JPH0127193B2 - - Google Patents

Description

[Detailed description of the invention]

[Industrial Field of Application] The present invention relates to a method for treating fibrous materials. More specifically, the present invention relates to a treatment method for imparting a durable flame retardant finish to cellulosic fibers or mixtures of cellulosic fibers and other fibers. [Prior Art] Conventionally, the following methods have been known as methods for imparting durable flame retardancy to fiber materials.
For 100% cellulose fiber, the Proban method (Albright
& Willson), N-hydroxymethyl-3dimethylphosphonopropionamide (Pyrovatex)
CP, CIBA-GEIGY product) and methylol melamine compound in the presence of a catalyst.
Stauffer Chemical Co.) and N-methylolacrylamide are polymerized in the presence of a catalyst. In addition, for polyester fibers, there is a method in which an aqueous dispersion of hexabromocyclododecane is used to diffuse it into the fiber by an exhaustion method in a bath or a thermosol method, or a dispersion of tris-dichloropropyl phosphate is used in a bath. A method of fixing by an exhaustion method or a thermosol method, and a method of fixing an aqueous solution of a phosphorus-containing cyclic compound by a thermosol method are known. [Problem to be solved by the invention] However, although these flameproofing methods are effective for fibers made of a single composition of cellulose or polyester, they are not effective for mixed products of polyester fibers and cellulose fibers. is not effective, especially when the blending ratio of polyester and cellulose is
For materials with a ratio of 70:30 to 30:70, it is difficult to obtain practical flame-retardant products, including flame retardance, texture, and physical properties. For example, a method of flameproofing a mixed product of polyester fiber and cotton using a combination of hexabromocyclododecane, antimony trioxide, and acrylic latex is known, but the texture of the processed product is It is hard and has disadvantages such as the dyed material's hue becoming white. Furthermore, a method has been proposed in which fibers are impregnated with a composition consisting of methylolmelamine and urea in a condensate of tetrakis hydroxymethylphosphonium salt and ammonia (THPN), and then heat cured after drying. (American Dyestuff Reporter 74, No. 1,
35-40 (1985)). Although the flame retardant properties of the treated products obtained by this method are relatively excellent, they have drawbacks such as not being able to withstand 50 washes for clothing and having a significantly hardened texture. The reason why it is difficult to apply durable flame retardant treatment to mixed products of polyester fibers and cellulose fibers is that cellulose achieves flame retardant properties by promoting carbonization, whereas polyester achieves its flame retardant properties by promoting melting. This is said to be because the presence of cellulose prevents polyester from melting and falling off due to differences in combustion behavior, which inhibits self-extinguishing properties. [Means for Solving the Problems] The present invention provides a fiber material containing (1) a tetrakishydroxymethylphosphonium compound or a condensate of a tetrakishydroxymethylphosphonium compound and ammonia, (2) methylolmelamine, and (3) urea. This treatment method is characterized by impregnating a treatment agent consisting of three components, thiourea or guanidine salt, and heating with a high-pressure steamer or heating with a microwave in the presence of water vapor. By treating with the method of the present invention, it is possible to impart flame retardancy to mixed products of polyester fibers and cellulose fibers, which was previously impossible, and the effect is durable enough for practical use. It is also extremely superior in terms of texture. In the present invention, the mixed product of polyester fiber and cellulose fiber is one in which the cellulose fiber is cotton, rayon, linen, etc., and the mixing ratio is 100% or more.
20%. Mixing refers to mixed spinning, mixed weaving, mixed twisting, mixed knitting, etc., and the properties thereof may be thread-like, cotton-like, fabric, woven fabric, knitted fabric, non-woven fabric, etc. These mixed products are subjected to a flame retardant treatment after undergoing a scouring and bleaching process, or after being further dyed with threne dyes. The (1) tetrakishydroxymethylammonium compound of the treatment agent used in the present invention is represented by the following general formula. (HOCH ₂ ) _{4 P} ⁺ X ^- [In the above formula, The product (THPN) is represented by the structural formula below. [In the above formula, X represents Cl, 1/2SO ₄ or OH] Commercially available THPS and THPC with a solid content of about 80% can be used. THPN can be easily obtained by reacting these with 1/2.5 mol of ammonia. (2) As the methylolmelamine, hexamethylolmelamine, trimethylolmelamine, etc. are used. The specific product name is Sumitomo Chemical Co., Ltd.
Examples include Sumitex Resin M-6, M-3, MC, and the like. As catalysts for methylolmelamine, organic acids such as malic acid and tartaric acid, salts of inorganic acids such as sulfuric acid, persulfuric acid, and nitric acid, and strong acid salts of organic amines are used. (3) As urea or thiourea, commercially available industrial powder products can be used as they are. Also,
As the guanidine salt, guanidine hydrochloride, guanidine phosphate, etc. can be used, and these can be obtained as industrial chemicals. (1), (2) and (3) can usually be applied to textile materials in the form of an aqueous solution. (1) is 20-80%, (2) is 2-30%,
