JPS5927771B2 - Nannenshiyorihouhou - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION This invention relates to a method for imparting flame retardancy to fibers and films made of hydrophobic synthetic polymeric materials.

Conventionally, the following methods have been used to make hydrophobic synthetic polymer materials flame retardant.

(1) A method of copolymerizing a flame retardant when synthesizing a hydrophobic synthetic polymer substance.

(2) A method of incorporating a flame retardant into a hydrophobic synthetic polymer material.

(3) A method in which a flame retardant is attached to the surface of fibers or films made of hydrophobic synthetic polymer substances in post-processing.

(4) A method in which a flame retardant is infiltrated into the fiber or film made of a hydrophobic synthetic polymer substance during post-processing. However (
Although the method 1) has good durability, it has the disadvantage of deteriorating the original physical properties of the synthetic polymer. Although the method (2) also has good durability, it has drawbacks such as deterioration of spinning properties and plasticization of the polymer, resulting in deterioration of physical properties. Furthermore, method (3) has disadvantages such as poor hand feel, staining, poor durability, and decreased color fastness because the flame retardant is attached to the surface. On the other hand, for method (4), tris(2,3 dibromopropyl) phosphate,
Phosphorus compounds such as brominated triphenyl phosphate are known, but substances that are liquid at room temperature may bleed at high temperatures and cause texture due to plasticizer effects when blended in the amount necessary to obtain sufficient flame retardancy. There are drawbacks such as deterioration, decreased dye fastness, and poor washing durability. In addition, even those with a high melting point have drawbacks such as being susceptible to hydrolysis. In order to improve these shortcomings, the present inventors conducted intensive research and found that various physical properties such as texture and touch, as well as processability such as dyeability and finishing, are impaired in fibers and films made of hydrophobic synthetic polymer substances. We have discovered a post-processing method that significantly improves the flame retardance of fibers and films, and also makes them durable, without causing any damage.

That is, the present invention relates to an improvement of the method (4) above,
A compound that has an affinity for fibers and films made of hydrophobic synthetic polymers and is solid at room temperature and can impart flame retardancy is infiltrated into the interior of the fibers or films to improve flame retardance and at the same time, dye treatment. The dyeability is improved by simultaneously applying flame retardant treatment and flame retardant treatment.

The present invention will be explained in detail below. The present invention comprises a flame retardant treatment method characterized in that fibers and films made of hydrophobic synthetic polymers are treated with an aqueous dispersion containing a compound represented by the following general formula and a dye under dyeing conditions.

Xl K; R1 -0R, 0(CHCHO)1H or /) 1C or none (where Y is a halogen, a number) p is O or an integer N of 1 to 4, . n': an integer of 1 to 5 The hydrophobic synthetic polymer materials of the present invention include polyamides, polyesters, polyacrylonitrile (including copolymers),
These include cellulose acetate, polyvinyl chloride, polyolefin, acetalized polyvinyl alcohol, polyurethane, and polycarbonate.

Fibers include long fiber yarns, short fibers, spun yarns, woven fabrics, knitted fabrics, nonwoven fabrics, etc., and may be composed of a single component or a composite component.

A film is a membrane-like substance, and also includes a fibrous substance obtained by tearing the film.

Examples of the compound represented by the above general formula include tetrapromubisphenol Al2.2-bis[3.5 dibrom-4(
2-hydroxyethoxy)phenyl]propane, brominated diphenyl, brominated diphenyl ether, brominated diphenyl sulfone, bis(3,5 dibromo-4-hydroxyphenyl) sulfone, brominated diphenylamine, brominated diphenylmethane, bromine and triphenyl.

Dyes include disperse dyes, acid dyes, acid medium dyes, basic dyes, reactive dyes, direct dyes, sulfur dyes, azoic dyes, vat dyes, and fluorescent dyes that can dye hydrophobic synthetic fibers and films. It will be done.

To prepare the aqueous dispersion of the flame retardant and dye in the present invention, after dissolving the above flame retardant in an organic solvent, one or more types of general anionic or nonionic surfactants used as emulsifiers and dispersants are added. After blending, the dye is dispersed in water together with the dye, or the flame retardant of the present invention is blended with one or two types of anionic or nonionic surfactant, and the dye is pulverized using a pulverization device such as a glass grinder. It can be obtained by dispersing it in water. As the organic solvent, methanol, ethanol, benzene, toluene, xylene, benzyl alcohol, mono-, di- and trichlorobenzene, dimethyl formamide, dimethyl sulfoxide, etc. are used.

