JPS59204649A - Acrylic polymer composition - Google Patents

Abstract

PURPOSE:To provide the titled composition having extremely excellent gloss, transparency, whiteness and dyeability as well as high flame retardancy, by adding a specific metal-containing water-soluble compound to a mixture obtained by the aqueous polymerization of acrylonitrile and a vinyl monomer. CONSTITUTION:A compound selected from metal-containing water-soluble compounds and their derivatives which lose their water-solubility by the pH adjustment or reaction with acid or alkali or by the dilution or reaction with water and form gelatinous precipitate or colloidal fine particles (including the compounds of tin, antimony, bismuth, iron, nickel, zirconium, titanium or zinc) is added to a polymerization reaction mixture obtained by the aqueous polymerization of 30-70wt% of acrylonitrile, 70-30wt% of a halogen-containing vinyl monomer and 0-10wt% of a vinyl monomer containing sulfonic acid group. The amount of the additive is 0.1-8wt%, in terms of metal, based on the polymer.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a novel acrylic polymer composition that has 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 a method of copolymerizing flame retardant additives, a method of adding and mixing a flame retardant to the spinning dope and post-spinning, and a method of adding 1IIt flame retardant in post-processing. There are known methods for attaching.

Generally, a method of adding a flame retardant to the spinning dope is often used because it can impart flame retardancy semi-permanently without impairing the physical properties of the fibers of the comparison source. Various kinds of flame retardants are known, such as halides containing chlorine and bromine, nitrogen-containing and phosphorous compounds, and other metal compounds, but there are few that are effective in making acrylic synthetic fibers flame retardant. Among these, metal compounds are relatively effective in improving the flame retardancy of acrylic synthetic fibers, but they have the disadvantage that they are insoluble in bath additives, resulting in a significant loss of fiber transparency and resulting in only products with degraded quality. has. Furthermore, when manufacturing fibers, acrylic fibers have the disadvantage of increasing the pressure during filtration of the spinning solution and easily clogging the nozzle. It is extremely difficult to develop synthetic fibers, and the reality is that no satisfactory product has yet been obtained.

In view of the above circumstances, the present inventors conducted intensive research to eliminate these drawbacks and find an acrylic synthetic fiber that satisfies both high flame retardancy and excellent gloss and transparency.1.
Surprisingly, acrylic fibers made using a completely new method of adding and containing metal-containing water-soluble compounds to a water-based polymerization reaction mixture are equivalent to conventional acrylic synthetic fibers and resins containing metal compounds. Production of fibers and resins that not only have a high degree of flame retardancy, but also have extremely excellent gloss and transparency, and also have extremely good properties such as white peel and dyeability. The present invention has been achieved based on the discovery that the present invention is suitable for the following.

That is, the present invention provides a polymerization reaction mixture obtained by aqueous polymerization of acrylonitrile and a vinyl monomer copolymerizable with the same, by adjusting the pH with an acid case or an alkali, or by diluting or reacting with water. The polymer composition contains a water-soluble metal compound that forms fine particles such as gel-like precipitates and colloids that do not lose their properties.

The polymer composition related to the present invention can be used as latex by adding various additives, or as resin by separating and refining the polymer, and further processed into fibers, films, or molded products to produce resin products and industrial products. Widely used for +A month, etc. For example, the fibers are not only used in various textile products like general acrylic synthetic fibers, but also in products that require a high degree of P resistance, such as interior products such as curtains and carpets, toys, and nightwear. Old people's, children's products, hospital bedding, as well as wool, animal hair-like filaments, yarn, which are preferred for their excellent gloss, transparency, dyeability, and texture.
Also suitable for bedding, high pile, etc.

The polymer composition referred to 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 %), preferably a copolymer composed of 70 to 30% of a halogen-containing vinyl monomer and 0 to 10% of a vinyl monomer copolymerizable with these. The halogen-containing vinyl monomer mentioned here is, for example, at least one type of monomer selected from vinyl chloride, vinyl chloride, vinyl bromide, vinylidene bromide, etc., and is also a copolymerizable vinyl monomer. The monomers include acrylic acid, methacrylic acid, and 0.5% methacrylic acid. Salts and esters thereof, acrylamide, vinyl acetate, etc. can be mentioned, but at least one of the vinyl yarn monomers that can be copolymerized is a vinyl yarn monomer containing a sulfonic acid group, such as methallyl sulfonic acid, styrene sulfone. More preferably, acids and their salts are selected.

In order to obtain the polymer composition of the present invention, aqueous polymerization, preferably emulsion polymerization method is used. Preferably, a metal-containing water-soluble compound is added and mixed with the polymerization reaction mixture at or after the completion of the polymerization reaction, but unless the compound significantly inhibits the polymerization reaction or the amount added, the entire amount or a portion thereof is added before or during the polymerization. You may add and mix the amount of 10 parts.

