JPS59204648A - Flame-retardant acrylic polymer composition - Google Patents

Abstract

PURPOSE:To obtain the titled composition having extremely excellent gloss, transparency, whiteness and dyeability as well as high flame retardancy, by adding a tin compound and an antimony compound to a mixture obtained by the aqueous polymerization of acrylonitrile and a vinyl monomer. CONSTITUTION:(A) 30-70wt% of acrylonitrile, (B) 70-30wt% of a halogen-containing vinyl monomer and (C) 0-10wt% of a vinyl monomer copolymerizable therewith, preferably a vinyl monomer containing sulfonic acid group, are polymerized in an aqueous phase (preferably by emulsion polymerization). The obtained reaction mixture is added with a tin compound and/or an antimony compound to obtain the objective composition. The amount of the additive is 0.1- 8wt%, preferably 0.3-5wt% in terms of metallic tin or metallic antimony, based on the polymer.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a polymer composition suitable for producing novel acrylic synthetic fibers and resins that have a high degree of flame retardancy and excellent gloss and transparency.

Conventionally, so-called modacrylic fibers, which are copolymerized with a relatively large amount of vinyl halide, have a certain degree of flame retardancy themselves, but social demands for flame retardancy are rapidly increasing due to recent hotel fires. Nowadays, there is a demand for fibers with even better flame retardancy. Methods for imparting flame retardancy to fibers include copolymerizing flame retardant monomers, adding and mixing flame retardants to the spinning dope and then spinning, and adding flame retardant to the fibers in post-processing. It has been known. Generally, a method of adding a flame retardant to the spinning dope is often used because it can impart flame retardance semi-permanently without impairing the physical properties of the fibers of the fiber for comparison. Various types of flame retardants are known, including halides containing chlorine and bromine, nitrogen-containing and phosphorus compounds, and other metal compounds, but there are few that are effective in making acrylic synthetic fibers flame retardant.

Among them, metal oxides such as tin oxide, antimony oxide, and magnesium oxide are relatively effective in improving the flame retardancy of acrylic synthetic fibers, but because they are insoluble in solvents, the transparency of the fibers can be significantly lost. , and the quality has deteriorated.
It has the disadvantage that it cannot be obtained (strength). Furthermore, when manufacturing fibers, it also has the drawback of increasing the pressure during filtration of the spinning solution and easily causing nozzle clogging, so Aku-1 Nor yarn synthetic fiber satisfies both high flame retardancy, gloss, and transparency. It is extremely difficult to develop acrylic resins and their products.These issues also apply to acrylic synthetic resins and their products.

As a result of intensive studies to solve this problem and provide acrylic synthetic fibers and resins that satisfy both high flame retardance, excellent gloss, and transparency, we added an inorganic tin compound and an antimony compound to the aqueous polymerization reaction mixture. Surprisingly, the acrylic polymer composition obtained by a completely new method that contains tin and/or tin has a high degree of flame retardancy equivalent to conventional acrylic synthetic fibers and resins containing tin and/or tin. It has been discovered that the present invention is suitable for producing fibers and resins that not only have the following properties but also have extremely excellent gloss and transparency, and also have extremely good properties such as whiteness and dyeability. reached.

That is, the present invention provides a flame-retardant acrylic polymer composition comprising a polymerization reaction mixture obtained by aqueous polymerization of acrylonitrile and a vinyl monomer copolymerizable therewith with a tin compound and/or an antimony compound. It is something whose content is a thing.

The polymer composition related to the present invention can be made into latex by containing various additives, or can be processed into resin by separating and refining the polymer, or can be further processed into fibers, films, or molded products to be used as industrial resin products. It is widely used for other purposes.

For example, the fibers are not only used in various textile products like general acrylic synthetic fibers, but also in advanced ):il[
Items that require flammability, such as interior goods such as curtains and carpets, toys, items for the elderly such as nightwear, children's goods, and hospital bedding, as well as those that require excellent gloss, transparency, dyeability, and texture. Hair, animal hair-like filaments, threads,
Also suitable for bedding, high heels, etc.

