JPH07789B2 - Aminophosphazene flame retardant finishing agent - Google Patents

Description

Detailed Description of the Invention [Industrial applications]

The present invention relates to a flame retardant finishing agent capable of imparting stable flame retardancy to fibers.

[Prior art]

As a method of making fiber materials such as thread and cloth flame-retardant, a Provan processing method using a condensate of tetrakis (hydroxymethyl) phosphonium sulfate and urea and N-methylol dimethylphosphonopropionamide (Pirovatex CP of Ciba Geigy) The method using (hereinafter, referred to only as “Pyrobatex CP method”) has been conventionally performed.

[Problems to be Solved by the Invention]

Among the above-mentioned methods, the Provan processing method has durability by forming Provan polymer in the fibrils of cotton fiber so that it has improved washing resistance and strength. Requires special equipment to perform ammonia cure. Moreover, an oxidation process with H ₂ O ₂ is required. Therefore, the texture of the cotton fiber is deteriorated, and the dyed product is discolored or the light resistance is deteriorated, so that reactive dyes are not used and only expensive vat dyes can be used. Further, the vat dye has a problem that the color tone is bad, and a large amount of formaldehyde is liberated from the processed cloth. On the other hand, in the Pyrovatex CP method, since methylolated melamine is used in combination, the strength of the fiber is reduced, especially the tear strength is greatly reduced, and the strength retention rate is reduced to about 50% (Tokyo Metropolitan Textile Industry Testing Station Research Report No. 32). Issue P.51 (1984)
Shin Saito, see Katsuo Akiyama). In addition, not only a large amount of formaldehyde is liberated from the work cloth, but also the work environment is deteriorated due to formaldehyde and the like even during the work. In addition, there is a problem that complicated process control is required, such as controlling the water content of the work cloth during the processing process and alkali soaping immediately after the curing process. In addition, a method of using tris (1-aziridinyl) phosphine oxide as a flame retardant for cotton fibers, tris (2,3-dibromopropyl) phosphate, bis (2,3-diphenyl) as a flame retardant for polyester fibers. Although there was a method using a brompropyl) phosphate compound or the like,
According to the Ministry of Health and Welfare's Law Concerning Regulation of Household Products Containing Hazardous Substances (Law No. 112 of 1973), it is banned from being used as a flameproofing agent, and it is no longer used. Moreover, regarding the free formaldehyde, the values detected by the above-mentioned laws are strictly regulated by the product. Moreover, in the case of polyester / cotton blended fabric (hereinafter referred to as “E / C”) cloth, the melt dripping of polyester fiber is prevented due to the so-called scaffold effect. Therefore, flammability is increased compared to the case of using polyester fiber and cotton fiber respectively, and flame-retardant processing becomes more difficult,
For E / C cloths and the like, there is currently no flame-retardant finishing agent with sufficient wash resistance (Shojiro Oe Polymer Processing 2
3 , 76 (1976), Yoshihisa Katsuura, Synthetic fiber monthly report 12 (4), 58 (1
974)).

[Means for Solving the Problems]