The metal-containing water-soluble compounds referred to in the present invention include tin, antimony, zircon, titanium, bismuth, zinc, nickel,
It is a water-soluble compound containing a metal selected from iron, and does not lose water by pII adjustment or reaction with acid or alkali, or dilution or reaction with water, and forms fine particles such as gel-like precipitates and colloids. It is a water-soluble compound that forms particles. Furthermore, an organic compound such as an organic acid metal salt may be added or mixed.

It is preferable that these metal-containing water-soluble compounds are added to the polymerization reaction mixture in a state dissolved in water and mixed uniformly and thoroughly. It can also be added as fine particles in the form of gel precipitates or colloids in water or mixed with other additives, or as a powder, or as a mixture of two or more metal-containing water-soluble compounds. Even if it is added, there is no problem as long as it is uniformly and sufficiently mixed into the polymerization reaction mixture. Regardless of the method used, the metal-containing water-soluble 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.

In addition, when adding and mixing as a water bath liquid or water mixture,
The particle size of the metal compound contained in final products such as fibers and films becomes smaller as the concentration of the water bath liquid or water mixture becomes lower. Therefore, for example, by setting the a degree of the aqueous solution or aqueous mixture to 30% or less, more preferably 15% or less, the particle size can be, for example, 100 mμ or less,
It is possible to obtain a product with better transparency and gloss.

Additionally, metal-containing water-soluble compounds can be added to the polymerization reaction mixture.
Before or after mixing, adjust the pH to 1 to 10, preferably 3.
It is desirable to adjust it to ~7. Thereafter, when the polymer and metal-containing compound are subdivided and purified from the aqueous system by a conventional post-treatment method of the aqueous polymerization reaction mixture, it is desirable from the viewpoint of the yield of the compound and the washing and removal of impurities and by-products.

If the pH is too low, the manufacturing process becomes corrosive, and if the pH is too high, the polymer may become colored.

Although it is not entirely clear why the polymer composition of the present invention produces products that are surprisingly superior in terms of gloss, transparency, and flame retardancy, it is clear that the polymer composition separates from water and the polymer aggregates. Because the metal-containing compound or its reactants are uniformly present in the polymer composition in an extremely fine state during the process of thickening and thickening, the metal-containing compound or its reactant remains in a fine state without agglomerating with each other or thickening. It is thought that it is taken into the surface or inside of the polymer particles. For this reason, metal-containing compounds can exist uniformly and finely dispersed even in polymer base materials such as fibers, do not impede the transmission of light, and have a large surface area.
It is thought to function extremely effectively as a fuel.

The flame retardancy in the present invention was evaluated for the polymer and the metal-containing compound by the oxygen index method.

That is, in the oxygen index method, 25 inches of filament with a total fineness of 5,400 denier is taken, twisted 75 times, and then two of them are combined and reverse twisted 45 times to form a cotton-like sample. The sample was heat treated at 170°C for 5 minutes and placed upright on the holder radar of an oxygen index sampler, and the percentage of oxygen required for the sample to continue burning for 5 ctn (σ) 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 evaluation criteria listed in 1-.

◎: Excellent flame retardancy.

○: Excellent flame retardancy.

△2 Poor flame retardancy.

×: There is almost no twisting property, which is poor.

The transparency of the fibers was determined by bath dissolving a fiber sample in dimethylformamide, measuring the light transmittance of the ICM bath solution at a wavelength of 650 mμ using a spectrophotometer, and comparing the results with the transmittance of dimethylformamide being 100. The transmittance measured using a 5% dimethylformamide solution of the fiber sample was defined as the A value. The larger the A value, the better the transparency.

Further, the transmittance measured using a solution in which a fiber sample was dissolved in dimethylformamide so that the metal content was O and Oa% 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 metal-containing compound or manufacturing method is different, especially when the B value is 50% or more. A feature of the present invention is that it exhibits extremely good transparency even to the naked eye.

The metal content referred to in the present invention is the metal 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 SMS), (omitted), 0.3% aqueous sodium lauryl sulfate solution, and ammonium persulfate to carry out emulsion polymerization.

5 kg of this polymerization reaction mixture (polymer content 22%, polymer composition AN48.2%, VD31.0%, VCl2.7
%, S M 31.1%), a predetermined amount of 10% tin tetrachloride aqueous solution was added and mixed, and the pH was adjusted to 6 using caustic soda to obtain a polymer composition, which was further salted out and washed with common salt. A polymer was obtained.

This polymer was mixed with acetone to a concentration of 30% and heated to form a spinning stock solution, which was then discharged into a 25% acetone aqueous solution through a spinneret with a pore diameter of 0.1 and 300 holes without external pressure or nozzle clogging. A single filament of 3 denier was obtained as Example 1 through the usual steps of washing with water and stretching.

On the other hand, for comparison, as Comparative Example 1, the polymerization reaction mixture of Example 1 was taken out without adding tin tetrachloride and spun as a spinning stock solution, and as Comparative Example 2, Comparative Example 1 Add Mextin acid to the spinning stock solution with an average particle size of 1.5
[mu]] was added at the same amount of metal tin content as the filament of Example 1, and the filament was spun and evaluated at the same time. The results are shown in Table 1.

