JPH0160593B2 - - Google Patents

Description

[Detailed description of the invention]

INDUSTRIAL APPLICATION FIELD The present invention relates to a cellulosic fiber fabric and a shrink-proofing method for a fabric containing the same. PRIOR ART Processing agents such as aminoplast resin are commercially available as processing agents to prevent shrinkage that occurs when fabrics containing cellulose fibers are repeatedly washed. However, fabrics processed with these processing agents do not contain formaldehyde when worn. may be released and cause skin damage. In recent years, non-formaldehyde resins have been commercially available to avoid the above-mentioned skin damage, but they are less effective in preventing shrinkage that occurs during repeated washing. Therefore, there is a need for a processing method that can yield a fabric containing cellulose fibers that is formaldehyde-free, has a soft texture, and has an extremely low shrinkage rate when repeatedly washed. On the other hand, regarding amidophosphazene compounds, US Pat. No. 2,782,133 discloses a method for flameproofing fabrics containing cellulose fibers using a substance obtained by reacting a chlorophosphazene compound with anhydrous ammonia. The substance disclosed in the above-mentioned US patent has the problem that the amidophosphazene compound is not dissolved in water at room temperature and is significantly decomposed when dissolved in boiling water, and also exhibits resonance in the range of 13 ppm to 20 ppm in ³¹ P NMR. do not have. Therefore, there is a problem that fabrics containing cellulose fibers processed with the above substances become hard. The US patent does not disclose the processing method of the present invention. Furthermore, Japanese Patent Publication No. 45636/1983 discloses a method for producing an aqueous solution of an amidophosphazene compound obtained by mixing an aqueous solution of a chlorophosphazene compound with aqueous ammonia and aminating it. Since the compound is unstable and decomposes in an aqueous solution, it cannot be stored as an aqueous solution, making it difficult to use industrially. Also, only less than 30% by weight of the compound exhibits resonances in the range of 13 ppm to 20 ppm in the ³¹ P NMR, and therefore the aforementioned Japanese Patent Publication No. 47-45636 does not disclose the processing method of the present invention. Problems to be Solved by the Invention The present invention aims to solve the problems of the prior art, namely, to provide a fabric containing cellulose fibers that is non-formaldehyde, has a soft texture, and has an extremely low shrinkage rate when repeatedly washed. The object of the present invention is to provide a method for processing the fiber, which can obtain the fiber. Means for Solving the Problems As a result of intensive research, the present inventors have conducted intensive research to develop a processing method for obtaining a fabric containing cellulose fibers that is formaldehyde-free, has a soft texture, and has an extremely low shrinkage rate when repeatedly washed. The present invention has been achieved by discovering that the above object can be achieved by treating a fabric with an amidophosphazene compound that satisfies the following conditions. That is, the present invention provides an amidophosphazene compound called AA-1000, of which 30% by weight or more has ^{a 13}
Impregnating a cellulosic fiber fabric or a fabric containing the same with an aqueous solution containing the amidophosphazene compound, which exhibits resonance in the range of ~20 ppm, is a white solid, and is water-soluble at room temperature, and an acidic catalyst, Next, the fabric is compressed, dried, heat treated, soaped, and dried, and the resulting processed fabric contains a cellulosic fiber fabric or a fabric containing the same, characterized in that the resulting processed fabric contains 0.13 to 5.0% by weight of an amidophosphazene compound. Fabric processing method. It is related to. One example of a method for producing the amidophosphazene compound used in the present invention is a method in which the chloro group of the chlorophosphazene compound is replaced with an amide group to obtain the amidophosphazene compound. This method is a method in which a solution of a chlorophosphazene compound is reacted with ammonia. It can also be hydrolyzed and replaced with hydroxyl groups. In this method, chlorophosphazene compounds in which most of the chloro groups are replaced with amide groups and those in which all of the chloro groups are substituted are included, and these are all referred to as amidophosphazene compounds. Amidophosphazene compounds have the general formula

