JPH0242944B2 - - Google Patents

Description

[Detailed description of the invention]

INDUSTRIAL APPLICATION FIELD The present invention relates to a processing agent for synthetic fiber products, particularly a processing agent suitable for flame retardant processing of polyester or polyamide fiber products, and a processing method using the same. Conventional technology Flame retardants for synthetic fiber products include 1, 2,
5,6,9,10-hexabromocyclododecane and tris(1,3-dichloropropyl) phosphate are commonly used, but although they provide wash resistance or flame retardancy, they have poor color fastness. There were problems such as a decrease in In particular, aliphatic bromine-based flame retardants such as the former tend to cause problems in the sunlight fastness of processed products, while phosphoric ester-based flame retardants such as the latter cause oiliness and bleed to the processed products. The problem was that the dyeing color fastness to rubbing was significantly reduced. Furthermore, when using these products, there was a risk of adhesion of dregs and tar to the processed cloth and contamination of the housing. OBJECTS OF THE INVENTION An object of the present invention is to provide a processing agent and a processing method that impart flame retardancy with good texture and good performance to synthetic fibers without adversely affecting color fastness. Structure of the Invention The present invention provides (a) an orthophosphoric triester of pentaerythritol in which three hydroxyl groups of the four hydroxymethyl groups are substituted with chlorine or bromine, that is, an orthophosphoric triester of the general formula This objective was achieved by using an orthophosphoric triester which is solid at room temperature and has the following properties: (where X represents chlorine or bromine). The processing agent of the present invention contains at least one of the above (a) orthophosphoric acid triester and (b) a dispersant and a protective colloid agent. Note that the processing agent of the present invention may contain water. Typical examples of the component (a) above include di(tribromoneopentyl)trichloroneopentyl phosphate, tris(dibromochloroneopentyl) phosphate, tris(tribromoneopentyl) phosphate, etc. Preference is given to using (tribromoneopentyl)phosphate. Next, as the component (b) above, for example, dispersants and protective colloid agents commonly used in the textile processing and dyeing industries can be used, and typical examples include ethylene oxide of aliphatic alcohols, fatty acids, or aliphatic amines. Dispersants such as adducts, ethylene oxide adducts of phenols and their sulfonates, aromatic sulfonic acids and their formaldehyde condensates, phosphoric acid di- or triesters of ethylene oxide adducts of alkylphenols, or polyvinyl alcohol, polyvinylpyrrolidone, polyvinyl pyrrolidone, etc. Protective colloid agents include water-soluble vinyl polymers such as acrylic acid and water-soluble modified celluloses such as carboxymethyl cellulose and hydroxyethyl cellulose. The processing agent according to the invention is normally used as an aqueous processing agent. The aqueous treatment agent is, for example, component 5 to (a)
75% by weight, preferably 20-60% by weight (particularly preferably 30-50% by weight) and 1-25% by weight of component (B) (with the exception of 0-25% by weight of dispersant and 0-25% by weight of protective colloid).
5% by weight, preferably 3 to 15% by weight of the dispersant and 0 to 2% by weight of the protective colloid agent) are charged into a glass ball crusher, sand crusher, steel ball crusher, etc. together with the remaining water to form an aqueous dispersion. It is manufactured by forming. In addition, the protective colloid agent may be added after pulverization, and the component (a) may have a particle size reduced by pulverization.
The thickness is preferably 0.5 to 20 μm, preferably 0.5 to 10 μm. Particularly good dispersions are obtained with particle sizes of 0.5 to 5 μm. The present invention also provides a method for flame retardant processing of synthetic fiber products, particularly polyester (including cationically dyeable polyester) or polyamide fiber products, using such an aqueous treatment agent. This method can be achieved by diluting the above-mentioned aqueous treatment agent with water to obtain a processing liquid, applying it to the synthetic fiber product by dipping treatment or the like, drying it, and then subjecting it to a heat treatment. The amount of component (a) attached to synthetic fiber products is
It is preferable to process the synthetic fiber product so that the dry weight becomes 0.5 to 8% by weight. After the processing liquid is applied, the drying temperature of the synthetic fiber product is preferably 120°C or less, for example, 80 to 120°C, and the heat treatment temperature is Preferably the temperature is 170-220°C. Generally, for polyester textile products, the heat treatment temperature is preferably 175-220°C, especially 190-210°C, and for polyamide textile products, 170-190°C,
In particular, the temperature is preferably 175 to 180°C. In addition, the heat treatment time is usually about 10 to 180 seconds, and generally 20 to 180 seconds.
~90 seconds is preferable. In the case of polyester fiber products, effective processing is also possible by exhausting the aqueous composition containing the processing agent of the present invention under heating. For example, in a high-pressure dyeing machine, using a processing liquid with a bath ratio of 1:5 to 1:50 (preferably 1:8 to 1:20),
