JPH0621421B2 - Flameproofing method for polyester textile products with excellent texture - Google Patents

Description

Description: TECHNICAL FIELD The present invention relates to a flameproofing method for a polyester fiber product having an excellent feeling.

In recent years, many fibers have been used in clothing, bedding, interior interior materials, automobile interior materials, aircraft interior materials, and the like.
Generally polyester, nylon, acrylic, rayon,
Fibers such as acetate, cotton and hemp are not self-extinguishing,
Since it is too defenseless against fire, it has caused a large number of lives to be lost in hotel fires and tunnel fires. Therefore, flameproofing of each fiber is required. Polyester fiber has many uses,
In recent years, there has been a marked trend in the increase in the amount used, so that flameproofing is becoming more important.

As a flameproofing method for polyester fibers, an internal addition method, a surface adhesion method by post-processing, a thermosol or an exhaustion method are known, but each processing method has advantages and disadvantages. For example, in the case of the internal addition method, it is excellent in terms of durability, but due to the limited application of the product, it is cost-effective because it does not end up in mass production, and the softening agent and repellant used as a post-treatment agent. There is a drawback in that the flameproofness, which is an influence of fiber resins such as water solutions and antistatic agents, can vary. The surface adhesion method by post-processing allows flame-proof processing according to the application and is easy in workability and economically advantageous, but since it is surface adhesion, the texture of the fiber, for example, a sticky feeling and a rough and rigid feeling. However, there is a drawback that it is difficult to process without impairing the hygroscopic feeling and the durability is difficult to obtain. Similar to the surface adhesion method, the thermosol or exhaust method can be flameproofed according to the application, and compared to the internal addition method, it can be sufficiently performed in the conventional processing process without using special equipment, and the surface adhesion method Since the flameproofing agent enters the inside of the fiber, there are few defects that impair the texture of the fiber and the durability is easily obtained. Therefore, the flameproofing method of polyester fiber is the most noticeable processing method in recent years. However, JP-A-54-18996
No. 59-36032 and JP-A-59-189.
As described in Japanese Patent No. 138, the thermosol or exhaust method has various restrictions on the flameproofing agent used, and there are problems that workability and physical properties of processed products should be improved. For example, when using an aqueous dispersion of hexabromocyclododecane, the average particle size of hexabromocyclododecane is 1 μm.
There is a limitation such that the dispersant cannot be used, and the workability is not evenly adhered to the fibers due to sedimentation of the treatment liquid or turling in the workability. In the physical properties, the hardness of the texture, the light resistance, the heat resistance and the friction fastness are reduced or a fiber auxiliary agent used in combination, such as a softener, a water repellent,
There are many problems such as deterioration of flameproofness due to antistatic agents. However, a flameproofing method that completely eliminates these problems has not yet been known. The present inventors have conducted research to solve the above-mentioned problems, and as a result, a combination of specific compounds is useful for imparting good flameproofness and various physical properties to polyester fibers in accordance with the requirements of each application. Heading
The present invention has been reached.

The present invention is an aqueous dispersion of hexabromocyclododecane,
General formula (In the formula, R is an optionally halogenated alkyl group having 2 to 3 carbon atoms, R ¹ is an alkylene group having 2 to 3 carbon atoms, a group-
OR ² —, —OR ² O— or —OR ² OR ² O— is shown, wherein R ² means an alkylene group having 2 to 3 carbon atoms, and the alkylene groups of R ¹ and R ² are halogenated. Alternatively, X represents a linear bond or an oxygen atom, n is an integer of 0 to 20 when X is a direct bond, and n is an integer of 1 to 20 when X is an oxygen atom). An aqueous dispersion of a phosphorus compound is mixed with 100 parts by weight of hexabromocyclododecane in an amount of 1 to 50 parts by weight as a phosphorus compound. It is a disaster prevention processing method by an exhaust method or a thermosol method of a polyester fiber product having an excellent texture, which is characterized by adhering 10%.

Hexabromocyclododecane used in the present invention,
It means 1,2,5,6,9,10-hexabromocyclododecane, and it is preferable that the average particle size is 20 μm or less.

Examples of the phosphorus compound of the formula I used in the present invention include a phosphoric acid ester oligomer, a halogenated phosphoric acid ester oligomer, a phosphonic acid ester, a phosphonic acid ester oligomer, a halogenated phosphonic acid ester, and a halogenated phosphonic acid ester oligomer.

Examples of phosphorus compounds of formula I are shown below. N in the formula has the above-mentioned meaning.

In practicing the present invention, an aqueous dispersion of hexabromocyclododecane and the phosphorus compound of formula I is prepared separately.