Cyclic amidophosphazene compounds of [formula] (where x is an integer of 3 or more), or general formulas P _o N _o (NH ₂ ) _2o (2) and P _o N _o-1 (NH ₂ ) _2o+3 (3)
(wherein n is a positive integer) is composed of a linear amidophosphazene compound, etc. In the formulas (1), (2) and (3), a portion of the amide group is substituted with an unsubstituted chloro group, a hydrolyzed hydroxyl group, a methoxy group, or an ethoxy group. The amidophosphazene compound slowly undergoes hydrolysis in an aqueous solution, and as the temperature increases,
Also, as the pH decreases, the rate of hydrolysis increases,
For example, rapid hydrolysis occurs in an aqueous solution at a temperature close to 100°C. Therefore, amidophosphazene compounds are unstable as aqueous solutions and cannot be stored. Furthermore, the amidophosphazene compound used in the present invention must be a white solid. The amidophosphazene compound may be a mixture with ammonium chloride produced as a by-product during production, and in the case of such a mixture, it is sufficient as long as the mixture is a white solid. The moisture content in the case of a white solid is 5
% or less, and if the water content is high, hydrolysis will proceed slightly even in solids. The moisture content is
It is expressed as % weight loss when dried to constant weight at a temperature of 105°C. The pH of the amidophosphazene compound is preferably 6-10; if the pH is too low, hydrolysis tends to occur during storage, and if the pH is too high, it is necessary to adjust the pH during use, which is uneconomical. The above pH is the pH of a saturated aqueous solution of the amidophosphazene compound. The amidophosphazene compound needs to be water-soluble at room temperature. When dissolved in high-temperature water, many of the amidophosphazene compounds are hydrolyzed during solution preparation, and the temperature further increases due to the heat generated during hydrolysis, and the pH of the solution decreases due to the hydrolyzate. , even more intense hydrolysis occurs. The normal temperature refers to a temperature of about 10 to 40°C. The amidophosphazene compound is ³¹ P-containing using an aqueous solution containing heavy water and/or DMF.
NMR analysis can be performed. In this case, 85%
The high magnetic field side is expressed as a negative value in ppm using phosphoric acid as an external reference. The present inventors have found a correlation between the ³¹ P NMR analysis chart of the amidophosphazene compound and the texture of a fabric processed using the amidophosphazene compound or the like. The amidophosphazene compound of the present invention is characterized in that 30% by weight or more of the amidophosphazene compound is ^31P .
It is necessary to exhibit resonance in the NMR range of 13 ppm to 20 ppm, and as the weight percentage increases, the flexibility of the fabric processed using them tends to increase, and the weight percentage is preferably 40% or more. The particularly preferable weight % is 50% or more. Weight%
When the weight percentage decreases to 30% or less, the texture becomes hard, but as the above weight percentage decreases, the weight of the component on the high magnetic field side increases from 13 ppm, and the high magnetic field side contains amidophosphazene with chloride residues. considered to be a thing. It is thought that the increase in the amount of amidophosphazene compounds having chloro residues makes the texture harder. The processing agent used in the present invention can also be obtained by reacting ammonia with a solution of a chlorophosphazene compound at low temperature for a long time, as shown in Reference Example 1. −1000Lot
No.FK−022, AA−1000P Lot No.FL−018, AA
−1000Lot No.FI−009, AA−1000Lot No.FH−
021, AA−1000 Lot No.FI−030, AA−1000
Lot No.FI−012, AA−1000 Lot No.FI−011,
AA−3800 Lot No.FH−01, AA−1000 Lot
No.FF−006, AA−1000 Lot No.FG−009, AA
−3800 Lot No.FG−003, AA3000 Lot No.EJ−
023, AA−3000L Lot No.FF−004, AA−
3000L Lot No.FK−018, AA−1000 Lot No.
GB−003, AA−1000A Lot No.GB−004,
AA3800 Lot No.FK−020, AA3800 Lot No.