The polymer composition discussed in the present invention is an acrylic polymer composition having a polymer having acrylonitrile as a main component as a base material, and the polymer contains 30 to 70% by weight of acrylonitrile (hereinafter simply abbreviated as %). ), a copolymer composed of 70 to 30% of a halogen-containing vinyl monomer and 0 to 10% of a vinyl monomer copolymerizable with these is preferable. The halogen-containing vinyl yarn monomers mentioned here include, for example, vinyl chloride, vinylidene chloride, vinyl bromide,
At least one type of monomer selected from vinylidene bromide, etc. Copolymerizable vinyl monomers include acrylic acid, methacrylic acid and their salts and esters, acrylamide, methacrylamide, and vinyl acetate. At least one of the copolymerizable vinyl monomers is a sulfonic acid group-containing vinyl monomer,
For example, it is more preferable to select methallylsulfonic acid, styrenesulfonic acid, salts thereof, and the like.

In order to obtain the polymer composition of the present invention, aqueous polymerization, preferably emulsion polymerization method is used. Preferably, a tin compound and/or an antimony compound is added to and mixed with the polymerization reaction mixture at or after the completion of the polymerization reaction, but unless the compound or the amount added significantly inhibits the polymerization reaction, it may be added or mixed before or during the polymerization. The whole amount or a portion thereof may be added and mixed.

The tin compounds referred to in the present invention include divalent and tetravalent compounds such as tin halides, tin oxyhalides, stannic acid or its salts, inorganic acid tin salts, and derivatives thereof, and antimony compounds. is antimony halide, antimony oxyhalide, antimonic acid 1
Examples include salts thereof, inorganic acid tin salts, and derivatives thereof, which are trivalent and pentavalent, respectively. Furthermore, organic compounds such as organic acid tin salts and organic acid antimony salts may be added or mixed, but preferably inorganic tin compounds and/or Containing it as an inorganic antimony compound is effective in enhancing flame retardancy.

In the present invention, the content of the tin compound and/or antimony compound is 0.1 to 8%, more preferably 0.3 to 5%, based on the polymer.
It is added and mixed within the following range. If the content is smaller than the above range, flame retardancy will be insufficient, while if it is larger, gloss and transparency will be adversely affected.

These tin compounds and antimony compounds are water-soluble tin compounds or water-soluble antimony that become fine particles such as gel-like precipitates or colloids by adjusting pH and H with acid or alkali or by reaction, or by dilution or reaction with water. The compound is preferably added to the polymerization reaction mixture in a dissolved state in water and mixed uniformly and thoroughly. It can also be added as a gel-like precipitate or colloidal fine particles mixed with water or other additives, or as a powder, or as a mixture of two or more types of inorganic tin compounds. Evenly and thoroughly mixed into the polymerization reaction mixture. Regardless of the method, the tin compound or antimony compound to be added is preferably added and mixed as a dilute aqueous solution or an aqueous mixture as long as it does not interfere with the production process, but is not particularly limited thereto. In addition, when adding and mixing a tin compound or an antimony compound as an aqueous solution or an aqueous mixture, the final "m"
-m % The particle size of the tin compound or antimony compound contained becomes smaller as the concentration of the aqueous solution or aqueous mixture becomes lower.

Thus, the tin compound or antimony compound in the water bath solution or water mixture can more preferably be 30% or less.

In addition, before or after adding and mixing a tin compound and/or an antimony compound to the polymerization reaction mixture,
~8, preferably L-( is desirably adjusted to 3 to 7. Afterwards, the polymer and the tin compound and 7/or antimony compound are separated and purified from the aqueous system by a normal post-treatment method for the aqueous polymerization reaction mixture. This is desirable from the viewpoint of the yield of tin compounds and antimony compounds and the cleaning and removal of impurities and by-products.If the pH of the polymerization product is too low, corrosiveness in the manufacturing process becomes a problem, while if it is too high, the polymer The problem of coloring arises.

The reason why the polymer composition of the present invention provides resins and fibers that are good in terms of gloss, transparency, and flame retardance is not necessarily clear, but the polymer composition separates from water and the polymer In the process of coagulation and enlargement, the tin compound, antimony compound, or their reactants are uniformly present in the polymer composition in an extremely fine state, so they do not aggregate or enlarge with each other. It is thought that the particles remain in a fine state and are incorporated into the surface or inside of the polymer particles. Therefore, tin compounds and antimony compounds can exist evenly and finely dispersed even in polymer base materials such as fibers, and have a large surface area without interfering with light transmission. It is thought that it functions as a fuel.

In the flame retardancy evaluation in the present invention, the polymer and the tin and/or antimony compound were separated and purified from the polymer composition to form fibers, and the fibers were evaluated by the oxygen index method.

In other words, the oxygen index method involves taking 25 inches of filament with a total fineness of 5,400 denier, twisting it 75 times, and twisting it 25 times.
This combination is twisted 45 times to form a cotton-like sample.

