JPH04300360A - Antiflaming processing of cellulosic yarn - Google Patents

Abstract

PURPOSE:To provide antiflaming processing of providing cellulosic yarn with excellent antiflaming properties, having washing resistance, drying cleaning resistance and a small amount of residual formalin free from rust of alloy of copper and zinc contained in metal print. CONSTITUTION:Cellulosic yarn is treated with a first solution containing N- methyloldimethylphosphonopropionamide, a triazine ring-containing compound and a catalyst and then with a solution containing a reducing agent. The catalyst contains diammonium phosphate and phosphoric acid in a weight ratio of 1:1.58-4.45. In the operation, the first solution contains 0.60-0.84wt.% diammonium phosphate and 1.33-2.67wt.% phosphoric acid and at least one of sodium bisulfite and sodium sulfite is used as the reducing agent contained in the second solution.

Description

[Detailed description of the invention]

0001

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for flameproofing cellulose fibers with washing resistance and dry cleaning resistance.

0002

[Prior Art] In order to provide flame-retardant clothing, curtains, etc., various methods have been studied for applying flame-retardant treatment to 100% cellulose fibers.
There has been a problem in that it is not possible to obtain a product that has excellent flame retardant properties and also has excellent washing resistance and dry cleaning resistance.

[0003] In order to solve these problems, various flame retardant processing methods have been studied. For example, tetrakis hydroxymethylphosphonium sulfate (THPS)
) or the proban method in which a condensate of tetrakishydroxymethylphosphonium chloride (THPC) and urea is cured with ammonia, and oligo(p-vinyl-p-oxo-1.
3-Dioxa-2-phosphapentylene) (Phylor 76, manufactured by Stauffer Chemical)
and a method for polymerizing N-methylol acrylamide in the presence of a catalyst, N-methylol dimethylphosphonopropionamide (Pyrovatex CP, Ciba-Gyig
y) and a triazine ring-containing compound (for example, methylated hexamethylolmelamine or methylated trimethylolmelamine) in the presence of a catalyst, or a method of heating reaction of phosphorous acid and polyalkylene polyamine dicyandiamide ammonium salt condensate. Methods to do this have been put into practical use.

Among these, the method most commonly used at present is a method in which N-methyloldimethylphosphonopropionamide and methylated hexamethylolmelamine are heated in the presence of a catalyst. This method has the advantage of being more economical and producing brighter colors than the above method.

However, when these agents are used, the texture becomes hard and the amount of residual formalin is as high as 200 to 300 ppm.Especially when the catalyst is an organic amine salt, its use is limited due to flame retardant performance. There is a problem that there are limitations. Further, when the catalyst is ammonium chloride, there is a problem that the alloy of copper and zinc contained in the metal print printed on the fiber rusts. Therefore, there is a demand today to improve the texture of fibers that have been imparted with flame retardant properties, to reduce the amount of residual formalin, and to establish methods for rustproofing metals.

[0006]

[Problems to be Solved by the Invention] The present invention solves the above problems, makes the texture practical without reducing flame retardant performance, reduces the amount of residual formalin, and prevents the metal alloy from rusting. It is an object of the present invention to provide a method for flameproofing cellulose fibers that enables such processing.

[0007]

[Means for Solving the Problems] The method for flameproofing cellulose fibers of the present invention comprises treating cellulose fibers with a first liquid containing N-methyloldimethylphosphonopropionamide, a triazine ring-containing compound, and a catalyst. It is then treated with a second liquid containing a reducing agent, and the catalyst mixes diammonium phosphate and phosphoric acid in a ratio of 1:1.5.
It is characterized in that it is contained in a weight ratio of 8 to 4.45.

[0008] Furthermore, the present invention provides a method in which the content ratios of diammonium phosphate and phosphoric acid in the first liquid are each 0.
．． It is also a method for flameproofing cellulose fibers, characterized in that the reducing agent contained in the second liquid is 60 to 0.84% by weight and 1.33 to 2.67% by weight.
Preferably, it is at least one of sodium bisulfite and sodium sulfite.