FK−021, AA−1000 Lot No.FI−010, AA−
Examples include 3000 Lot No. FB-03 (all product names). Furthermore, many of the processing agents used in the present invention contain ammonium chloride, which is a by-product during the production of amidophosphazene compounds. Furthermore, to explain the amidophosphazenes described in this specification, amidophosphazenes (hereinafter referred to as AA-3000) with the trade names AA-3000 and AA-3000L are:
A mixture of phosphorus pentachloride (PCl ₅ ) and ammonium chloride is reacted in an organic solvent to produce chlorphosphazene oligomer (PNCl ₂ )n, and then a trimer (6-membered ring) is produced from this chlorphosphazene oligomer. The chlorphosphazene trimer is then purified and separated, and then ammonia gas is blown into the chlorophosphazene trimer dissolved in an organic solvent to produce a mixture of the amidophosphazene trimer and ammonium chloride as a by-product. Since chlorophosphazene is sufficiently purified and amidated, more than 90% of the resulting amidophosphazene is a trimer. AA−3000
Fabrics containing cellulose fibers processed with AA-3000 exhibit excellent shrinkage resistance against repeated washing and excellent flexibility. , very expensive. Amidophosphazene (hereinafter referred to as AA-3800) with the trade name AA-3800 is produced by reacting a mixture of phosphorus pentachloride (PCl ₅ ) and ammonium chloride in an organic solvent to form chlorphosphazene oligomer (PNCl ₂ ). n, and then a trimer (6-membered ring) and a 4-membered ring from this chlorophosphazene oligomer.
After purifying and separating only the chlorophosphazene trimer and tetramer (e.g., Example 7 of US Pat. No. 2,782,133), ammonia gas was blown into a mixture of chlorphosphazene trimer and tetramer dissolved in an organic solvent. It is produced as a mixture of amidophosphazene trimer and tetramer and ammonium chloride as a by-product. Fabrics containing cellulose fibers processed with AA-3800 exhibit extremely excellent shrinkage properties against repeated washing, but their texture varies depending on the production lot of AA-3800. However, like AA-3000, AA-3800 is very expensive because it purifies the intermediate chlorophosphazene produced during production. Product name AA-1000, AA-1000P and AA-
Amidophosphazenes labeled 1000A (in this specification, all these amidophosphazenes are
AA-1000) shall be included in the term AA-1000) by reacting a mixture of phosphorus pentachloride ( _PCl5 ) and ammonium chloride in an organic solvent to form chlorphosphazene oligomer ( _PNCl2 )n, followed by It is produced by blowing ammonia gas into chlorphosphazene oligomer dissolved in an organic solvent to form a mixture of amidophosphazene oligomer and ammonium chloride as a by-product.In order to amidate the intermediate chlorphosphazene without purifying it, The resulting amidophosphazene contains various amidophosphazene compounds such as trimer, tetramer, pentamer or more cyclic and linear compounds, and the content of these compounds varies depending on the production lot. For this reason, fabrics containing cellulose fibers processed with AA-1000 exhibit extremely excellent shrinkage properties against repeated washing, but their texture varies from coarse and hard to soft depending on the production lot. AA−1000 is AA−
Unlike 3000 and AA-3800, AA-
It is very inexpensive compared to 3000 and AA-3800. The base material, which is the fiber base material of the fabric according to the present invention, is a cellulose fiber, such as viscose rayon filament, viscose rayon staple, strong viscose rayon filament,
Examples include strong viscose rayon staples, polynostics, Kyupra filaments, Kyuplas staples, cotton, ramie and linen. Further, the base material may contain a small amount of fibers other than the base material, such as organic synthetic fibers such as polyamide, polyester, polyacrylonitrile, polypropylene, and spandex, and inorganic synthetic fibers such as glass fiber, carbon fiber, and silicon carbide fiber. They may be mixed, and the fabric may be in any form such as woven fabric, knitted fabric, non-woven fabric, resin-treated fabric, sewn product, etc. As the acidic catalyst, all acidic catalysts used for resin processing of fabrics are effective, such as urea-formaldehyde, melamine-formaldehyde, methylated methylolmelamine, dimethylolethylene urea, dimethyloluron, and tetramethylolacetylene dihydride. Diammonium phosphate, ammonium chloride, organic amine hydrochloride, zinc chloride, magnesium chloride, zinc nitrate, borium used in aminoplast resin finishing agents such as urea, dimethylol triazone and trimethylol melamine, and glyoxal resin finishing agents. Catalysts such as zinc fluoride, hydrochloric acid and phosphoric acid are preferred. At least one amidophosphazene compound and at least one acidic catalyst can be included in the aqueous solution. In addition to the amidophosphazene compound and acidic catalyst, a small amount of resin processing agent, softener,
Penetrants, water repellents, cellulose crosslinking agents, etc. may also be added. The concentration of the amidophosphazene compound in the aqueous solution is preferably 5 g/
~150g/. Further, the concentration of the acidic catalyst is preferably 1 g/ to 140 g/. The method for attaching the aqueous solution to the fabric is as follows:
This can be carried out by immersing the fabric in an aqueous solution and then squeezing it as it is or with a roll or mangle, or by spraying or applying the aqueous solution onto the fabric. The aqueous solution is applied to the fabric and then heat treated. As a heat treatment method, any heat source such as hot air, infrared rays, micro web, steam, etc. can be used. The heat treatment may be performed once or twice or more. The preferred heat treatment temperature is 50-190℃ and the preferred heat treatment time is 1-30℃.