In order to solve the above-mentioned problems, the inventors of the present invention impregnate the raw material fibers with aminophosphazene, and after drying and curing,
It has been found that flame resistance can be imparted to the raw material fibers. However, aminophosphazenes are generally synthesized from chlorophosphazenes and ammonia. Aminophosphazene synthesized by such a method contains ammonium chloride in an amount of about 58% by weight, and when cured, ammonium chloride acts as an acid catalyst, causing a decrease in tear strength and a dye. It has been found that there are problems such as discoloration of the resin and that the flame-retardant effect is reduced after washing with the medium-temperature washer method. Therefore, the present inventor has conducted a flame-retardant treatment using the previously purified aminophosphazene and aminophosphazene derivative. A method (see Japanese Patent Publication No. 1-49827 and Japanese Patent Publication No. 1-49828) was proposed. The method of the above invention is capable of obtaining a flame-retardant finishing agent having a high aminophosphazene concentration, can obtain a flame-retardant fiber excellent in tear strength and wrinkle resistance, and is excellent in that no formaldehyde is generated. However, there was room for further improvement in the stability of the processing agent. Then, as a result of further diligent studies to provide a flame-retardant finishing agent having excellent stability and capable of improving the flame retardancy of the fiber, the present invention has been completed. That is, the aminophosphazene flame retardant finishing agent according to the first aspect of the present invention is an aminophosphazene oligomer hydrochloride salt,
A compound having at least one amino group selected from the group consisting of amines, amino alcohols, guanidine carbonate, urea and its derivatives, thiourea and its derivatives, amides, amino acids, polyethyleneimine, and melamine, and / or many It is characterized by being an aqueous solution containing a polyhydric alcohol. Then, add a pH adjuster to the above aqueous solution to adjust the pH to 7 to 1.
It is preferable to adjust to 0. The aminophosphazene flame retardant finishing agent according to the second invention is an aminophosphazene oligomer hydrate, an acid catalyst, amines, amino alcohols, guanidine carbonate, guanidine hydrochloride, guanidine phosphate, guanidine sulfamate, Aqueous solution containing guanidine nitrate, urea and derivatives thereof, thiourea and derivatives thereof, amides, amino acids, compounds containing at least one amino group selected from the group consisting of polyethyleneimine and melamine, and / or polyhydric alcohols It is characterized by being.

[Action]

According to the aminophosphazene flame-retardant finishing agent according to the present invention, wrinkle resistance, especially moisture wrinkle resistance is improved, and shrink resistance, pilling resistance, and abrasion resistance are improved, and the dyeing fastness of the dyed product and It has the effect of improving the weather fastness, but in particular,
It is possible to obtain a durable, flame-retardant processed textile material having excellent tear strength, excellent washability against washing with water, and excellent resistance against dry cleaning. Moreover, there is no discoloration or reduction in strength of the work cloth,
The stability of the work cloth during the process and the stability of the work cloth are excellent. Furthermore, since the processing agent itself has excellent stability, it is easy to manage, and the residual liquid can be reused, which is very economical. Further, since it is not necessary to use the ammonia curing method and the oxidation step, there is no problem such as discoloration of the reactive dye. Further, since formaldehyde is not generated at all, various problems associated with the generation of formaldehyde can be solved.