The sample was heat-treated at 170°C for 5 minutes, then stood upright in the holder of an oxygen index sampler, and the percentage of oxygen required for the sample to continue burning for 5 r:m was measured. The higher the number indicated by the oxygen index method, the more flame retardant.

The oxygen index, its combustion state, and the sample after combustion were observed, and a comprehensive evaluation of flame retardancy was performed based on the following evaluation criteria.

三＝＃＝≠ ◎: Very good flame retardancy.

○: Excellent flame retardancy.

△: Poor flame retardancy.

X: There is almost no flame retardancy, which is poor.

The transparency of the fibers was determined by dissolving a fiber sample in dimethylformamide, measuring the light transmittance of a 1 ann solution at a wavelength of 650 mμ using a spectrophotometer, and comparing the results with the transmittance of dimethylformamide being 100. 5 fiber samples
The transmittance measured as a % dimethylformamide solution is A
value. The larger the A value, the better the transparent pouring. Further, the transmittance measured using a solution in which the fiber sample was dissolved in dimethyl formamide such that the content of metallic tin and metallic antimony was 0.03% was defined as the B value. The higher the B value, the better the transparency of the product using the polymer composition obtained even if the tin compound, antimony compound, or manufacturing method is different.
A feature of the present invention is that it shows extremely good transparency even to the naked eye when the value is 0% or more. The metallic tin content or metallic antimony content as referred to in the present invention is the tin content or antimony content contained in a sample measured by atomic absorption spectrometry according to a conventional method.

Hereinafter, the present invention will be explained in more detail with reference to Examples and Comparative Examples, but the present invention is not limited thereto.

Example 1, Comparative Examples 1 to 2 Acrylonitrile (hereinafter abbreviated as AN), vinylidene chloride (hereinafter abbreviated as VD), vinyl chloride (hereinafter abbreviated as VC), sodium methallylsulfonate (hereinafter abbreviated as S'MS) Emulsion polymerization was carried out using o, s% sodium lauryl sulfate water bath solution and ammonium persulfate.

This polymerization reaction mixture 5 had a VC polymer content of 22%, a polymer composition of AN of 48.2%, a VD of 31.0%, and a VCl of 2.7%.
%, SMS 1.1%), add and mix a predetermined amount of 10% tin tetrachloride aqueous solution, and adjust the pH to 6 using caustic soda.
A polymer composition was obtained. Further, a polymer was obtained by salting out and washing with common salt, and this polymer was dissolved in acetone for 30 minutes.
%, mix and heat to make a spinning stock solution with a pore size of 0.
Discharged into a 25% acetone aqueous solution without increasing pressure or clogging the nozzle from a spinneret with a diameter of 300 holes.
A single filament of 3 denier was obtained as Example 1 through the usual steps of washing with water and stretching.

For comparison, as Comparative Example 1, the polymerization reaction mixture of Example 1 was taken out and spun as a spinning dope without adding tin tetrachloride, and as Comparative Example 2,
Metastannic acid (average particle size 1.5μ) was added to the spinning stock solution of Comparative Example 1.
A filament spun with the same amount of metal tin content as the filament of Example 1 was also evaluated at the same time. The results are shown in Table 1.

Table 1 From Table 1, the fiber of Example 1 not only efficiently contains the tin compound and has extremely good flame retardancy;
It also has excellent properties in terms of gloss and transparency. Furthermore, it is also excellent in general fiber properties such as white skin and dyeability.

On the other hand, Comparative Example 1 does not contain an inorganic tin compound, so as expected, the gloss and transparency are good, but the flame retardance is poor. On the other hand, Comparative Example 2, which is a conventional flame retardant fiber, has excellent flame retardancy, but the fibers are whitened near the flame retardant particles and have poor transparency.

Examples 2 to 7, Comparative Examples 3 to 8 Emulsion polymerization was carried out in the same manner as in Example 1, and the polymer composition A l
A polymerization reaction mixture containing 20% of a polymer consisting of \1560%, VD 42.9%, and SM 31.1%? 8
Ta.

Take 5 kg of each of these polymerization reaction mixtures, add and mix a 10% tin dichloride water mixture at $2 so that the metallic tin content shown in the table is contained in the fibers, and adjust the pH using caustic soda.
was adjusted to 4 to salt out the polymer. These polymers were dissolved in dimethylformamide and spun to give Examples 2 to 7.