It's a minute. The temperature and time may be appropriately selected so as not to damage the fabric. By heat treatment, the amidophosphazene compound becomes poorly soluble in water and is fixed to the fabric. It is preferable to remove water-soluble components in the fabric by washing with hot water or the like after the heat treatment. The preferred weight percent phosphorus content in the fabric is 0.05 to 2.0 weight percent
It is. When this is converted into an amidophosphazene compound, the unit compound of amidophosphazene {-PN
(NH ₂ ) ₂ } is 0.13 to 5.0% by weight based on the ratio of the molecular weight of 77 and the atomic weight of P to 31. In addition, a method for measuring the weight percent of an amidophosphazene compound exhibiting resonance in the range of 13 ppm to 20 ppm in ³¹ P NMR, a method for measuring the weight percent of phosphorus content, a method for measuring free formaldehyde, and a method for measuring the shrinkage rate after washing 45 times. The method and method for measuring bending resistance are as follows. (1) Method for measuring the weight percent of an amidophosphazene compound showing resonance in the range of 13 ppm to 20 ppm in ³¹ P NMR Add amidophosphazene to 1 of a 20% aqueous solution of heavy water (or a 20% aqueous solution of DMF if it does not dissolve in an aqueous solution of heavy water). A ³¹ P NMR analysis was performed using a solution containing 150 g of the compound as a test solution to obtain a resonance spectrum and its integral curve. The high magnetic field side is expressed as a negative value in ppm using 85% phosphoric acid as an external standard. The weight percent of P in the range of 13 ppm to 20 ppm was determined from the two curves, and this weight percent of P was directly determined as the weight percent of the amidophosphazene compound. (2) Method for measuring phosphorus content weight % The phosphorus content weight % in the fabric was determined by the sulfuric acid decomposition-colorimetric method shown below. Sulfuric acid decomposition - Weight % phosphorus content in fabric by colorimetric method
Measuring reagent 1 Sulfuric acid for precise analysis (special grade reagent, 98%) 2 60% perchloric acid 3 Ammonium molybdate solution: Ammonium molybdate (first grade reagent)
Dissolve 17.7g in water to make 500ml. 4 Ammonium metavanadate solution: Dissolve 0.6 g of ammonium metavanadate (first grade reagent) in water, add 100 ml of 60% perchloric acid, and dilute to 500 ml with water. Measuring equipment Chemical balance, 50ml Kjeldahl flask, 10ml
Whole pipette, 5 ml whole pipette, Kjeldahl thermal decomposition table, 25 ml volumetric flask, 50 ml volumetric flask, 50 ml measuring cylinder, 500 ml volumetric flask, 100 ml measuring cylinder, zeolite, spectrophotometer Procedure 1 Decomposition treatment of sample 200 to 300 mg of bone-dried sample to chemical Weigh accurately using a balance and transfer to a 50ml Kjeldahl flask. Add 5 ml of water, 5 ml of sulfuric acid, and 2 to 3 grains of zeolite (made of glass), set on a Kjeldahl thermal decomposition stand, and heat decompose. When the sample carbonizes and dissolves in the sulfuric acid and turns brown (approximately 30 minutes after starting heating), stop heating, let it cool for 5 minutes, add 3 drops of 60% perchloric acid, and heat decompose again. The operations of heating, cooling, and adding perchloric acid are repeated until the decomposed liquid becomes colorless and transparent for complete decomposition. Cool to room temperature, wash the decomposed solution into a 25 ml volumetric flask with water, and dilute to the balance. 