【Example】

The aminophosphazene flame-retardant finishing agent according to the first aspect of the present invention (hereinafter referred to as "processing agent" only) is aminophosphazene oligomer hydrochloride, amines, amino alcohols, guanidine carbonate, urea and its derivatives, thiourea. And a compound having at least one amino group selected from the group consisting of derivatives thereof, amides, amino acids, polyethyleneimine, and melamine (hereinafter referred to as “compound (1)”) and / or polyhydric alcohols In the above structure, the aminophosphazene oligomer is represented by the following formula It is a molecule represented by the chemical formula of n = 3 to 15 or a mixture thereof. The aminophosphazene oligomer hydrochloride is preferably as pure as possible. For example, a crude aminophosphazene oligomer is dissolved in the same amount to about 5 times the amount of water, and the solution is poured into 5 times the amount of alcohol such as methanol. Then, the method of precipitating only the aminophosphazene oligomer hydrochloride, or by pouring the powder of the crude aminophosphazene oligomer into about 10 times to about 25 times the amount of alcohol such as methanol, and the temperature from 0 ° C to the boiling point of the alcohol. within,
It is preferable that ammonium chloride is dissolved in alcohol by stirring and washing for a short period of time to obtain the aminophosphazene oligomer hydrochloride alone by precipitation. Incidentally, the same effect can be obtained even if the cleaning with alcohol is carried out in a small amount in several times. The aminophosphazene oligomer hydrochloride obtained by the above method has a remarkably high solubility in water, and a processing agent having a high aminophosphazene oligomer concentration can be obtained. The concentration of the aminophosphazene oligomer in the processing agent is 1 to
50% by weight, preferably 5 to 30% by weight is good. If it is less than 1% by weight, flame retardant effect cannot be expected. If it is less than 5% by weight,
Although it has a flame retardant effect, it tends to lack durability.
If it exceeds 30% by weight, the flame retardant effect is sufficient, but the texture tends to be hard depending on the case. If it exceeds 50% by weight,
Further improvement of flame retardant effect can hardly be expected. Since the aminophosphazene oligomer hydrochloride is used in the first invention, this hydrochloride also functions as an acid catalyst. That is, it is not necessary to add a compound that acts as an acid catalyst. Therefore, as the compound (1), a compound containing no strong acid salt that acts as a strong acid is used. More specifically exemplifying the compound (1), examples of amines include butylamine, sec-butylamine, triethylamine, hexamethylenediamine, and triethylenetetramine. 2-amino ethanol etc. are mentioned as amino alcohols. Examples of urea and its derivatives include urea, glyoxal-urea addition compounds, N, N'-dimethylurea and the like. Examples of thiourea and its derivatives include thiourea and ethylene thiourea. Examples of the amides include formamide, dimethylformamide, succinamide, acrylamide, polyacrylamide and the like. Examples of amino acids include glycine and alanine. The polyhydric alcohols are not particularly limited, but examples thereof include dihydric alcohols such as ethylene glycol, polyhydric alcohols such as glycerin, ethers of dihydric or polyhydric alcohols such as diethylene glycol, saccharides, starches, and polyvinyl alcohol. Can be mentioned. By using the compound (1) or a polyhydric alcohol in combination with the aminophosphazene oligomer hydrochloride, it is possible to improve the adhesion rate of the flame retardant finishing agent, the washing resistance of the flame retardant treated cloth, and the like. Moreover, since the compound (1) suppresses the hydrolysis of the aminophosphazene oligomer, it can be used as a processing agent for a long time. That is, it is considered that the compound (1) forms the salt with the excess hydrochloric acid generated from the aminophosphazene oligomer hydrochloride, reduces the acid concentration, and keeps it at an appropriate level, so that the above-mentioned effects are exhibited. The amount of compound (1) used is 1% by weight to 500% by weight based on the aminophosphazene oligomer in the aqueous solution.
It is preferable to adjust the degree. When it is 1% by weight or less, the effect of improving durability such as washing resistance and the effect of improving the adhesion rate of the flame retardant to the fiber are hardly recognized. 50
If it exceeds 0% by weight, the tendency of the flame-retardant adhesion to the fiber not increasing increases. In addition, the above-mentioned processing agent, the pH adjusting agent is further added
Is preferably adjusted to a range of 7 to 10, preferably 8 to 9.5. By adjusting the pH to 7 to 10 as described above, the storage stability of the processing agent is further improved without changing the balance between the aminophosphazene oligomer hydrochloride and the compound (1), and the flame-retardant processing is performed. It is possible to improve the washing resistance of the cloth. Examples of the pH adjusting agent include basic salts such as Na ₂ CO ₃ and K ₂ CO ₃ or buffering agents such as CH ₃ COONa and CH ₃ COONH ₄ , which may be used alone or in combination. You can The amount of pH adjuster used is 0.1% to 2.0% by weight in the processing agent.