On the other hand, in Comparative Examples 3 to 8, tin dichloride was not added to the polymerization reaction mixture, but various amounts of metastannic acid were added to the spinning stock solution for spinning. The results are shown in Table 2.

Table 2 Examples 2 to 7 have good gloss, transparency, and flame retardancy, while comparative examples made by the conventional flame retardant reinforcement method show poor results when the amount of metastannic acid added is increased. Although flame retardancy improves, gloss and transparency deteriorate, making it difficult to obtain the desired quality. Comparing the transmittance B of the example and the comparative example, it can be seen that the present invention is clearly superior.

Examples 8 to 15 Using the polymerization reaction mixture of Example 1, various types of tin compounds were added and mixed so that the tin compound in the fibers had a metallic tin content of 0.7%. A polymer composition was obtained, and a sample was obtained by spinning in the same manner. The results are shown in Table 3.

As shown in Table 3, all exhibited extremely good gloss and transparency.

Example 16, Comparative Example 9 A polymer composition was obtained by changing the 10% tin dichloride water mixture of Example 5 to a 10% antimony trichloride water mixture (Example 16)
The metastannic acid of Comparative Example 6 was mixed with ammonium trioxide (average particle size 1.5 μm) and tested in the same manner as Comparative Example 9.

The results are shown in Table 4.

Table 4 As is clear from Table 4, Example 16- has excellent flame retardancy, gloss, and transparency, whereas Comparative Example 5 and Comparative Example 9 are inferior in gloss and transparency.

Examples 17-18, Comparative Examples 10-11 Emulsion polymerization was carried out in the same manner as in Example 1 to obtain a polymer composition AN4.
A polymerization reaction mixture was obtained containing 8.0% of polymer, 52.2% of V C and 0.8% of sodium styrene sulfonate.

Using a 5% aqueous solution of tin tetrachloride (Example 17) and a 5% aqueous solution of antimony trichloride (Example 18), metal tin was also added to the polymer (〈=2% in the content of antimony metal). 11) Add and mix a predetermined amount of the polymer composition. From this polymer composition, the polymer and the tin or antimony compound are separated and purified, and further 1
It was made into a 0% acetone solution.

At the same time, only the polymer was taken out without adding tin or antimony compounds to this polymerization reaction mixture, and conventional flame retardants metastannic acid (average particle size 1.5 It) (comparative example 10) and antimony trioxide (average particle size 1.5 μ) (ratio 1 bite case 1
1) is added in a predetermined amount to the polymer so that the content of metal tin or antimony is 2%,
Similarly, a 10% acetone solution was prepared.

These 10% acetone solutions were applied onto a glass plate to form a film, and the transparency thereof was evaluated. The results are shown in Table 5.

Table 5 Films prepared using the polymer composition of the present invention have gloss,
Although the film of the comparative example has good transparency, it is cloudy and has poor transparency due to the added flame retardant particles.

Patent requester Kanebuchi Kagaku Kogyo Co., Ltd. Procedure Neho (self-proposal) 1982 Patent Application No. 79801 2, Name of invention Flame-retardant acrylic polymer composition 3, Relationship with the amended person case Patent Applicant Address: 3-2-4 Nakanoshima, Kita-ku, Osaka Name (094)
) Representative of Kanebuchi Chemical Industry Co., Ltd. Representative Director Takashi 1)
4, Agent address: 3-2-4-5 Nishitenma, Kita-ku, Osaka, subject of amendment: “Detailed description of the invention” 6, Contents of amendment

Claims (1)

[Claims] 1. Arylonitrile and vinyl z copolymerizable with it
To the polymerization reaction mixture obtained by aqueous polymerization of the monomer,
A flame-retardant acrylic polymer composition containing a tin compound and/or an antimony compound. 2. The polymer of the polymerization reaction mixture obtained by aqueous polymerization contains 30 to 70% by weight of acrylonitrile, 70 to 30% by weight of a halogen-containing vinyl monomer, and 0 to 30% of a vinyl monomer copolymerizable therewith. A polymeric composition according to claim 1, consisting of 10% by weight. 3. The polymer composition according to claim 2, wherein at least one of the copolymerizable vinyl monomers is a sulfonic acid group-containing vinyl monomer. 4. The polymer composition according to claim 1, wherein the aqueous polymerization is emulsion polymerization. 5. A tin compound and/or an antimony compound is added to the polymer of the polymerization reaction mixture obtained by aqueous polymerization at a metal tin content and/or a metal antimony content of o, 1 to 1.
8% by weight of the polymer composition according to claim 1.