2 Measurement Weigh the decomposition solution into a 50 ml volumetric flask according to the estimated phosphorus content, add 30 ml of water, then add 5 ml of ammonium molybdate solution and 5 ml of ammonium metavanadate solution, and dilute to the balance line with water. In parallel, perform a blank test using the same operation. After standing for 30 minutes, absorbance at 400 nm is measured using Blank as a control solution. Estimated phosphorus content Decomposition fluid collection amount 0.15-15% 0.5ml 0.1-3% 2.5ml 3 Calculation P (%) = 25 / Decomposition fluid collection amount × 50 / 1000 × 11.65 ×
Absorbance x 100/sample collection amount (mg) (11.65mg/=Ab1.0
) = 125/amount of decomposed liquid collected x 11.65 x absorbance/amount of sample collected (mg) Since the phosphorus content of the processed fabric is 3% or less, the amount of decomposed liquid collected is 2.5 ml and calculated using the following calculation. P (%) = Absorbance × 11.65 × 50 / Amount of sample collected (mg) (3) Method for measuring free formaldehyde Measurement was performed according to JIS L 1096-1979 Section 6.39.1.2 (1) B-1 method. (4) Method for measuring shrinkage after 45 washings (a) How to collect samples and make test pieces JIS L-1042-1983: 40 x 40 cm test pieces according to the method of sample collection and test piece preparation described in Section 7. It was created. (b) Washing The test was carried out as follows in accordance with the water washing test method of Fire and Disaster Management Agency Notification No. 11 dated June 1, 1972, ``Standards for washing resistance performance related to flame retardant performance (hereinafter referred to as ``Notification No. 11''). . (i) Wash continuously for 75 minutes with a 60°C solution. Note that the method of Notification No. 11 requires 15 minutes to wash, but this method requires 15 minutes x
5 (times) = 75 minutes. Washing test methods other than washing time are as follows:
Same as Notification No. 11. However, the detergent used was powder washing detergent (type 1 specified in JIS K3303), and 1 g was used per 1 water. (ii) Washing method in (i) (60℃ water supply → Add detergent → Add test specimen → Wash with 60℃ solution for 75 minutes → Drain, water supply, rinse for 5 minutes with 40℃ water ×
9 times (3 times → drain → dehydrate for 2 minutes → dry at 60℃)
Repeated times. In addition, (i) washing test is 5
This corresponds to repeating the process 9 times, which corresponds to a total of 45 repetitions. (c) Measurement After washing, measurements were carried out according to the method described in JIS L-1042-1983: Section 9. (d) Calculation The calculation was performed according to the calculation method described in JIS L-1042-1083: Section 10. That is, the average value of the length of the three lines in the vertical direction and the horizontal direction was calculated, and the shrinkage rate was calculated using the following formula, and was expressed as the average value of the three lines in the vertical direction and the horizontal direction. Progressive shrinkage rate (%) = L-L'/L x 100 where, L: Length before washing (mm) L': Length after washing (mm) (5) Measuring method of bending resistance JIS L 1096-1979 Section 6.19.3 Method C (Clarke method) Reference example 1 10 parts of a 6-membered ring 100% chlorophosphazene compound (white solid) was dissolved in 100 parts of carbon tetrachloride, and ammonia gas was added while stirring thoroughly. Blowing at approx. 0℃
The reaction was carried out for 2 hours. The reaction product was filtered, and the filtrate was thoroughly dried under reduced pressure. The product obtained is a white solid, which is dissolved in water at 20°C.