A degree is preferable. If it is less than 0.1% by weight, the effect of controlling the pH is not sufficient, and if it is more than 2.0% by weight, there is a risk that an excessive amount of alkali component acts on the aminophosphazene oligomer to accelerate its hydrolysis. A desired fiber material is impregnated with this processing agent, dried, and then cured to make the fiber material flame-retardant. The steps of impregnation, drying, and curing are not particularly limited, but they can be continuously performed by using an ordinary pad-dry curing method. The drying temperature is preferably about 80 to 150 ° C. If the temperature is lower than 80 ° C, the drying time tends to be long. The curing is performed in air, and the temperature during curing is 80 to 200 ° C.
If the degree is less than 80 ° C., which is preferable, the treatment time becomes longer, and the flame-retardant washing resistance tends to decrease. If it exceeds 200 ° C, it becomes difficult to shorten the treatment time, and the strength tends to decrease and the fiber tends to discolor. Materials that can be made flame-retardant with this processing agent include cotton, linen,
Examples include fiber materials such as rayon, silk and wool, and cellulosic materials such as wood, plywood, paper and rush. In general, the fiber material is flame-retarded in the state of fiber material such as thread or cloth. The fiber material may be a mixed fiber or a mixed knitted fabric. Next, examples will be described in detail. Example 1 Crude aminophosphazene oligomer (Nippon Soda Co., Ltd.)
Product name AA-1000, about 58% ammonium chloride, and about 4
With 2% pure aminophosphazene oligomer,
Aminophosphazene oligomer with n = 3 65%, n
= 4 of 15%, n = 5 to 15 of 15% to 20%) 50g of powder into 300ml of methanol, liquid temperature
The mixture was stirred at 35 ° C for about 30 minutes and the insoluble matter was collected. The same operation was followed by washing twice to obtain 26.2 g of purified aminophosphazene oligomer hydrochloride. Elemental analysis result P
= 34.19% Cl = 14.06%. 1 dip of cotton satin with an aqueous solution consisting of 20% by weight of purified aminophosphazene oligomer hydrochloride and 20% by weight of urea.
After nipping and impregnation to a squeezing ratio of 101%, it was dried at 100 ° C. for 3 minutes. Then, it was cured at 160 ° C. for 3 minutes, washed with hot water at 65 ° C. for 5 minutes and dried to obtain a work cloth having an adhesion rate of 18.68%. Next, this processed cloth is washed with water by the flame proof association.
After washing once and 30 times, the carbonized area and carbonized length were measured, but no change was observed. In addition, after this processed cloth is treated in a constant temperature and humidity chamber at 60 ° C and 95% RH for 3 days, 5 days, and 7 days, it is washed at 65 ° C for 5 minutes with hot water and washed with water (medium temperature). The washer method) The flame retardancy was measured once, but no change was observed. The results are shown in Table 1. In addition, the washing method is revised “the criteria of the washing resistance performance related to the flameproof performance” on February 21, 1986, the Fire Service Agency Notification No. 1 and the “flameproof product performance test standard”, the flameproof product certification committee, revised Showa According to the method described in “Additional Laundry Procedure as Pretreatment for Flameproof Products” on August 1, 1986. The flame retardancy was measured by heating for 1 minute in accordance with JIS L 1091 A-1 method 45 ° micro-burner method, "Test method for flammability of textiles". It can be seen from Table 1 that this processed cloth has excellent durability against washing with water and its flame retardancy does not change even after being treated at 65 ° C and 95% RH for 7 days. Also,
It shows that the change over time due to hydrolysis is very small, and stable and sufficient flame retardancy is maintained. (Examples 2 and 3) Crude aminophosphazene oligomer (Nippon Soda Co., Ltd.)
(Trade name: AA-1000) manufactured by K.K., was dissolved in 125 ml of water to form an aqueous solution, which was poured into 750 ml of ethanol to obtain 23 g of purified aminophosphazene oligomer hydrochloride. This purified aminophosphazene oligomer hydrochloride and urea were dissolved in water at the ratios shown in Table 2 to prepare a processing agent, which was impregnated into cotton satin as a fiber material by dipping 2 dips and 2 nips. Then, the flame-retardant processed cloth was obtained in the same manner as in Example 1. (Comparative Example 1) A flame-retardant processed cloth was obtained by the same processing method as in Example 2 using an aqueous solution of 15% by weight of aminophosphazene oligomer hydrochloride purified by the same operation as in Example 2. (Comparative Example 2) Flame-retardant with the same processing method as in Example 2 in an aqueous solution containing 15% by weight of aminophosphazene oligomer hydrochloride purified by the same operation as in Example 2 and 2.0% by weight of 85% phosphoric acid. A processed cloth was obtained. Comparative Example 3 15% by weight of aminophosphazene oligomer hydrochloride and 7.5% by weight and 85% of urea purified by the same operation as in Example 2