Examples of anionic surfactants include fatty acid salts, alkyl sulfate ester salts, alkylbenzene sulfonates, alkylnaphthalene sulfonates, alkyl phosphate ester salts,
These include dialkyl sulfosuccinate salts, naphthalene sulfonic acid formalin condensates, and polyoxyethylene alkyl sulfate salts.

Nonionic surfactants include polyoxyethylene alkyl ether, polyoxyethylene alkyl phenol ether, polyoxyethylene fatty acid ester, sorbitan fatty acid ester, polyoxyethylene sorbitan fatty acid ester, glycerin fatty acid ester, oxyethylene oxypropylene block polymer. There is first class.

Fibers or films made of a hydrophobic polymer substance, preferably polyester, are immersed or padded in the water dispersion of the flame retardant component and dye obtained in this manner, and then treated under dyeing conditions. Or it is fixed by penetrating into the inside of the film.

In addition, in this case, pre-treatment with a fiber swelling penetrant or use of a swelling penetrant in the same bath will increase the absorption of the flame retardant into the fibers and films, allowing the flame retardant to be absorbed at a lower temperature and in a shorter time. It becomes possible to process. Phenol as a swelling penetrant,
Cresol, benzyl alcohol, benzoic acid and its derivatives, methylnaphthalene, mono-, di- and trichlorobenzene, 0-chlorophenol, p-chlorophenol, p-promophenol, 2.4.6-trichlorophenol, 2.4.6-trichlorophenol. Promphenol, dimethylformamide, dimethyl sulfoxide, formic acid, salicylic acid and its derivatives, acetophenone, benzophenone,
Examples include monobromobenzene, p-dibromobenzene, orthophenylphenol. The treatment method is carried out at any suitable step from the time the fibers and films are formed to the final product by applying an ordinary pressure dyeing method, a high temperature and high pressure dyeing method, and a thermosol dyeing method.

The gist of the present invention is to carry out dyeing and flame retardation simultaneously, and only by doing so can the purpose be achieved.

That is, if a flame retardant treatment is performed before or after dyeing, the dye fastness and dyeability generally decrease, and the flame retardant falls off or is insufficiently exhausted. However, if it is carried out simultaneously with dyeing, these drawbacks will be eliminated and practical dyeing and flame retardation will become possible.
The flame retardant component of the present invention needs to be adjusted to be contained in an amount of 1 to 25%, preferably 3 to 20%, based on the fibers and films to be treated.

If it is less than 3%, the flame retardancy will be insufficient, and if it is more than 25%, the texture and physical properties of the treated object will deteriorate, making it impractical.

The characteristics of the flame retardant processing method of the present invention are as follows. According to the invention it is necessary that the flame retardant be brominated.
That is, since the flame retardant of the present invention has a relatively high molecular weight but is brominated, it has extremely high permeability into synthetic fibers and films. For example, although bisphenol A and tetrachlorobisphenol A have poor exhaustion properties for polyesters, the tetrabisphenol A of the present invention exhibits excellent exhaust properties. In addition, brominated aromatic ring compounds with low molecular weights have poor durability even when exhausted. Furthermore, according to the treatment method of the present invention, as a result of infiltrating the flame retardant into the interior of fibers and films, a flame retardant effect with very excellent washing resistance can be obtained. There is no bleeding of the flame retardant from inside the fiber at high temperatures and no change in texture due to the effect of the plasticizer, which are disadvantages of the treatment with tris(2,3 dibromopropyl) phosphate or the like. In addition, there are no problems such as stickiness, dirt, or rough hardness that occur when adhering to a surface. Furthermore, the method of copolymerizing the flame retardant has the advantage that, compared to the method of kneading it, the flame retardant is absorbed into the amorphous portion of the hydrophobic polymer material, so that its physical properties are less likely to deteriorate. Furthermore, the treatment method of the present invention has the advantage that existing equipment can be used as is. Next, examples of the present invention will be shown.

Example 1 0.4 t of disperse dye Resolin Blue FBL (manufactured by Bayer AG) was added to 2.07 t of a flame retardant obtained by mixing equal amounts of a finely divided compound of the compound shown in Table 1 and a naphthalene sulfonic acid formalin condensate as a dispersant. was added and then 300 ml of water was added to prepare a dispersion of flame retardant and water in water.