A 250 g/aqueous solution was prepared. A separately prepared saturated aqueous solution of this white solid had a pH of 7.0 and a moisture content of 1.0%. The phosphorus content in the product was also measured, and the weight percent of the amidophosphazene compound in the product was determined from the phosphorus content, which was 41.5 weight percent (the phosphorus content of the amidophosphazene compound was 40.3 (calculated as weight %). This product is manufactured by VARIAN.
An analytical curve was obtained using a FT-80 type ³¹ P NMR analyzer. The analytical curve is shown in FIG. Weight% showing resonance in the range of 13ppm to 20ppm from the curve in Figure 1
The result was 87%. 160 g of the above product (about 41.5% of amidophosphazene compound, about 58.5% of ammonium chloride), 3 g of nonionic penetrant/
The pick-up after soaking the dyed sfumos (30/1 x 30/1/68 x 60) in an aqueous solution containing 30/1 x 30/1/68 x 60 and squeezing it with a mangle was 100%. Next, it was dried at 100°C for 5 minutes and then heat treated at 150°C for 4 minutes. Then, it was washed with hot water and dried. Table 1 shows the properties of the obtained fabric amidophosphazene compound of the present invention. Reference example 2 AA−3000 Lot No.FB−03 [manufactured by Shin Nisso Kako Co., Ltd.,
Product name] amidophosphazene compound 74g/,
Ammonium chloride 20g/, nonionic penetrant 3
The same sfumos as in Reference Example 1 was immersed in an aqueous solution containing g/g and squeezed with a mangle. Then 5 at 100℃
After drying for 4 minutes, it was heat-treated at 155°C for 4 minutes. Table 1 shows the properties of the obtained fabric of the present invention and the amidophosphazene used. Example 1 AA-1000P Lot No.FL-018 [Shin Nisso Kako Co., Ltd.
Amidophosphazene compound 78g/
The same sfumos as in Reference Example 1 was immersed in an aqueous solution containing 15 g of ammonium chloride and 3 g of a nonionic penetrant and squeezed with a mangle. Next, Table 1 shows the properties of the fabric of the present invention obtained by performing the same treatment as in Reference Example 1 and the amidophosphazene compound used. Examples 2, 3 and Reference Examples 3 and 4 Amidophosphazene compounds 155 shown in Table 1
The same sfumos as in Reference Example 1 was immersed in an aqueous solution containing 3 g/g of nonionic penetrant and 3 g/g of a nonionic penetrant, and squeezed with a mangle. Next, Table 1 shows the properties of the fabric of the present invention obtained by performing the same treatment as in Reference Example 1 and the amidophosphazene compound used. NMR of Example 2 obtained in the same manner as Reference Example 1
Fig. 4 shows the analytical curve according to the method. The weight percentage exhibiting resonance in the range of 13 ppm to 20 ppm was determined from the curve of FIG. 4 and was found to be 58 weight percent. As is clear from these results, this product constitutes the processing agent used in the present invention. Comparative Example 1 A product was obtained by the method of Reference Example 1 of US Pat. No. 2,782,133. The obtained product was used as Reference Example 1 of the present invention.
The content of amidophosphazene compound in the product determined by the same method as above was 42.0% by weight. This product was dissolved in a solution of 20 parts of dimethylformamide and 80 parts of heavy water and treated in the same manner as in Reference Example 1 of the present invention.