A flame-retardant processed cloth was obtained by the same processing method as in Example 2 in an aqueous solution containing 2.0% by weight of phosphoric acid. The work cloths obtained in Examples 2 and 3 and Comparative Examples 1 to 3 were measured for the adhesion rate of the flame retardant and the flame retardancy after home washing. The results are shown in Table 2. The washing method used was a home washing method according to JIS L 0217 (1) Washing method 103, “Display symbols and display methods for handling textile products”. The flame retardancy was measured using the same method as in Example 1. From Table 2, it can be seen that the addition amount of urea is improved and the flame retardancy after 20 times of home washing is greatly different. Example 4 20% by weight of aminophosphazene oligomer hydrochloride purified by the same operation as in Example 2, 3% by weight of ethylenethiourea, and 5% by weight of formamide were dissolved in water to prepare a processing agent. Then, this processing agent was impregnated into cotton satin as a fibrous material by 2 dips and 2 nips to obtain a processed cloth in the same manner as in Example 1. (Comparative Example 4) 3% by weight of ethylenethiourea and 5% by weight of formamide
A processed cloth was obtained in the same manner as in Example 4 except that the processing agent to which and were not added was used. (Comparative Example 5) 3% by weight of ethylenethiourea and 5% by weight of formamide
Instead of, a working cloth was obtained in the same manner as in Example 4 except that a processing agent containing 1% by weight of 85% phosphoric acid was used. Regarding the processed cloths obtained in the above Example 4 and Comparative Examples 4 and 5, the drawing ratio, the flame retardant adhesion rate, the flame resistance of the finished processed cloth,
Flame-retardant after 50 washes with water, flame-retardant after 5 times with washing with water, and flame-retardant after 5 times with dry-cleaning, treated for 7 days under conditions of 60 ° C and 95% RH, after washing with hot water at 65 ° C for 5 minutes Furthermore, the flame retardancy after washing with water and washing 5 times was measured. The results are shown in Table 3. In addition, the washing method is revised “the criteria of the washing resistance performance related to the flameproof performance” on February 21, 1986, the Fire Service Agency Notification No. 1 and the “flameproof product performance test standard”, the flameproof product certification committee, revised Showa According to the method described in “Additional Laundry Procedure as Pretreatment for Flameproof Products” on August 1, 1986. The flame retardancy was measured by heating for 1 minute in accordance with JIS L 1091 A-1 method 45 ° micro-burner method, "Test method for flammability of textiles". (Example 5) Purified aminophosphazene oligomer hydrochloride 20% by weight and hexamethylenediamine 5 obtained in the same manner as in Example 1
A processing agent was obtained by dissolving wt% in water. This processing agent was impregnated into polynosic as a fiber material with 2 dips and 2 nips to impregnate it with a pickup rate of 90%, and then a processed cloth was obtained in the same manner as in Example 1. (Example 6) Example 5 was repeated except that sufmusulin was used as the fiber material.
A processed cloth was obtained in the same manner as in. About the work cloth obtained in Examples 5 and 6, the adhesion rate of the flame retardant,
The carbonized area, carbonized length, and LOI (Limited Oxygen Index) of the finished cloth and after washing with water 5 times were measured, and the results are shown in Table 4. The washing method and the flame retardancy measuring method were performed in the same manner as in Example 1, and the LOI was measured based on "a combustion test method for a polymer material by the oxygen index method" JIS K 7201. (Examples 7 to 10) 20% by weight of aminophosphazene oligomer hydrochloride and 10% by weight of urea purified by the same operation as in Example 2, and a basic salt as a pH adjuster at a ratio as shown in Table 5. Alternatively, a buffering agent was dissolved and mixed in water to obtain a processing agent. This processing agent was impregnated into cotton satin as a fiber material in the same manner as in Example 2, then dried and cured to obtain processed cloths. Furthermore, after storing the above-mentioned processing agent at room temperature for one month, a flame-retardant processed cloth was obtained by the same processing method. (Comparative Example 6) Example 7 except that 20% by weight of aminophosphazene oligomer hydrochloride purified by the same operation as in Example 2 and 10% by weight of urea were dissolved and mixed in water to obtain a processing agent. A processed cloth was obtained in the same manner. Comparative Example 7 20% by weight of aminophosphazene oligomer hydrochloride purified by the same procedure as in Example 2, 10% by weight of urea, and 2.0% by weight of 85% phosphoric acid as an acid catalyst were dissolved and mixed in water. A processed cloth was obtained in the same manner as in Example 7 except that the processing agent was obtained. The flame retardant adhesion rate of each of the processed cloths obtained in Examples 7 to 10 and Comparative Examples 6 and 7, the flame resistance of the finished processed cloths, and home washing 30