To prepare an aqueous dispersion of hexabromocyclododecane, 10 to 60 parts by weight of hexabromocyclododecane, preferably 30 to 50 parts by weight, 0.1 to 10 parts by weight of a surfactant and 0.1 to 10 parts of a protective colloid agent are used. It is preferable to use 5 parts by weight and disperse in water to obtain 100 parts by weight. As the surface active agent, a nonionic surface active agent such as a hydrocarbon-substituted phenol ethylene oxide adduct, or an anionic surface active agent such as a hydrophobic organic compound sulfonate is used. As the protective colloid agent, for example, polyvinyl alcohol, sodium alginate, hydroxymethyl cellulose, carboxymethyl cellulose, sodium polyacrylate, starch and the like are used.

To prepare an aqueous dispersion of a phosphorus compound of formula I, phosphorus compound 1
It is preferable to disperse 0 to 60 parts by weight, preferably 30 to 50 parts by weight, in water using 1 to 20 parts by weight of a surfactant to obtain a total amount of 100 parts by weight. The above compounds are used as the surfactant.

Then, an aqueous dispersion of hexabromocyclododecane and an aqueous dispersion of the phosphorus compound of formula I are mixed to prepare a working fluid. The proportion of hexabromocyclododecane and phosphorus compound of formula I in the working liquid is 100: 1 to 50 by weight. If the proportion of the phosphorus compound is lower than this, the stability of the working liquid is reduced, the flameproof effect varies, and the texture of the processed product becomes hard. If the proportion of the phosphorus compound is higher than this, the processed product will have a slimy feel. The concentration of hexabromocyclododecane in the working fluid is 0.1
2.0% by weight is preferred.

Then, the polyester fiber is processed by using this processing liquid, and the solid content of the processing liquid is 0.3 to 10% with respect to the fiber product.
Attach it. If the solid content is less than 0.3%, the flameproof effect is not sufficient. Even if the amount of adhesion is more than 10%, the flameproof effect is not particularly improved, and the texture may be impaired.

Since this processing liquid is a water dispersion type, it is easy to handle, and for example, during dipping processing, the concentration of the processing liquid can be easily controlled according to the liquid adsorption amount of the textile product or the drawing pressure of the machine.
Further, if necessary, it can be used in combination with a fiber processing aid such as a dye, a softening agent, a water repellent, an antistatic agent, or a flameproofing aid such as an antimony compound, and can be processed with excellent workability in a wide range.

According to the method of the present invention, hexabromocyclododecane having a relatively large average particle size can be used, and an ordinary surfactant and protective colloid agent can be used as the water dispersant. The processing liquid used in the present invention is excellent in compatibility with dyes during dyeing in the same bath during dyeing, and stability against sedimentation and terring. Therefore, according to the method of the present invention, dyeing unevenness, there is no unevenness of adhesion of the flameproofing agent, the texture is soft and light resistance,
A processed product having excellent heat resistance and stable flame resistance can be obtained. Further, even if a fiber resin such as a softening agent, a water repellent, or an antistatic agent is added to the processing liquid, flameproofness, feeling, etc. do not deteriorate. For example, when a polyester curtain cloth for interior interior material is processed, a processed product having no dyeing unevenness, drapeability, good texture and excellent durability can be obtained. In addition, polyester fibers used for clothing, bedding and the like can be flameproofed without impairing the texture, gloss, brilliance of dyeing, and texture. Furthermore, the polyester fiber used for automobile interior materials can be flameproofed without impairing the surface quality.

Example 1 An aqueous dispersion of 1,2,5,6,9,10-hexabromocyclododecane (hereinafter referred to as HBCD) having an average particle size of 5 μm (containing 40% as HBCD) and an aqueous dispersion of a phosphorus compound of the formula I. Working liquids 1 and 2 shown in Table 1 were prepared using the liquid (containing 40% as a phosphorus compound). As the phosphorus compound, a chlorinated phosphonate compound (Compound 8, n≈5) was used.

Polyester drape curtain cloth (300 g / weight)
m ² ) was processed using a high temperature high pressure dyeing machine. The treatment conditions were a bath ratio of 1:15, a temperature increase of 2 ° C./min, and a temperature of 130 ° C. for 40 minutes. After the treatment, a solution containing a nonionic surfactant, caustic soda and hydrosulfite at 1 g / each was reduced and washed at 80 ° C. for 10 minutes, washed with water and dried.
The amount of the working fluid deposited as solid content is 3.
It was 0%. The flame resistance and physical properties of the obtained processed product were tested by the following methods. The results are shown in Table 2. The working fluid 1 showed some settling, but the working fluid 2 was stable.