In the flameproofing method of the present invention, methylated hexamethylolmelamine, methylated trimethylolmelamine, etc. are suitable as the triazine ring-containing compound contained in the first liquid. If necessary, chemicals such as surfactants, water and oil repellents, water repellents, and softeners may be added. Therefore, by using the first liquid containing such various chemicals, the physical properties of cellulose fibers can be changed in various ways in the present invention.

In the flameproofing method of the present invention, the amount of N-methyloldimethylphosphonopropionamide contained in the first liquid is generally 31 to 44% by weight o.
w. f. and preferably 31 to 37% o. lol
．． f. It is. On the other hand, the amount of methylated hexamethylolmelamine is generally 5 to 7.5% o. w. f. and preferably 5.5 to 6.9% by weight o. w. f. It is. In addition, a modified amino silicone resin may be added to the first liquid, and the amount added in this case is 1.2 to 3.1% by weight. w. f. is preferred.

Cellulose fibers that can be flame-retardant by using the flame-retardant processing method of the present invention include natural cellulose fibers such as cotton and hemp, and semi-synthetic cellulose fibers such as rayon and polynosic. The shape may be thread-like, cotton-like, cloth, knitted fabric, non-woven fabric, etc.
There are no limitations on its use either.

In the present invention, when treating cellulose fibers with the first liquid, the method of soaking, squeezing, and drying is most suitable in that it can be applied continuously and stably. In addition to the treatment methods, methods such as spraying and foam application can be used.

Further, as the heat treatment in the flameproofing method of the present invention, dry heat treatment using a curing box is generally suitable, and heating using far infrared rays or microwaves is also effective. The heating conditions at this time were 150 to 170°C;
for 2 to 5 minutes, preferably 155 to 165°C,
The duration is 2.5 to 3.5 minutes. Note that the interval between drying and heat treatment is preferably as short as possible in order to prevent moisture from being absorbed.

Furthermore, in the present invention, after the above-described heat treatment, hot water washing and water washing are performed to remove unfixed chemicals, but this treatment is generally carried out by hot water washing in an aqueous soda ash solution. After that, wash it with hot water. After the above treatment, the product is washed with water using a second agent containing a reducing agent. At this time, the content of sodium bisulfite or sodium sulfite used as the reducing agent is 1 g/l to 20 g.
/l is suitable, preferably from 5g/l to 10g/l
It is l.

Further, in the present invention, in order to obtain cellulose fibers with vivid colors, it is preferable to pre-treat the cellulose fibers by dyeing or printing with a reactive dye, but in particular, The method is not limited to this method.

By treating cellulose fibers using the flame retardant processing method of the present invention described above, it is possible to suppress the reaction of methylated hexamethylol melamine, which was difficult in the past, and improve the balance between the flame retardant agent and the catalyst. Since it is possible to create a reaction system with good properties, the texture of the resulting product is extremely excellent. Further, the amount of residual formalin can be significantly reduced by a deformalinization reaction during washing with water.

The present invention will be explained in detail below by giving examples of the flameproofing method of the present invention. In addition, Example 1 shown below
- 8 and Comparative Examples 1 to 4, the test methods and evaluation methods for each characteristic are as follows.

a) Washing method Using 1 g of powdered laundry soap (JIS K3303 Class 1) per 1 liter of water, 60°C water was supplied, detergent was added, the test specimen was added, and then the 60°C liquid was added. and washed for 15 minutes. Next, draining water, supplying water, rinsing with water at 40° C. for 5 minutes three times, and draining and dehydrating the sample for 2 minutes were performed, and the test fabric was washed five times with this as one cycle.

b) Dry cleaning method The dry cleaning method specified in Fire and Disaster Management Agency Notification No. 1 (1986) was used. However, before dry cleaning, the samples were treated with hot water (40° C. x 30 minutes) and dried normally.

c) Flame retardant performance test method The fabric treated with each treatment solution was
Test specimens were prepared by cutting 5 pieces into 5 mm-sized pieces, which were processed by the above-mentioned washing method and dry cleaning method, and then dried for 24 hours in a constant temperature dryer at 50 ± 2 °C, and then placed in a desiccator containing silica gel. The condition of each specimen was adjusted by drying for 2 hours or more. Then, the flame retardant performance of this test specimen was evaluated according to the performance test standards for fire retardant products (Japan Flame Retardant Association clothing test method) shown below.