The flame retardancy after rotation was measured, and the results are shown in Table 5. The measurement was performed in the same manner as in Example 2. From Table 5, cotton satin processed with a basic salt or a processing agent to which a buffer is added shows sufficient flame retardancy even after 30 times of home washing, and the processing agent stored for one month has the same resistance. A processed cloth having a washability was obtained, and the stability of the processing agent was improved by adding a basic salt or a buffer. (Example 11) 20% by weight of purified aminophosphazene oligomer hydrochloride, 0.5% by weight of urea and 1% by weight of potassium carbonate were dissolved in water to obtain a processing agent. This processing agent is impregnated with cotton satin as a fiber material by dipping 1 dip 1
It was dried at 30 ° C for 30 seconds and cured at 160 ° C for 3 minutes. Then, it was washed with hot water at 65 ° C. for 5 minutes and dried to obtain a processed cloth. (Example 12) A processed cloth was obtained in the same manner as in Example 11 except that the purified aminophosphazene oligomer hydrochloride was 15% by weight and the urea was 45% by weight. (Example 13) A processed cloth was obtained in the same manner as in Example 11 except that urea was changed to 20% by weight. The drawing ratio was 93%. About the processed cloths obtained in Examples 11 to 13, the flame retardant adhesion rate, the carbonized area and carbonized length of the finished processed cloth, and the carbonized area and carbonized length of the processed cloth after washing under the washing conditions shown in Table 6 were measured. The results are also shown in Table 6. (Example 14) 50 g of crude aminophosphazene oligomer was dissolved in 100 ml of water, and this aqueous solution was put into 500 ml of methanol to obtain 20.5 g of purified aminophosphazene oligomer hydrochloride. The elemental analysis results are P = 31.30%, N = 38.93%, Cl = 13.3
It was 1%. 20% by weight of this purified aminophosphazene oligomer hydrochloride
And 10% by weight of diethylene glycol were dissolved in water to obtain a processing agent. 2 dips of this processing agent on cotton satin as a fiber material
I nipped. The draw ratio was 102%. Further, this cotton satin was dried at 100 ° C. for 3 minutes and cured at 160 ° C. for 3 minutes to obtain a processed cloth. (Comparative Example 8) A processed cloth was obtained in the same manner as in Example 14 except that diethylene glycol was not added. The work cloths obtained in Example 14 and Comparative Example 8 above were treated with flame retardant adhesion rate (initial adhesion rate) after washing with hot water at 65 ° C. for 5 minutes, and the work cloth was treated at 60 ° C. and 95% PH for 3 days. After one household washing and accelerated aging treatment, after the flame retardant adhesion rate and LOI of the processed cloth and 60 ° C, 95% RH for 7 days, one household washing and one accelerated laundry treatment The flame-retardant adhesion rate and LOI of the processed fabric were measured. The results are shown in Table 7. The LOI of cotton satin fabric is 18.1. The flame retardant finishing agent according to the second invention is an aminophosphazene oligomer hydrate, an acid catalyst, amines, amino alcohols, guanidine carbonate, guanidine hydrochloride, guanidine phosphate, guanidine sulfamate, guanidine nitrate, and urea. A compound containing at least one amino group selected from the group consisting of its derivative, thiourea and its derivative, amides, amino acids, polyethyleneimine, sulfanilic acid, and melamine (hereinafter referred to as "compound (2)"), and And / or polyhydric alcohols are dissolved in water. The aminophosphazene oligomer hydrate is preferably as pure as possible. For example, a method of dissolving a crude aminophosphazene oligomer in dilute aqueous ammonia and then adding it to a large amount of alcohol for precipitation, or It is preferable to obtain the aminophosphazene by using a method in which ammonium phosphazene is poured into concentrated aqueous ammonia and stirred to dissolve and remove ammonium chloride. In addition to the above methods, there are a method of removing ammonium chloride by liquefied ammonia and a method of removing ammonium chloride by refluxing with diethylamine in chloroform for a long time. However, these methods have problems in the following points, and are preferable. Absent. That is, in the former method, it is necessary to make the temperature as low as −33 ° C. and there is a risk of explosion due to the mixture of air and ammonia. On the other hand, the latter method is economically disadvantageous because the treatment takes a long time. Although the aminophosphazene oligomer hydrate has low solubility in water, it can be made to have a high