(3) is used in a concentration range of 2-30%. As a method for applying it to the fibrous material, a pad mangle drawing method is generally used, but a spray method, a kiss roll method, a foaming method, etc. may also be used. The treatment according to the invention is characterized by microwave irradiation in the presence of water. An example of a device that can be used for this purpose is the electronic reactor Apollotex manufactured by Ichikin Kogyo Co., Ltd. Compared to the normal dry heat curing method, there is less migration of the flame retardant treatment agent, and by uniformly heating from deep inside the fiber material, the distribution is uniform across the cross section of the fiber material, and it is highly cross-linked. The result of forming a polymer is a flame retardant product that is much more resistant to washing. Microwave irradiation is from 0.2 to 2450MHz frequency.
At a power of 20kW, preferably between 2 and 10kW,
It is carried out for 10 seconds to 60 minutes, preferably 10 minutes to 30 minutes. During this time, it is carried out in the presence of water vapor with a direct vapor pressure of 0.1 to 3 Kg/cm ² . Without water vapor, uniform irradiation with microwaves is not performed, and the treatment agent tends to migrate to the surface of the fiber material. Alternatively, the treatment of the present invention is carried out by heating with a high pressure steamer. This treatment uses saturated steam at a rate of 0.1-3Kg/cm ² , preferably 0.5-3Kg/cm 2 .
Under pressure of 2.5Kg/ ^cm2 , preferably for 10-120 minutes
It is best to do it for 30 to 90 minutes. Next, a soaping process is performed to remove unfixed processing agent. This treatment is preferably carried out for 5 to 30 minutes in hot water or soda ash aqueous solution at 80 to 100°C. As a device for soaping, a jet dyeing machine is excellent in terms of the kneading effect, but a wince or other commonly used devices may be used, and the type thereof is not particularly limited. The adhesion rate of flame retardant to the fiber material after soaping and drying is 5 to 45% by weight, preferably 10 to 30% by weight.
A weight percent range is desirable. The fibrous material thus obtained has much better flame retardancy than those made by the prior art, and also has significantly better resistance to washing and dry cleaning. It also has the characteristics of little hand hardening and little decrease in tear strength. Such processing effects are obtained because the flame retardant consisting of three components is highly crosslinked by microwave irradiation and is evenly distributed over the fiber material. [Example] The physical property evaluation method and Examples will be described below. Washing method: Use 1g of powdered laundry soap (JIS K3303 Class 1) per 1 ounce of water, supply 60℃ water, add detergent, add the test specimen, and then wash with 60℃ liquid for 15 minutes. . Next, drain water, supply water, rinse 3 times for 5 minutes with water at 40°C, and drain and dehydrate for 2 minutes.
Washed twice. Dry cleaning method The dry cleaning method specified in Fire and Disaster Management Agency Notification No. 1 (1988) was used. However, before dry cleaning, the sample should be treated with hot water (40℃ x 30℃).
minutes) and then dry as usual. Flame retardant performance test method 1 Vertical methane burner method (clothing test method) Dimensions of test specimens: 89 mm x 254 mm each Number of test specimens: 5 Conditioning of test specimens: After drying in a constant temperature dryer at 50 ± 2 ° C for 24 hours, 2 in a desiccator containing silica gel
Dry for more than an hour. B. Measure the length of the flame upward from the highest point of the burner, adjust it to 38mm, and check that the flame is stable. Move the burner and apply indirect flame to the test specimen for 3.0±0.2 seconds. After removing the burner flame from the test specimen, check the combustion condition and flame droplet ignitability on the test specimen support frame. (b) The average carbonization length for the five fabric test specimens is
178mm or less, and the maximum carbonization length must be less than 254mm. No flame drop ignitability. 2 45° mecenamine method (bedding test method) Dimensions of test specimen: 35 cm x 25 cm Number of test specimens: 3 Conditioning of test specimen: 24 in a constant temperature dryer at 50 ± 2 ° C
After drying for an hour, dry in a desiccator containing silica gel for at least 2 hours. B. Stack the test specimen on the wire mesh of the test specimen support frame, secure it to the specimen support frame without loosening, and place Mecenamine (Ellie Lilly Product No.
1588 (trade name: mecenamine)) in a way that it will not be easily moved. (b) Ignition is performed using a matchstick, and after ignition, the glass window of the combustion test box is immediately closed and left until combustion is complete. C. The carbonization length shall be the maximum longitudinal length of the carbonized portion of the test specimen, and the maximum length for the three test specimens shall be 70 mm or less and the average value shall be 50 mm or less. Example 1 and Comparative Example 1 Fabric weight of polyester/cotton (65/35) blend
200 g of plain woven fabric was impregnated with an aqueous solution containing a drug having the following composition. THPS (solid content 80%) 30% Sumitex Resin M-6 9% Ammonium persulfate 1% Urea 7% Next, the impregnation rate was reduced to 75% using a mangle. This was reacted using an electronic reactor Apollotex under the following conditions. Microwave output: 7.0 kW Reaction time: 30 minutes Direct steam: 0.7 Kg/cm ² Winding speed: 10 m/min Thereafter, it was washed in hot water at 80°C for 20 minutes in a jet dyeing machine and dried. For comparison, a fabric impregnated with flame retardant was heated to 120℃.
The sample was dried using a tenter, cured for 2 minutes at 180°C, and dried after soaping (Comparative Example 1). The flame retardant adhesion rate and flame retardant evaluation results are shown in Table 1.