The treatment may be carried out at 140°C (preferably 130 to 135°C) for 20 to 60 minutes, and the treatment may be carried out in the same bath as the disperse dye or fluorescent dye. The polyester and polyamide fiber products that can be flame-retardant according to the present invention may be filament or staple cotton, yarn, tow, woven fabric, knitted fabric, non-woven fabric, etc., and may be dyed. In the present invention, polyester means polyethylene terephthalate-based polyester, and polyamide means 6-nylon or 6,6-nylon. Polyester and polyamide fiber products treated with the finishing agent of the present invention exhibit excellent flame retardancy that is durable even after multiple home washings and dry cleanings. There are no oily feel, bleed, or low dye fastness to rub that is often seen when dyeing, or low sunlight fastness that is often seen when using aliphatic bromine flame retardants. Example of manufacturing a dispersion containing a flame retardant (A) 400 g of tris (tribromoneopentyl) phosphate, 1 mol of lauryl alcohol and 13
40 g of a molar ethylene oxide (hereinafter referred to as EO) adduct and 500 g of water were ground in a steel ball grinder until the average particle size was 5 μm or less. Thereafter, 60 g of a 5% aqueous solution of polyvinyl alcohol was added and mixed well. The resulting dispersion is stable for a long time and can be diluted as desired. (B) 360 g of tris(tribromoneopentyl) phosphate, 58 g of a formaldehyde condensate of naphthalene sulfonic acid, 2 g of sodium carboxymethyl cellulose, and 580 g of water were ground in a steel ball grinder until the average particle size was 5 μm or less. The resulting dispersion flows easily and can be diluted as desired. (C) 300 g of tris(tribromoneopentyl) phosphate, 1 mole of styrenated phenol and
40 g of a 20 mole EO adduct and 660 g of water were ground in a glass ball grinder until the average particle size was 3 μm or less. The resulting dispersion can be diluted and will form a precipitate if left to stand for a long time, but can be reconstituted by simple stirring. (D) 360 g of tris(tribromoneopentyl) phosphate, 30 g of the diethanolamine salt of a phosphoric diester of an alcohol prepared by adding 4 moles of EO to 1 mole of nonylphenol, 35 g of a formaldehyde condensate of naphthalene sulfonic acid, and water.
475g was crushed into a glass ball with an average particle size of 2μ.
It was pulverized until it was less than m. After pulverization, 100 g of a 5% aqueous solution of hydroxyethyl cellulose was added and mixed. The resulting dispersion is stable for a long time and can be diluted as desired. (E) A dispersion was obtained in the same manner as in (B) above, except that 360 g of tris (dibromochloroneopentyl) phosphate was used instead of 360 g of tris (tribromoneopentyl) phosphate. The resulting dispersion flows easily and can be diluted as desired. (F) 250 g of di(tribromoneopentyl)trichloroneopentyl phosphate, 50 g of sulfate ester sodium salt of 20 mole EO adduct of styrenated phenol, and 700 g of water were ground in a porcelain bead (diameter 6 mm) mill to reduce the average particle size. The powder was crushed until it became 5 μm or less. The resulting dispersion can be diluted and will form a precipitate if left for a long time, but
It can be restored with a simple stirring. (G) 360 g of tris (tribromoneopentyl) phosphate, 40 g of an adduct of styrenated phenol and 20 moles of EO, 50 g of sulfuric acid ester sodium salt of an adduct of styrenated phenol and 20 mole of EO, and 450 g of water were crushed in a steel ball mill to reduce the average particle size. The powder was crushed until it became 5 μm or less. After grinding, acrylic acid/
100 g of a 5% aqueous solution of sodium salt of maleic acid copolymer was added and mixed. The resulting dispersion is stable over a dilution period and can be diluted as desired. (H) 1,2,5,6,9,10 instead of 360g of tris(tribromoneopentyl)phosphate
- A dispersion was produced in the same manner as in Production Example (D) except that 360 g of hexabromocyclododecane was used (known flame retardant). (I) 360 g of tris(1,3-dichloropropyl) phosphate, 40 g of 20 mole EO adduct of styrenated phenol and
Sulfate ester sodium salt of EO20 mole adduct
50 g were mixed and emulsified in a homomixer while adding 550 g of water to obtain an emulsion with an average particle size of 0.5 μm (known flame retardant). Examples 1 to 5 and Comparative Examples 1 to 4 The dispersions obtained in Production Examples A, C, D, and E (processing agents of the present invention) and the dispersions obtained in Production Examples H and I (known processing agents) were were used to prepare the aqueous processing fluids shown in Table 1, and these were used to prepare polyester fabrics (220
g/m ² ) was thermosol processed. The polyester fabric was padded with the above aqueous processing solution, dried at about 110°C for 5 minutes, and then heat treated under the conditions shown in Table 1. After that, 2 g of soda ash and 10 moles of EO adduct of nonylphenol were added in 1000 ml.
Washed with an aqueous solution containing 0.5 g for 5 minutes, rinsed with running water, and dried. The physical properties of the obtained product were measured by the following method.
The results are shown in Table 1. Amount of chemical adhered Approx.
50g of fabric was dried at 105°C for 1 hour, and the weight increase at each stage is expressed as a percentage based on the weight accurately weighed to two decimal places. Flame retardant adhesion efficiency The weight increase after soaping and drying with respect to the theoretical adhesion amount of flame retardant is shown in % by weight. Flame retardant initial and Fire and Disaster Management Agency Notification No. 1 dated February 21, 1985
After washing and dry cleaning five times each, the product was subjected to a flame retardant test using the 45° coil method (JIS L-1091 D method). Hunter whiteness Digital colorimeter according to JIS P-8123
Measured using ND-101D (manufactured by Nippon Denshoku Kogyo Co., Ltd.). Light resistance: The film was exposed to light for 100 hours using a carbon arc lamp fade-o-meter model FAL-3H (manufactured by Suga Testimonials) at a black panel temperature of 83°C, and evaluated using a gray scale for discoloration. As is clear from the results in Table 1, the processing agent according to the present invention not only provides excellent flame retardancy to polyester fabrics, but also has good whiteness, texture, and light resistance.