■ Vertical methane burner method Measure the length of the flame upward from the highest point of the burner to 38
After confirming that the flame is stable, move the burner and apply indirect flame to the test specimen for 3.0 ± 0.2 seconds, then remove the burner flame and remove the flame from the test specimen. The state of combustion on the support frame and flame droplet ignitability were evaluated. still,
The criteria for determining flame retardancy are as follows. ○: Average carbonization length of 5 fabric test pieces is 178 m.
m or less, and the maximum carbonization length is less than 254 mm, and there is no flame drop ignition property ×: The above conditions are not met.

■45° micro burner method The flame retardant property was determined according to the 45° micro burner method according to the Fire and Disaster Prevention Test Regulations of the Ministry of Home Affairs. The determination criteria in this case are as follows. ○: Carbonized area is 30 cm2 or less, afterflame time is 3 seconds or less,
Residual dust time 5 seconds or less ×: The above conditions are not met

d) Free formaldehyde test JIS L
1041-1983 Acetylacetone method Performed according to Method B.

e) Tear strength Tear strength was determined according to JIS L 1096-1990 6.15.5 D method (pendulum method). The displayed value is
Shows the average value of vertical + horizontal.

f) Flexibility ■JIS L 1096-1990 6.19.5 E
(handle-o-meter method). Note that the slit width was 10 mm. The displayed value shows the average value of vertical + horizontal. (2) A sensory evaluation was conducted by hand, and the evaluation was made in five stages based on the criteria shown below. 5: Softer than untreated cloth 4: Slightly flexible 3: No change in flexibility compared to untreated cloth 2: Slightly hard 1: Hard

g) Discoloration of metal print Bronze
80 copies of Binder N and Gold Powde
A composition consisting of 20 parts of r2L-7A (all manufactured by Matsui Shokuryo Co., Ltd.) was printed on cotton using a 100 mesh screen mold, dried at 120°C, and then heat-treated at 150°C for 3 minutes. Then, using this test cloth, the above-mentioned flameproofing treatment was performed, and the state of discoloration of the metal print was visually evaluated. The evaluation criteria were: 3: No discoloration, 2: Slight discoloration, 1: Significant discoloration.

[0027]

[Example] [Preparation method of first liquid] Example 1 First, 500 g of Pyrovatex CP New (manufactured by Ciba Geigy, N-methyloldimethylphosphonopropionamide), Sumitex Resin M-6 (manufactured by Sumitomo Chemical, hexamethylol), 100 g of melamine), 15 g of phosphoric acid (89%), and 70 g of diammonium phosphate (12%) were weighed, dissolved in water, and then water was added to make a total volume of 1 liter.

Examples 2 to 8 and Comparative Examples 1 to 4 Solutions having the compositions shown in Table 1 below were prepared in the same manner as in the preparation method described in Example 1 above. Furthermore, Table 1
The numerical values shown in are the number of grams of each component per liter of solution.

[0029]

[Table 1]

[Flame retardant processing method] Next, the first liquid prepared as described above (Examples 1 to 8 and Comparative Examples 1 to 4) was added to a
The liquid was padded onto a plain-woven cotton fabric of 81 g/m2, squeezed to a squeezing rate of 62%, and then heated at 110°C.
dried with. Furthermore, after heat treatment at 160°C for 3 minutes, washing with a 2g/l aqueous soda ash solution at 40°C, washing with hot water at 60°C, and washing with water, using a 5g/l aqueous sodium bisulfite solution as a second liquid. After that, the cylinder was washed with water and dried in the cylinder.

[0031] The cotton fabric that had been flame-retardant treated by the above method was washed with water five times by the method a) above, and the flame retardant performance of the washed test piece was evaluated by the test method c above. In addition, dry cleaning was performed 5 times using method b above,
Flame retardant performance was evaluated using the same method. The measurement results and judgment results at this time are shown in Table 2.

