JPS63105108A - Flame-retardant acrylic fiber - Google Patents

Abstract

PURPOSE:To provide the titled fiber outstanding in both light and heat resistances, capable of production without any trouble in the operation such as nozzle cloggings, consisting of a phosphorus-containing acrylonitrile-based polymer incorporated with aluminum or zinc hydroxide fine particles. CONSTITUTION:The objective fiber consisting of a phosphorus-contg. acry lonitrile-based polymer (hereafter, phosphorus-contg. AN-based polymer) incorpo rated with aluminum or zinc hydroxide of a particle size <=0.1mu. The recommended production process for this fiber is as follows. An inorganic sol vent solution of a phosphorus-contg. AN-based polymer is incorporated with an aluminum or zinc salt soluble to said solvent to prepare a spinning stock solution, which is then subjected to spinning and after-treatment. The phosphorus-contg. AN-based polymer mentioned above is preferably made from 60-90wt% of acrylonitrile, 3-20wt% of a phosphorus-contg. vinyl monomer such as diethylallyl phosphonate, 5-25wt% of a halogen-contg. vinyl monomer and 0-20wt% of another vinyl monomer.

Description

DETAILED DESCRIPTION OF THE INVENTION (Industrial Field of Application) The present invention relates to a flame-retardant acrylic IX/fiber with good light and heat resistance.

(Prior art) Acrylic fiber has a bulky texture similar to wool, excellent physical properties and dyeability, and is used in a wide range of applications, including interior applications such as carpets and curtains, In certain fields of use, such as nursing clothing for infants, there is a strong demand for flame retardant properties.

Typical examples of flame retardant means include copolymerizing a halogen-containing vinyl monomer with 7-crylonitrile (hereinafter referred to as AN), or mixing a flame retardant polymer such as polyvinyl chloride with an AI polymer. Using halogen-containing AN thread polymer,
A method for producing fibers using a phosphorus-containing AN, 1 subpolymer obtained by copolymerizing a phosphorus-containing vinyl monomer can be mentioned.

However, halogen-containing AN polymers cause dehydrohalogenation by light or heat, and the dehydrohalogenation forms a so-called polyene structure, resulting in coloration. Therefore, various stabilizers have been proposed to prevent the deterioration of such Hagen-containing subaggregates due to light and heat, and among the generally known light-resistant and thermal stabilizers (A)
Main stabilizers such as metal soaps such as lead, cadmium, barium, calcium, and zinc, and scum compounds, as well as phosphite-based stabilizers that are said to be effective when used in combination with the main stabilizers. Solenite Nether], Epoxy Prefecture,
Stabilizing aids such as polio/I/beams, β-diketo compounds, chelating agents, etc. are included. However, none of these could satisfy both the light and heat resistance stabilizing effect and the operability.

In addition, phosphorus-containing AN-based polymers are also unstable to light and heat, and are particularly susceptible to hydrolysis when heated in a beam where moisture is present, resulting in a significant deterioration of light and heat resistance. I see no practical means to do so.

(Problems to be Solved by the Invention) The purpose of the present invention is to solve problems such as clogging in the filtration process in the ionization manufacturing process, pressure increase troubles, etc., and nozzle/l/clogging in the spinning process.
Flame-retardant ac with good light and heat resistance without problems such as thread breakage! The objective is to provide I/l/iE fibers.

(Means for Solving the Problems) The object of the present invention as described above is to provide a flame-retardant fiber containing hydroxide of aluminum or zinc with a particle size of 0.4 ti or less, which is made of phosphorus-containing A Achieved by Acrylic JI/Fiber.

The present invention will be explained in detail below.