A ^31P NMR analysis curve was obtained. The obtained curve is the second
As shown in the figure. The weight percent of the component exhibiting resonance in the range of 13 ppm to 20 ppm was determined to be 6% from the curve in FIG. 2. An attempt was made to prepare an aqueous solution containing 155 g of the above product and 3 g of the nonionic penetrant, but the solution did not dissolve at room temperature, and when the temperature was raised to near the boiling point, it dissolved, but intense heat generation occurred and the aqueous solution boiled violently. It was assumed that the heat generation was due to rapid hydrolysis. Because it does not dissolve in water, 20 parts of dimethylformalide and 80 parts of water
A solution of 155 g of the above product and 3 g of the nonionic penetrant was obtained by dissolving the product in a solution containing 155 g of the product and 3 g of the nonionic penetrant, and a fabric was obtained in the same manner as in Reference Example 1. Table 1 shows the properties of the fabric and amidophosphazene compound obtained. Comparative Example 2 A product was obtained by the method of Example 7 of US Pat. No. 2,782,133. The content of amidophosphazene compound in the product was 41.7% by weight. A ³¹ P NMR analysis curve was obtained in the same manner as in Comparative Example 1. The obtained curve is shown in FIG. From the curve in Figure 3
Weight % of components exhibiting resonances in the range 13ppm to 20ppm
The result was almost 0%. The product, like the product of Comparative Example 1, was not soluble in water. Therefore, a fabric was obtained by processing in the same manner as in Comparative Example 1. Table 1 shows the properties of the fabric and amidophosphazene compound obtained. Comparative Examples 3 to 4 Fabrics were obtained by processing the amidophosphazene compounds shown in Table 1 according to the methods of Examples 2 and 3 and Reference Examples 3 and 4. Table 1 shows the properties of the fabric and amidophosphazene compound obtained. Comparative Example 5-6 A fabric was processed in the same manner as Comparative Example 3-4, except that a mixture of 20 parts of dimethylformamide and 80 parts of water was used instead of water to dissolve the amidophosphazene compound. Obtained. Table 1 shows the properties of the fabric and amidophosphazene compound obtained. Comparative Example 7 Commercially available non-formalin resin processing agent Betscamine NF
-5 (manufactured by Dainippon Ink & Chemicals Co., Ltd.) 100g/
, Catalyst GT (manufactured by Dainippon Ink & Chemicals Co., Ltd.) 40g/and nonionic penetrant 3g/
The pick-up after soaking the same sfumos as in Reference Example 1 in an aqueous solution containing and squeezing it with a mangle is 100%.
It was hot. After drying at 100℃ for 5 minutes, dry at 155℃.
Table 1 shows the various performances of the fabric obtained by heat treatment for 4 minutes.

[Table] Effects of the invention Dyeing of sfumos used in Examples and Comparative Examples
The shrinkage rate in the vertical direction after washing 45 times reached about 14%, and when processed with a commercially available non-formalin resin processing agent.
After washing 45 times, the shrinkage rate in the warp direction is improved to about 7%, but it is not as high as the value of about 3% of the present invention. In addition, the bending resistance of the finished dyeing of the sfumos used in the Examples and Comparative Examples (the smaller the value is, the more flexible it is) is approximately 33, which indicates that the fabric processed with the processing agent of the present invention has a flexible texture. This is clear from the examples. Fabrics processed with the processing agent of the present invention have extremely low shrinkage when washed repeatedly, are non-formalin-proprietary, and have a soft texture, so they can be used in clothing that comes in direct contact with the skin, such as infant clothing, pajamas, lingerie, bed sheets, blouses, and dress shirts. The uses are extremely wide.

[Brief explanation of drawings]

FIG. 1 shows the NMR resonance spectrum and its integral curve of the amidophosphazene compound of the present invention of Reference Example 1. FIG. 2 shows the NMR resonance spectrum and its integral curve of the amidophosphazene compound of Comparative Example 1. FIG. 3 shows the NMR resonance spectrum and its integral curve of the amidophosphazene compound of Comparative Example 2. FIG. 4 shows the NMR resonance spectrum and its integral curve of the amidophosphazene compound of Example 1.

Claims (1)

[Claims] 1 An amidophosphazene compound called AA-1000, of which 30% by weight or more is ^31P
A cellulosic fiber fabric or a fabric containing the same is impregnated with an aqueous solution containing the amidophosphazene compound, which exhibits resonance in the range of 13 to 20 ppm, is a white solid, and is water-soluble at room temperature, and an acidic catalyst. , then squeezing, drying, heat treatment,
Soaped, dried, and the resulting processed cloth,
A method for processing a cellulosic fiber fabric or a fabric containing the same, characterized in that it contains an amidophosphazene compound in an amount of 0.13 to 5.0% by weight.