[0032]

[Table 2]

From the experimental results shown in Table 2, the test specimens treated using the first liquid of Comparative Examples 3 and 4 were the same as those of Examples 1 to 4.
It was found that the flame retardant properties were inferior to those treated using the first liquid of No. 8 and Comparative Examples 1 to 4.

Next, regarding the test specimens treated using the first liquid of Examples 1 to 8 and Comparative Examples 1 to 4, the above d to g
Free formaldehyde test, according to the method described in
Tear strength, stiffness, and discoloration of the metal print were evaluated. The measurement results and judgment results at this time are shown in Table 3.

[0035]

[Table 3]

From the experimental results shown in Table 3, Comparative Examples 1-
The test specimens treated using the first liquid of Examples 1 to 8 were
Compared to those treated using the first liquid, the amount of residual formaldehyde was large, and in the case of Comparative Examples 1, 2, and 4, the sensory stiffness was inferior, and in the case of Comparative Example 2, the metal Significant discoloration of the print was observed.

Comparative Examples 5 to 9 Furthermore, in order to investigate the relationship between the addition ratio of phosphoric acid and diammonium phosphate contained and the flame retardant property, Table 4 below was used.
A first liquid (Comparative Examples 5 to 9) having the composition shown below was prepared. The numerical values shown in Table 4 indicate the number of grams of each component per liter of solution.

[0038]

[Table 4]

Then, a cotton fabric similar to that described in Example 1 was subjected to the same flame retardant treatment method as in Example 1, and then washed 5 times using the method a above, and washed at 45° micro Flame retardancy was evaluated using the burner method. Table 5 shows the measurement results of the carbonized area at this time.

[0040]

[Table 5]

From the experimental results shown in Table 5, Comparative Examples 5 to
It was found that all of the test specimens treated using the first liquid No. 9 had poor flame retardancy.

[0042]

[Effects of the Invention] As can be seen from the above experimental results, by using the flameproofing method of the present invention, cellulose fibers can be imparted with excellent flameproofing properties, and the resulting product has excellent washing resistance. Since the flame retardant property and dry cleaning resistance are very excellent, the flame retardant property does not decrease due to washing or dry cleaning. In addition, in the flameproofing method of the present invention, the catalyst system contained in the first liquid is composed of diammonium phosphate and phosphoric acid, so there is a problem that the alloy of copper and zinc contained in the metal print will rust. It is stable in terms of processing steps and can produce flame-retardant textile products that meet consumer needs.

Furthermore, the cellulose fiber product obtained using the flameproofing method of the present invention has excellent flameproofing performance and has a small amount of residual formalin. In addition, it has a much better texture than those made by conventional techniques, so it can be used in various fields such as clothing, clothes, interior or exterior goods, sports goods, work clothes, and upholstery. For example, by using the present invention, it is possible to manufacture curtains and clothing that have practical flame retardant properties, and when these are used, it is possible to live a safe and comfortable life. The flameproofing method of the present invention can also be applied to metal-printed fibers, so by using this method, it is also possible to produce products with luxurious aesthetics that can be used as interior goods. can.

Claims (3)

[Claims] Claim 1: Cellulose fibers are treated with a first liquid containing N-methyloldimethylphosphonopropionamide, a triazine ring-containing compound, and a catalyst, and then treated with a second liquid containing a reducing agent. The above catalyst mixes diammonium phosphate and phosphoric acid in a ratio of 1:1.58.
A method for flameproofing cellulose fibers, characterized by containing cellulose fibers at a weight ratio of ~4.45. 2. The content ratio of diammonium phosphate and phosphoric acid in the first liquid is 0.60 to 0.84, respectively.
2. The flameproofing method according to claim 1, wherein the amount is 1.33 to 2.67% by weight. 3. The flameproofing method according to claim 1, wherein the reducing agent contained in the second liquid is at least one of sodium bisulfite and sodium sulfite.