First, as the phosphorus-containing AN, R1 polymer, one type of polymer or a mixture of two or more types of polymers containing AN and a phosphorus-containing vinyl monomer bonded as essential copolymerization components, h
Examples include mixtures of N-ken z-combination and polymers consisting of phosphorus-containing vinyl element M, and in both cases,
N 40-98% by weight, preferably 60-90%, phosphorus-containing vinyl monomer 2-60%, preferably 3-20%
, halogen-containing vinyl monomers are bonded within a range of 0 to 30%, preferably 5 to 25%, and other vinyl monomers are bonded within a range of 0 to 40%, preferably 1 to 20%. Something is desirable.

Here, as a phosphorus-containing H = /L/ single mouse body, Binu (
2-ri proech) V) Vinyl Honuho Badge (2)
-promoethinone) vinylhonuhobut, vinyl (2-chloroethyl fumetharylhonufonate, 1hin (2-bup-moethyl) methallylhonufonate, diethylallylhonufonate, N-honufonomethylacrylamide, etc. unsaturated phonufonic acids; unsaturated phosphates such as 2-hydroxyethyl methacrylate acidophonufate, diphenyl 2-methacryloyloxyethyl phosphate, and dibutyl 2-methacryloyloxyethyl phosphate;

Examples of the halogen-containing vinyl monomer include vinyl halides and hynylidene halides such as vinyl chloride, vinyl bromide, vinyl fluoride, vinylidene chloride, and vinylidene bromide, and other vinyl/I/based monomers. Examples of polymers include monomers such as (meth)acrylic acid monotyl, ethyl, butyl, octyl, phenyl, cyclohexyl, etc.; vinyl acetate, vinyl pionate, ffJa vinyl, etc. ; Acrylamide and its alkyl-substituted products; Unsaturated carboxylic acids such as (meth)acrylic acid, maleic acid, itaconic acid, and their salts; Bicol-nulfonic acid, (methaneallyl-nulfonic acid, P-, L
Examples include vinyl compounds such as /phonic acid, vinyl ketone, methyl/rehenyl ether, allyl alcohol, hinyl biridine, dimethyl rareminoethyl methacrylate, vinylidene cyanide, memethlynitrile, and glycidyl methacrylate. In addition, methods for producing these polymers include known emulsion polymerization, 1 aqueous precipitation polymerization, aqueous suspension polymerization,
Methods such as solution polymerization can be employed.

Next, the means for incorporating aluminum or zinc hydroxide with a particle size of 0.4μ or less, preferably 0.1μ or less into the mechanical fibers is not limited, but the above-mentioned hydroxide with a predetermined particle size can be used. It is difficult to obtain these substances industrially, and even if one were obtained, the particles would aggregate when mixed into the spinning dope (polymer solution), resulting in clogging in the filtration process, pressure increase problems, and nozzle clogging in the spinning process. Since this causes problems such as thread breakage and ultimately makes it impossible to obtain the desired fiber, the following measures are recommended.

That is, an inorganic solvent solution of a phosphorus-containing AM polymer,
Preferably, a spinning dope is prepared by blending a soluble aluminum or zinc salt in the solvent, and the spinning dope is spun and post-treated according to a conventional method.

The salt of aluminum or zinc may be used as long as it can be dissolved in the above solvent, and examples thereof include nitrate, sulfate, hydrochloride, acetate, etc. of aluminum or zinc. In addition, examples of inorganic solvents include: Concentrated aqueous solutions of rhodan salts such as Rotan-Da-10-Dankali, Rotan-An-7-N, and Rodan Calcium, which are known as AN-based polymerization solvents; 1-thick water M solutions of chlorides such as zinc chloride and calcium chloride; A PiL aqueous solution of strong acids such as nitric acid and sulfuric acid is reduced, and known ANNs such as dimethylformamide, dimethylacetamide, dimethylsulfoxide, ethylene carbonate, r-butyrolactone, acetone, etc. are added to these solvents within a range that does not inhibit the dissolution ability. It is also possible to use a mixed solvent containing an organic solvent for system polymerization.