concentration by adding an acid catalyst. The aminophosphazene oligomer hydrate concentration in the processing agent is 1 to 50% by weight, preferably 5 to 30% by weight. If it is 1% by weight or less, the flame retardant effect cannot be expected, and if it is 5% by weight or less, the flame retardant effect is exhibited but the durability tends to be insufficient. If it exceeds 30% by weight, the flame retardant effect is sufficient, but the texture tends to be hard. When it exceeds 50% by weight, further improvement of the flame retardant effect can hardly be expected. The acid catalyst is not particularly limited, but an acid catalyst used in ordinary resin processing, for example, a protic acid such as phosphoric acid, a metal salt such as zinc nitrate, zinc borofluoride, zinc chloride, 2-amino-2- Examples thereof include organic amine hydrochlorides such as methyl propanol hydrochloride, and these are used alone or in combination. The concentration of the acid catalyst is preferably about 0.1% by weight to 10% by weight. If it is less than 0.1% by weight, the flame retardant has poor washing resistance. On the other hand, if it exceeds 10% by weight, the tear strength of the flame-retarded fiber material is lowered or the color is changed. That is, there is an optimum value for the amount of acid catalyst, and an excessive amount of acid catalyst rather promotes hydrolysis of aminophosphazene, lowers wash resistance, and deteriorates flame retardance due to aging. The compound (2) used in the second invention forms a salt with an acid generated from an acid catalyst, and in order to keep the acid concentration at an appropriate level, the rate of attachment of the flame retardant agent, the washing resistance of the flame retardant cloth, etc. Improve
Then, it suppresses the hydrolysis of the aminophosphazene oligomer in the processing bath so that it can be used for a long time as a processing agent. More specifically exemplifying this compound (2), examples of amines include butylamine, sec-butylamine, triethylamine, hexamethylenediamine, and triethylenetetramine. 2-amino ethanol etc. are mentioned as amino alcohols. Examples of urea and its derivatives include urea, glyoxal-urea addition compounds, N, N'-dimethylurea and the like. Examples of thiourea and its derivatives include thiourea and ethylene thiourea. Examples of the amides include formamide, dimethylformamide, succinamide, acrylamide, polyacrylamide and the like. Examples of amino acids include glycine and alanine. The polyhydric alcohols are not particularly limited, and examples thereof include dihydric alcohols such as ethylene glycol, polyhydric alcohols such as glycerin, ethers of dihydric or polyhydric alcohols such as diethylene glycol, saccharides, starches, and polyvinyl alcohol. Can be mentioned. (Example 15) 50 g of crude aminophosphazene trimer was added to 28% ammonia water 1
It was put into 00 ml and stirred for 1 hour. Then, suction filtration was performed to obtain 11.2 g of purified aminophosphazene trimer hydrate. As a result of elemental analysis, P = 35.07% and N = 46.95%. 20% by weight of the purified aminophosphazene trimer hydrate thus obtained, 3.0% by weight of phosphoric acid as an acid catalyst, and 3.0% by weight of urea were dissolved in water to obtain a processing agent. (Example 16) A processing agent was obtained in the same manner as in Example 15 except that dextrin was 10% by weight instead of urea 3.0% by weight. Example 17 40 g of crude aminophosphazene trimer was dissolved in 250 ml of 5.7% (3N) aqueous ammonia, and this solution was added to 1125 m of ethanol.
Then, the mixture was filtered, and 15.4 g of purified aminophosphazene trimer hydrate was obtained. The result of elemental analysis is P = 37.
It was 50%, N = 47.66%, and Cl = 2.94%. 20% by weight of the purified aminophosphazene trimer hydrate thus obtained, 3.0% by weight of phosphoric acid as an acid catalyst, and 10% by weight of glycerin were dissolved in water to obtain a processing agent. (Comparative Example 9) A processing agent was obtained in the same manner as in Example 15 except that urea was not added. (Comparative Example 10) A processing agent was obtained in the same manner as in Example 16 except that dextrin was not added. (Comparative Example 11) A processing agent was obtained in the same manner as in Example 17, except that glycerin was not added. Each of the processing agents obtained in Examples 15 to 17 and Comparative Examples 9 to 11 was dipped and dipped in 2 pieces of cotton satin as a fiber material, dried at 100 ° C. for 3 minutes, and then cured at 160 ° C. for 3 minutes, and then 65 It was washed with hot water at ℃ for 5 minutes to obtain a work cloth. With the flame retardant adhesion rate and LOI of this processed cloth, accelerated aging treatment at 60 ° C 95% RH for 3 days, followed by one home washing and accelerated aging treatment at 60 ° C 95% RH for 7 days, After that, after performing home washing once, the flame retardant adhesion rate and LOI were measured. The results are shown in Table 8. From Table 8, it can be seen that by adding the compound (2) and the polyhydric alcohols, a flame-retardant processed cloth having an increased deposition rate and durability can be obtained.