10y of polyethylene terephthalate long fiber fabric (fabric weight 807/m'') was immersed in this dispersion and treated at 130°C for 45 minutes.Next, after washing with water at 40°C for 10 minutes, 47th Be'caustic soda, amylazine D (Nonionic activator, manufactured by Daiichi Kogyo) and hydrosulfide (1 each)
Reduction cleaning was performed at 90° C. for 30 minutes in a 7/l aqueous solution. Next, it was thoroughly washed under running water and then dried. Next, part of the treated fabric was 17/I? ．． 60'C in an aqueous Marcel soap solution of
I washed it for 15 minutes. Next, it was washed three times with 4'C water for 5 minutes and then dried. This washing, water washing, and drying operation was repeated five times. Table 1 shows the results of examining the exhaustion rate and flame retardancy of the treated fabric before and after washing. The exhaustion rate was determined by measuring the weight increase before and after treatment. Flame retardancy was measured by the number of times of flame contact in the 45-front coil method (JISLlO9l D method). It is clear that the flame retardants 1 to 6 according to the present invention have high exhaustion properties and do not fall off due to washing and do not have deterioration in flame retardancy. Furthermore, there were no problems such as hardening of the dyeing property or the like. Example 2 Acrylic Blue GRL (manufactured by Nippon Kayaku) 0.37 was added to a solution 57 consisting of 2 parts of 2 moles of ethylene oxide adduct of tetrapromubisphenol A, 2 parts of benzyl alcohol, and 1 part of polyoxyethylene sorbitan monooleate. Then, 300 ml of water was added and mixed well with stirring to prepare a dispersion of the flame retardant and dye in water.

In this dispersion, polyacrylonitrile short fiber knitted fabric 107 was added.
was immersed and treated at 100°C for 45 minutes. This was thoroughly washed under running water and then dried. Next, a portion of the treated fabric was washed in the same manner as in Example 1. Table 2 shows the results of examining the exhaustion rate and flame retardancy of the treated fabric before and after washing. No shedding of the flame retardant or decrease in flame retardancy due to washing was observed. Furthermore, there were no problems with dyeability, texture, stickiness, etc. Example 3 A dispersion was prepared using the following compound in the same manner as in Example 1, and a polyethylene terephthalate long fiber fabric was treated in the same manner as in Example 1.

The flame retardant exhaustion rate of the treated fabric after treatment was 5.4%, and the exhaustion rate after washing was 4.7%. The flame retardancy measured by the same method as Example 1 was 4.1 immediately after treatment and 3.7 after washing.
showed good results. Example 4 Compounds 1 to 4 shown in Table 1 were pulverized and a dispersion liquid was prepared in the same manner as in Example 1.

A polyethylene terephthalate biaxially stretched film (thickness: 120μ) 107 was immersed in this dispersion and heated to 135°C for 4 hours.
It was treated in the bath for 0 minutes. Then, after washing with water at 40°C for 10 minutes, 47. Be's caustic soda and sundetsudo G-
The sample was washed at 90°C for 20 minutes in an aqueous solution containing 17/l of each of 29 (nonionic activator), washed with water, and then dried. A portion of this treated film is used as a synthetic detergent (Kao Soap: Sub).
17/l using a household electric washing machine at 50℃Xl
The washing operation was repeated five times, with one wash for O. The flame retardant exhaustion rate and flame retardance of the treated film before and after washing were evaluated and shown in Table 3. From Table 3, it was found that the flame retardant of the present invention exerts a good flame retardant effect on films as well.

Claims (1)

[Claims] 1. A dyeing process characterized by treating a fiber or film made of a hydrophobic synthetic polymer with an aqueous dispersion containing at least one compound represented by the following general formula and a dye under dyeing conditions. Combustion method. ▲There are mathematical formulas, chemical formulas, tables, etc.▼ Alkyl, R' and R'' are H or CH_3, but R',
R″ does not become CH_3 at the same time. l is an integer from 1 to 4) A; -O-, -NH-, -CH_2
-, -SO_2-, ▲There are mathematical formulas, chemical formulas, tables, etc.▼
, ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ or none (here, Y is halogen, p is 0 or an integer from 1 to 4) m, m'; 0
or an integer n, n' of 1 to 4; an integer of 1 to 5;