The amount of the salt to be added is 0.05 to 20%, preferably 02 to 5.0% (0.01 to 6% based on the weight of aluminum or zinc) based on the weight iJ of the polymer.
%, preferably within the range of 0.005 to 1.0%), and if it is outside the lower limit of this range,
It has no effect of imparting light resistance i+, IT thermal stability and flame retardancy,
Furthermore, even if the amount exceeds the upper limit, the effect will reach a plateau (or the physical properties of the fibers finally obtained will deteriorate), which is not desirable.

In addition, the method of blending the salt is as follows: - Dissolve the phosphorus-containing AN polymer in an inorganic solvent, and add a predetermined amount of the salt to the powder.
Alternatively, it may be added and mixed in the form of an aqueous solution or the like. Note that if the pH of the solution is high, the salt will not dissolve in the bath, so it is desirable to adjust the pH of the solution to 60 or less, preferably 4.0 or less. In addition, if heating is required to dissolve the polymer, the salt should be added and mixed in a so-called nullary state before heating and dissolving, since the phosphorus-containing AN polymer will already deteriorate during this step. or desirable.

In this way, the phosphorus-containing AN-based yarn (spinning stock solution) containing aluminum or zinc salts is subjected to spinning, coagulation, washing, stretching during and/or after washing, moist heat stretching, and drying according to conventional methods. Through these steps, the fiber is formed into a fiber containing aluminum or zinc hydroxide with a particle size of 04 μm or less, preferably 01 μm or less, and having excellent performance without any problems in the manufacturing process.

(Function) Although the reason why the fibers of the present invention have excellent double-light and heat-resistant stability is not fully understood, it is speculated as follows.

In other words, phosphorus-containing vinyl monomer II is unstable to light and heat, and especially in the presence of moisture, the bond is broken at the dotted line as shown in equation 11 below.
hydrolysis) to produce -P-OH (and type),
On the other hand, aluminum or zinc present uniformly and finely in the fiber captures the released acidic substances and coordinates with the generated 1-P-OH to stabilize it. I can think about things.

In addition, when the IB fiber-formed vehicle assembly contains a hydrogen halide, the hydrogen halide desorbed by light or heat, or the reaction product of the hydrogen halide and a metal such as iron, nickel, or cobalt, acts as a catalyst. To act as a catalyst and promote dehydrohalogenation,
While coloring progresses by forming a polyene structure in the polymer, aluminum or zinc present uniformly and finely in the fiber captures hydrogen halide and has a catalytic effect on the metal halide formed. This is thought to effectively suppress the progress of the dehydrohalogenation reaction.

In addition, the aluminum or zinc salts recommended in the present invention are:
It is uniformly dissolved and mixed (contained at the molecular level) with the polymer in the spinning dope, and therefore causes problems such as clogging and pressure increase problems in one filtration process, nozzle clogging in the spinning process, and yarn breakage. Furthermore, water-insoluble metal hydroxides are formed sequentially by increasing pH during coagulation, washing, stretching, etc. processes, and it is thought that they can be present uniformly and finely in the shell material e-fibers. .

(Effects of the Invention) As described above, a notable industrial advantage of the present invention is that a flame-retardant acrylic fiber with good light and heat resistance can be provided without any problems in the manufacturing process.

In addition, since fine particles of aluminum or zinc hydroxide are uniformly present in the fibers of the present invention, there are problems with the transparency of the fibers, the vividness of dyeing, etc., and the product equipment is not damaged in any way. This is also an advantage of the present invention.

(Example) Examples are shown below to facilitate understanding of the present invention.
These parts and proportions are merely illustrative and the gist of the present invention is not limited thereto.The parts and proportions shown in the examples are based on the weight of the special product. The light resistance, heat resistance, and particle size of aluminum or engineering ship hydroxide present in the fibers were measured and evaluated as follows.