Test method: The flameproof test was carried out by a 1-minute heating and 3-second heating test by the 45 degree micro-burner method of the Fire Defense Law curtain test and a 45 degree coil method. For light resistance, use a fade meter,
The samples were examined by exposing them to UV light at 63 ° C. for 40 hours. Friction fastness is 200g, 100 times /
Dry friction and wet rubbing were carried out under the condition of minutes for examination. The moisture absorption rate was measured after leaving the sample cloth under conditions of a temperature of 20 ° C. and a relative humidity of 90% for 48 hours. For rusting property, after washing with hydrochloric acid, thoroughly washing with water, twelve dried lionworm pins were stabbed with a test cloth, and the number of rusting after standing at 20 ° C. for 48 hours in a saturated saline desiccator was examined. The uneven dyeing was judged by visual observation, and the feeling was judged by the feel of the hand. In the table, In is the initial product, HL is the product after 5 times of washing with water, and DC is the product after 5 times of dry cleaning.

Example 2 Using the aqueous dispersion of HBCD (containing 40% as HBCD) and the aqueous dispersion of chlorinated phosphonate compound (compound 5) (containing 40% as compound 15) having an average particle diameter of 15 μm, the processing liquid of Table 3 was used. Was prepared. Polyester lace curtain cloth (100 g / m ^{2 in} basis weight) was immersed in the processing liquid at a bath ratio of 1:10, and processed in the same manner as in Example 1. The deposition amount of the working liquid was 3.5% as a solid content with respect to the fiber weight. The flameproofness and physical properties of the processed product were tested in the same manner as in Example 1. The results are shown in Table 4. Although the working fluid 1 showed sedimentation, the working fluids 2 and 3 were stable.

Example 3 10 parts by weight of an aqueous dispersion of HBCD having an average particle diameter of 3 μm (containing 40% as HBCD), 1 part by weight of a fluorine-based water repellent (Asahi Guard AG-730 manufactured by Asahi Glass Co., Ltd.), a trimethylolmelamine resin (Sumitomo Chemical Sumitex resin M manufactured by Kogyo Co., Ltd.
-3) Working fluid 1 (comparative example) was prepared by mixing 0.5 parts by weight and 88.5 parts by weight of water. Further, 8 parts by weight of the above HBCD aqueous dispersion and an aqueous dispersion of a chlorinated phosphonate compound (Compound 8, n≈3) (40% content as Compound 8)
Working fluid 2 was prepared in the same manner as working fluid 1 except that 2 parts by weight was used.

Polyester knit car seat cloth (weight per unit area 250g / m ² )
Processing fluids 1 and 2 are used for the thermosol method to produce 1d
It was processed under the conditions of wet pick up 70% with ip-1nip. Then heat treat at 190 ℃ for 2 minutes,
Wash with anhydrous sodium carbonate 5g / solution at 80 ° C for 5 minutes,
It was washed with water and dried. The amount of the processing liquid deposited was 2.0% based on the fiber weight as a solid content. The flame resistance of the processed product was tested by the FMVSS-302 method, the light resistance was tested by a fade meter at 83 ° C. for 200 hours, and other physical properties were tested in the same manner as in Example 1. The results are shown in Table 5. It should be noted that sedimentation was observed in the processing liquid 1, but the effective liquid 2
Was stable.

 ─────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor Toyohisa Takenaka 2-17-19 Tenjinyama-cho, Kishiwada City, Osaka Prefecture (56) References JP-A-60-259674 (JP, A) JP-A-59-15572 (JP) , A) JP 60-21973 (JP, A) JP 61-119776 (JP, A)

Claims (1)

[Claims] 1. An aqueous dispersion of hexabromocyclododecane and a general formula (In the formula, R is an optionally halogenated alkyl group having 2 to 3 carbon atoms, R ¹ is an alkylene group having 2 to 3 carbon atoms, a group-
OR ² —, —OR ² O— or —OR ² OR ² O— is shown, wherein R ² means an alkylene group having 2 to 3 carbon atoms, and the alkylene groups of R ¹ and R ² are halogenated. And X represents a direct bond or an oxygen atom, n is an integer of 0 to 20 when X is a direct bond, and n is an integer of 1 to 20 when X is an oxygen atom). An aqueous dispersion of a phosphorus compound is mixed with 100 parts by weight of hexabromocyclododecane in an amount of 1 to 50 parts by weight as a phosphorus compound. A flame-proofing method by an exhaust method or a thermosol method for a polyester fiber product having an excellent texture, which is characterized by 10% adhesion.