[Table] In the inventive example, the adhering flame retardant does not come off much when washed and has sufficient flame retardancy even after 50 washes, whereas the comparative example has initial flame retardancy, but does not come off when washed. I know I can't stand it. Example 2 and Comparative Example 2 For a plain woven fabric with a basis weight of 100 g made of 100% cotton,
A drug having the following composition was impregnated as an aqueous solution. THPS (solid content 80%) 40% Sumitex Resin M-6 12% Diammonium phosphate 1% Urea 10% The impregnation rate was reduced to 100% using a mangle, and the mixture was reacted using Apollotex under the following conditions. Microwave output 7.0kW Reaction time 30 minutes Direct steam 0.7Kg/cm ² Winding speed 10m/min Next, wash in hot water at 80℃ for 30 minutes in a jet dyeing machine.
Dry. For comparison, a fabric impregnated with flame retardant was prepared at 120
Pre-dry at 180 °C using a loop dryer.
Heat treatment was performed at ℃ for 3 minutes. Then, it was soaped and dried (Comparative Example 2). The flame retardant adhesion rate and flame retardant evaluation results are shown in Table 2.

[Table] In the examples of the present invention, the adhered flame retardant hardly comes off when washed, and shows durable flame retardant properties.
Although the comparative example has sufficient initial flame retardancy, it easily falls off when washed and lacks durability. Example 3 A twill fabric made of a polyester/rayon (50/50) blend and having a basis weight of 150 g was impregnated with a chemical having the following composition as an aqueous solution. THPN (solid content 80%) 35% Sumitex Resin M-6 10% Diammonium phosphate 1% Urea 12% The impregnation rate was reduced to 80% using a mangle, and reaction was carried out using Apollotex under the following conditions. Microwave output: 5 kW Reaction time: 40 minutes Direct steam: 0.5 Kg/cm ² Winding speed: 8 m/min Thereafter, using a jet dyeing machine, it was washed with hot water at 90°C for 40 minutes and dried. The flame retardant adhesion rate of this fabric was 20%. The flame retardant evaluation results are shown in Table 3.