(1) Light resistance Light resistance measurement conditions Measuring device: Made by Nuga Test Instruments Co., Ltd.
Fade meter FAL-3H machine Plack spring / 1 / wetness: 66 ± 6 ° C Exposure time = 40 hours Sheath leakage method Guerraine kale (J
5L-0844). Note that the higher the grade, the better the light resistance.

(2) Heat resistance Heat resistance measurement conditions Measuring device: manufactured by Tabai Co., Ltd. p? , Air dryer temperature
(, T-work 5L-0804). By the way, which one has a higher grade? It shows that the quality is excellent.

(6) Particle size Using a transmission electron imaging microscope (TIM) manufactured by Hitachi, Ltd., examine a cross section of a 7-eye diameter microscope (magnification: 150,000 times) to determine the average particle size of the metal hydroxide. Ta.

Example Using a Rudotsukunu catalyst, AN using the normal aqueous precipitation 1 method.
84 parts, bis(2-p-ethyl)vinylphonone)
(C) A polymer (AJ) consisting of 16 parts of CVPJ was produced.

Next, when preparing a solution of polymer (A) with a polymer concentration of 12% and 40% using Rodan soda, first mix a predetermined amount of the polymer with a solvent, and before heating and dissolving it, add aluminum nitrate. Added 0.2% (in terms of aluminum) to the polymer, and adjusted the pH to 3.
8 and then melted at 70° C. for 1 hour using an ordinary stirrer to prepare a spinning dope.

The obtained stock solution was spun into a 13% Rodan soda aqueous solution at a temperature of -6°C, and washed with water, stretched, dried, and heat treated according to conventional methods to produce a 10 d fiber (1). The knit LO1 value of the obtained fiber (1) was 22. In addition, as a comparative example, after heating and melting the polymer, the fibers (2) were strained in the same manner as above except that aluminum nitrate was added. ) was created.

Table 1 shows the results of evaluating the light resistance and heat resistance of the 1B fibers (1 to 6).

From Table 1 and above, the product of the present invention has excellent flame retardancy and 1
It is clearly understood that the light resistance and heat resistance are also significantly improved.

Example 2 is similar to the fiber (1) of Example 1, and six types of -M (4
~9) were produced.

The results of light resistance and heat resistance ff are also listed in Table 2.

From the table above in Table 2, the stabilizer addition M and stock solution P recommended in the present invention
It is understood that within the range of H, the effect of improving the light resistance and heat resistance is particularly remarkable.

Example 3 Eight types of fibers (10 to 17) were prepared in the same manner as fiber (1) in Example 1, except that the stabilizer type a was used as shown in Table 3 below, and the pH of the stock solution was increased. did.

The results of evaluating light resistance and heat resistance are also listed in Table 6.

From the above Table 6, it is understood that the products of the present invention have an excellent effect of improving light and heat resistance.

Example 4 72 parts AN, 6 parts Methyl acrylate/I/8 parts CIVP,
Vinylidene chloride μ part and methallylnulfonic acid sorter 0.
A polymer (B) consisting of three parts was prepared in the same manner as in Example 1, and a solution of 10% polymer concentration and 45% Rodan soda was used. (18) was produced.

The fiber (18) had a leek LO value of 23, and the fiber had good light resistance of 4th to 5th grade and heat resistance of 6th to 4th grade.

Claims (1)

[Scope of Claims] 1. A flame-retardant acrylic fiber made of a phosphorus-containing acrylonitrile polymer and containing aluminum or zinc hydroxide with a particle size of 0.4 μm or less. 2. The polymer is based on weight: AN60-90%, phosphorus-containing vinyl monomer 3-20%, halogen-containing vinyl monomer 5
The flame-retardant acrylic fiber according to claim 1, which is a polymer comprising 25% to 25% of other vinyl monomers and 0 to 20% of other vinyl monomers. 3. The flame-retardant acrylic fiber according to claim 1, which contains 0.01 to 3.0% of aluminum or zinc hydroxide based on the weight of aluminum or zinc.