【The invention's effect】

The flame-retardant finishing agent according to the first invention and the flame-retardant finishing agent according to the second invention, which are configured as described above, are excellent in tear strength, wrinkle resistance, particularly moisture wrinkle resistance, and have a good texture. It is possible to obtain a flame-retardant processed cloth which is soft, has excellent washing resistance and dry cleaning resistance, and has a flame-retardant effect and excellent durability. Moreover, it can be processed by the usual pad-dry-cure method,
There is no discoloration of reactive dyes and no generation of formaldehyde. Furthermore, in the flame-retardant finishing agent according to the first aspect of the present invention, if a pH adjusting agent is added, the effect can be maintained even after long-term storage.

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Claims (3)

[Claims] 1. An aminophosphazene oligomer hydrochloride,
A compound having at least one amino group selected from the group consisting of amines, amino alcohols, guanidine carbonate, urea and its derivatives, thiourea and its derivatives, amides, amino acids, polyethyleneimine, and melamine, and / or many An aminophosphazene flame-retardant finishing agent, which is an aqueous solution containing a polyhydric alcohol. 2. An aminophosphazene flame-retardant finishing agent obtained by adding a pH adjusting agent to the aqueous solution according to claim 1 to adjust the pH to 7-10. 3. An aminophosphazene oligomer hydrate,
Acid catalysts, amines, amino alcohols, guanidine carbonate, guanidine hydrochloride, guanidine phosphate, guanidine sulfamate, guanidine nitrate, urea and its derivatives,
Amino acid which is an aqueous solution containing thiourea and its derivative, amides, amino acids, polyethyleneimine, a compound containing at least one amino group selected from the group consisting of melamine and / or polyhydric alcohols Phosphazene flame retardant finishing agent.