[Table] The treated product has excellent flame retardant properties and has sufficient durability for practical use in sheets and clothing. Example 4 Made of polyester/cotton (65/35), fabric weight 250
The twill fabric of g was refined and bleached in a conventional manner, immersed in the following dye bath, and then squeezed with a mangle to an impregnation rate of 80%. Dye bath Resolin Blue FBL ^*1 2.5g/ Mikethren Blue GCD ^*2 5.5g/ Sodium alginate 1.0g/ *1 Disperse dye manufactured by Bayer *2 Thren dye manufactured by Mitsui Chemicals, Inc. After drying at 120°C for 5 minutes, dry at 200°C Heat set for 1 minute. After immersion in the treatment bath described below, the impregnation rate was reduced to 80% using a mangle, steamed for 1 minute in saturated steam, and then oxidized for 1 minute at room temperature in a treatment bath containing 10 g/35% hydrogen peroxide. Finally, soap in the following soaping bath at 100℃ for 5 minutes,
Dry at °C. Treatment bath Hydrosulfite 60g / Caustic soda 60g / Sodium sulfate 40g / Soaping bath Marcel soap 2g / Nonionic penetrant 2g / Sodium carbonate 1g / The dyed fabric thus obtained was placed in the following flame retardant bath. Soaked. THPN (solid content 80%) 35% Sumitex Resin M-6 12% Tartaric acid 0.5% Thiourea 9% Then, the impregnation rate was reduced to 80% using a mangle. This product was reacted using Apollotex under the following conditions. Microwave output 6.0kW Reaction time 40 minutes Direct steam 0.7Kg/cm ² Winding speed 8m/min 40 minutes at 100℃ in a jet dyeing machine for soaping
Treated for minutes and dried. The amount of flame retardant attached to the fabric was 26%. When the flame retardancy of the treated fabric was evaluated using the vertical methane burner method at the initial stage, after washing 50 times, and after dry cleaning 5 times, the carbonization length was 20 mm, 44 mm, and 23 mm, respectively, which passed the flame retardant standards for clothing. It was hot. Example 5 The dyed polyester/cotton blend fabric used in Example 4 was impregnated with a flame retardant composition having the following composition. THPS (solid content 80%) 35% Sumitex Resin M-6 10% Potassium persulfate 0.5% Guanidine hydrochloride 10% Next, the impregnation rate was reduced to 80% using a mangle. This product was reacted using Apollotex under the following conditions. Microwave output 6.0kW Reaction time 40 minutes Direct steam 0.7Kg/cm ² Winding speed 20m/min Pour into jet dyeing machine for soaping, 5g/cm
of sodium carbonate for 30 minutes, and then washed in hot water at 90°C for 60 minutes. The fabric was dried at 120°C and heat set at 180°C.
The amount of flame retardant attached to the fabric was 22%. When the flame retardancy of the treated fabric was evaluated at the initial stage and after 50 dyeings using the vertical methane burner method, the carbonization length was
They were 38 mm and 69 mm, which passed the flame retardant standards for clothing. Example 6 Mixed woven fabric of 65% polyester/35% cotton (basis weight
100g/m ² ) was subjected to burning, desizing, scouring, bleaching, heat setting and dyeing according to conventional methods,
The following composition was applied. THPS (solid content 80%) 50 parts by weight Urea 10 parts by weight Sumitex Resin M-3 10 parts by weight Ammonium phosphate 1 part by weight Emulgen 909 0.1 part by weight Next, using a high-pressure steamer, the vapor pressure was 1.7.
Kg/cm ² reaction fixation was carried out for 60 minutes, followed by soaping and drying. The amount of flame retardant composition adhered to the fabric was 25%. When the flame retardant properties of the treated fabric were evaluated using the vertical methane burner method at the initial stage, after washing 30 times, and after washing 50 times, the carbonization length was 28 mm, 40 mm, and 45 mm, respectively, which passed the flame retardant standards for clothing. It was hot.

Claims (1)

[Scope of Claims] 1 A fiber material containing (1) a tetrakishydroxymethylphosphonium compound or a condensate of a tetrakishydroxymethylphosphonium compound and ammonia, (2) methylolmelamine, and (3) urea, thiourea or guanidine salt, 1. A method for treating fibrous materials, which comprises impregnating them with a treatment agent consisting of the following: and then heating them with a high-pressure steamer or subjecting them to microwave heat treatment in the presence of water vapor.