From Table 1, the fiber of Example 1 efficiently contains the tin compound and has extremely good tiI! Not only does it have flammability, but it also has excellent 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 and has poor flame retardancy. On the other hand, Comparative Example 2, which is a conventional flame retardant fiber, has excellent flame retardancy, but the fibers turn white due to the flame retardant particles and have poor transparency.

Examples 2 to 9, Comparative Examples 3 to 10 Using the polymerization reaction mixture used in Example 1, SnC/
2.5bC18, Zr(SO+)2, 'I'1 (SQL
)2, Bi(NOB)2, ZnS04, N1(NOB
)2, F"eSO4 (7) Add and mix the aqueous solutions of each inorganic compound to the polymerization reaction mixture in the same manner as in Example 1, adjust the pH to 3 to 10" using caustic soda, salt out with common salt,
Washing was performed to obtain a polymer. This polymer was spun in the same manner as in Example 1 to obtain one filament of 3 denier.

For comparison, a conventional metal-containing inorganic flame retardant was added to the spinning stock solution of the polymer of Comparative Example 1, and a 3-denier filament was similarly obtained. The flame retardancy, gloss and transparency of these filaments are shown in Table 2.

In Examples 2 to 9, the comparative examples made with gloss, transparency, and flame retardancy exhibit good flame retardancy, but the gloss and transparency are clearly inferior.

Comparing Transmittance of Example and Comparative Example] 3, it can be seen that the present invention is clearly superior.

Table 2 Examples 10 to 13, Comparative Examples 11 to 14 Emulsion polymerization was carried out in the same manner as in Example 1, and the polymer composition A N
A polymerization reaction product containing a polymer of 48.0%, V C5-2.2%, and sodium styrene sulfonate 0.8% was obtained. Similar to Examples 2 to 9, 5nCd2, Sb0g8, Zn
(SO4)2, Ti, (SO4)2 (7) A water bath solution of each inorganic compound was added to and mixed with the polymerization reaction mixture to obtain a polymerization composition. A polymer and a metal-containing compound were purified to P41+ from this polymer composition, and a 10% acetone solution was prepared. At the same time, only the polymer was taken out without adding any metal-containing compounds to this polymerization reaction mixture, and metastannic acid dioxide 77, which is a conventional d@ fuel agent, was extracted. = 7, Zr(O
H) 4 and Ti02 were each added in predetermined amounts to the polymer so that the metal content was the same as in Examples 10 to 13, and a 10% acetone solution was prepared in the same manner. A film was made by spreading these 10% acetone solutions on a glass plate, and its transparency was evaluated. The results are shown in Table 3.

Table 3 Films made using the polymer composition of the present invention have gloss,
Although the film of the comparative example has good transparency, it is cloudy due to the added flame retardant particles and has poor transparency.

Patent applicant Kanebuchi Kagaku Kogyo Co., Ltd. Procedural amendment stamp button 1, Indication of the case Patent application No. 81433 of 1981 2, Name of the invention Acrylic polymer composition 3, Person making the amendment Relationship to the 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 1) On page 4, line 12 of the specification, insert [polymer composition] after "acrylic system" .

2) On page 6, line 13 of the specification, insert [methacrylamide,] after “crylamide.” 3) On page 7, line 20 of the specification, replace “in water” with [water. ] to be corrected.

4) Page 16 of the specification, line 6, r Zn (S04.
)z −1 is corrected to (Zr (SO4)2).

5) On page 16, line 13 of the specification, "antimony zuronic acid trioxide" is corrected to "antimony zuronic acid, antimony dioxide".

that's all

Claims (1)

[Claims] (2) A metal-containing aqueous solution that does not lose water solubility and forms fine particles such as gel-like precipitates or colloids by p I-I adjustment or reaction with acid or alkali, or by dilution or reaction with water. 1. A polymer composition comprising at least one compound selected from acrylonitrile and its derivatives contained in a polymerization reaction mixture obtained by aqueous polymerization of acrylonitrile and a vinyl monomer copolymerizable therewith. 2. The water fa '19E metal compound is a water-soluble inorganic compound containing at least one element selected from tin, antimony, bismuth, iron, nickel, zircon, titanium, and zinc. Polymerization composition. 3. The polymer contained in the polymerization reaction mixture obtained by aqueous polymerization contains 30 to 70% by weight of 7crylonitrile, 70 to 30% by weight of halogen-containing vinyl monomer, and those capable of copolymerizing with them. The polymer composition according to claim 1, which comprises 0 to 10% by weight of a vinyl monomer. 4. The polymer composition according to claim 3, wherein at least one of the copolymerizable vinyl monomers is a sulfonic acid group-containing vinyl monomer. 5. The polymer composition according to claim 1, wherein the aqueous polymerization is emulsion polymerization. 6. Claim 1, which comprises adding a metal-containing water-soluble compound at a metal content of 0.1 to 8% by weight to the polymer contained in the polymerization reaction mixture obtained by water-based model numbering. The polymeric composition described in .