53 fi using a nozzle with a hole size of 1076 m, and after solvent removal treatment, it was placed in hot water for 60 min.
The fibers were stretched twice and treated by immersing an oil solution and a bisphenol A type water-soluble epoxy resin (InM-101 manufactured by Nagase Kaoru Kogyo Co., Ltd.) into an aqueous dispersion that was continuously supplied to the fibers as shown in Table 1. After application, it was dried at 140°C and subjected to thermal relaxation treatment to obtain a 1.75 denier fiber.

The fibers of was evaluated.

Table Example 2 A polymer (specific viscosity 1.1 o ) consisting of acrylonitrile 5&5 weight t4, vinylidene chloride 40 weight liter, sodium methacrylsulfonate 1.5 weight scratches (specific viscosity 1.1 o) was dissolved in dimethylacetamide at 40°C, and the polymer concentration was 25. A weight best spinning stock solution was obtained. This spinning stock solution was spun into a dimethylacetamide-water mixture (30°C) of 55 weight by weight using a nozzle with a hole diameter of LO76+W, and after being subjected to solvent removal treatment, it was stretched 6 times in hot water, and an oil solution was drawn. and bisphenol A type water-soluble Epoquine resin (ml: M-10!S manufactured by Nagase Chemical Industries)
was applied to the fibers by immersion in an aqueous dispersion that was continuously supplied as shown in Table 2, dried at 140° C., and subjected to a moist heat relaxation treatment to obtain fibers of 1.75 denier. This fiber was evaluated by the method described above.

Table 2 Example 3 Acrylonitrile 5a A polymer consisting of 40% by weight of vinylidene chloride and 1.5% by weight of sodium methacrylsulfonate (specific viscosity 1.10) was dissolved in dimethylacetamide at 40°C, A spinning dope with a combined density of 25 times was obtained. This spinning stock solution was spun into a 533 weight dimethylacetamide-water mixture (30°C) using a nozzle with a pore size of 076 mm, and after being subjected to solvent removal treatment, it was stretched 6 times in hot water (oil agent). and the epoxy compound shown in the above formula (1) (Bunacol KM-125 manufactured by Nagase Chemical Industries)
was applied to the fibers by immersion in an aqueous dispersion continuously supplied as shown in Table 3, dried at 140° C., and subjected to a moist heat relaxation treatment to obtain fibers of 1.75 denier. This fiber was evaluated using the method previously described.

Table Example 4 A polymer (specific viscosity 1.10) consisting of 5% by weight of acrylonitrile 5a, 40% by weight of vinylidene chloride, and 1.5% by weight of sodium methacrylsulfonate was dissolved in dimethylacetamide at a concentration of 400%, and the polymer concentration was 25% by weight. A spinning stock solution of Yu was obtained. This spinning stock solution was spun into a 533 weight dimethylacetamide-water mixture (30°C) using a nozzle with a hole diameter of 76 wr, and after solvent removal treatment, it was placed in hot water for 6 hours.
Stretched 1. A water-soluble epoxy resin (IIIM-1 (11 Nagase Kasei Kogyo #)) containing an oil agent button and bisphenol is immersed in an aqueous dispersion solution that is continuously supplied to the fibers so that the fibers are coated in an extremely large amount. After processing and applying 14
It was dried at 0°C and subjected to moist heat relaxation treatment to obtain a 1.75 denier fiber. The rust prevention effect of this fiber was 30 points, and the same rust prevention effect as that obtained by adhering the fiber by mixing it with a spinning oil was obtained. (
Experiment A17) Comparative Example 1 Acrylonitrile 5a5 weight, vinylidene chloride 40i
Amount: 1 Sodium methacrylsulfonate t 5 fg A polymer (specific viscosity: 1.10) consisting of the following was dissolved in dimethylacetamide at 40°C to obtain a stock solution for spinning on top with a polymer concentration of 25 times. This spinning stock solution was spun into a dimethylacetamide-water mixture (30°C) with a pore size of [1L076] using a nozzle with a pore diameter of [1L076], and after solvent removal treatment, it was stretched 6 times in hot water. The oil agent and the epoxy compound shown in Table 4 were separately immersed in an aqueous dispersion that was continuously supplied so that the weight of the fiber was 1.0% by weight, and then dried at 14°C. A 1° denier fiber was obtained by thermal relaxation treatment.

No. table Epoxy compound ■ Bunacol old To Manufactured by Nagase Kakai Industries Epoxy compound ■ Bunacol Kx- Manufactured by Nagase Chemical Industries Epoxy compound ■ Bunacol ff1X-31 Manufactured by Nagase Kaoru Kogyo EIR Oh! OOH heavy-〇H-OH snow \0/ Rni -OH1 or 100H bird0H-OH.

\0' Epoxy compound Bunacol KX-81 OH Snow-0H-oHt manufactured by Nagase Chemical Industries OOH, H, OOH, 01 (
-OH food \0/ \0/
Effects of the Invention> The present invention improves the rusting problem of chlorine-containing acrylic fibers such as vinylidene chloride and vinyl chloride, and provides flame retardant fibers with excellent tip stability and transparency. This makes it possible to provide acrylic fibers, which can be used as flame-retardant fibers, and can meet demands from various fields related to improving the safety of the social environment.

Claims (1)

Scope of Claims: 45-70% by weight of acrylonitrile, 30-55% by weight of vinylidene chloride or vinyl chloride, 0.5-3% by weight of sulfonic acid group-containing monomers, and 0-5.5% by weight of unsaturated monomers. % of a polymer, the fiber surface is coated with bisphenol A type water-soluble epoxy resin or the following formula (1).
A flame-retardant acrylic fiber with excellent rust prevention properties, characterized in that 1.0 to 1.5% by weight of the epoxy compound shown in the following is attached to the fiber. ▲There are mathematical formulas, chemical formulas, tables, etc.▼Formula (1) However, in the formula, a = 1.6, b = 4.4, R = alkyl group