[Table] Examples 6 to 9 and Comparative Examples 5 to 9 Dispersions obtained in Production Examples C and G (processing agent of the present invention)
and dispersions obtained in Production Examples H and I (known processing agents)
A flame retardant single exhaustion treatment and a dye bath exhaustion treatment were carried out on a 265 g/m ² polyester fabric using the following under the conditions shown in Table 2. Note that a blank test without using flame retardant was also conducted at the same time. Mini color 12 using the treatment bath (1000ml) listed in Table 2
Using a dyeing tester (pot capacity 1800ml), raise the temperature from 50℃ to 130℃ at a heating rate of 2℃/min, and then
Keep it for 30 minutes. After observing the residual bath, drain it and add 2 g of sodium hydrosulfite and 2 g of soda ash per 1000 ml of fabric.
g and 0.5 g of EO10 mole adduct of nonylphenol
was washed for 5 minutes in a solution at 80°C, rinsed with running water, and dried. Sumikalon UL Blue GF (manufactured by Sumitomo Chemical Industries, Ltd.) was used as the dye, and Disper N-700 (manufactured by Meisei Chemical Industries, Ltd.) was used as the dispersion and leveling agent. The physical properties of the product are shown in Table 2, but the chemical adhesion rate was determined by drying 20g of fabric at 105°C for 1 hour with the periphery melted and cut to prevent fraying. The weight increase is shown in % based on the weight accurately weighed to the nearest digit. In addition, the flame retardant adhesion efficiency was determined only when the flame retardant was exhausted alone.
The weight increase after reduction cleaning and drying was expressed in % with respect to the theoretical weight of the flame retardant in the dispersion added to the bath. Flame retardancy and light resistance were measured in the same manner as in Example 1. Color fastness to rubbing was measured using a Gakushin type rubbing fastness tester (JIS L-0849 method). As is clear from the results in Table 2, according to the processing agent of the present invention, extremely excellent flame retardance can be obtained, and the stability of the dispersion in a high-temperature exhaust bath is good, so that the agent can be efficiently absorbed. It has the advantage that there is less risk of adhesion of scum and tar to processed fabrics and contamination of the housing, which are common with conventional processing agents.

[Table] Examples 10 to 11 Using the dispersion obtained in Production Example G, 150 g/m ² of 6-nylon fabric and 180 g/m ² of 6,6-nylon fabric were prepared in the same manner as in Example 1. Thermosol treated. The processing conditions are shown in Table 3. All physical property tests were conducted in the same manner as in Example 1. The test results are shown in Table 3. As is clear from these results, the processing agent of the present invention can impart sufficient flame retardancy even to nylon fabrics, and exhibits good results in terms of whiteness, texture, and light resistance.

[Table] Effects of the Invention The processing agent of the present invention can be used with good workability without worrying about tar adhesion to processed cloth or contamination of the casing. It is possible to impart good hand feel, wash resistance, and excellent flame retardancy without adversely affecting color fastness.

Claims (1)

[Claims] 1 (a) General formula (wherein, X represents chlorine or bromine); and (b) at least one of a dispersant and a protective colloid agent. 2. An aqueous composition containing the processing agent according to claim 1,
A flame retardant processing method for synthetic fiber products, which is characterized by attaching the product to the synthetic fiber product, drying it, and then heat-treating it at 170 to 220°C. 3. A method for flame-retardant processing of polyester fiber products, which comprises exhausting the aqueous composition containing the processing agent according to claim 1 to the polyester fiber products at 110 to 140°C.