JPH0284562A - Processing agent for cellulosic material and method for processing - Google Patents

Abstract

PURPOSE:To obtain the subject processing agent, consisting essentially of an aqueous solution of an aged amidophosphazene-based compound, having soft feeling with ultralow shrinkage factor in repeated washing and hardly any fouling with fluorescent dyes, etc., in a detergent and suitable as infant clothes, etc. CONSTITUTION:The objective processing agent consisting essentially of an aqueous solution of an aged amidophosphazene-based compound. The above- mentioned agent is preferably applied to a cellulosic fabric and heat-treated to carry out processing. Furthermore, a compound composed of a cyclic amidophosphazene compound expressed by the formula (x is >=3), linear amidophosphazene compound, etc., is preferably used as the above-mentioned compound.

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial Application Field] The present invention relates to a processing agent for cellulosic materials and a method for adding cellulosic materials, particularly fabrics thereof, using the processing agent.

[Prior Art] Aminoblast resin and other processing agents are commercially available as processing agents to prevent shrinkage that occurs when cellulose-based materials, especially their fabrics, are washed repeatedly, but fabrics processed with these processing agents are difficult to wear. Sometimes formaldehyde is released and may cause skin damage. Avoiding the aforementioned skin disorders in recent years
Non-formaldehyde resins are commercially available to
It is less effective in preventing shrinkage that occurs when washing repeatedly.

Therefore, no processing method has yet been developed that can produce cellulose-based fabrics that are formaldehyde-free, have a soft texture, and have extremely low shrinkage when washed repeatedly.

On the other hand, regarding amidophosphane compounds,
No. 45636 discloses a method for producing an ammonia aqueous solution of this compound, and U.S. Patent No. 2.782,
No. 133 discloses a method for carburizing a cellulose material, particularly a fabric thereof, using an aminophosphazene compound, and its outcome, but none of these techniques concern an aged amidophosphazene compound. Furthermore, cellulose processed with the substance disclosed in the above-mentioned U.S. patent
There is a problem with black-based fabrics because they are visible. In addition, △△-1000A type 1, which is a commercially available amidophosphazene compound,
"Manufactured by Nippon Soda Co., Ltd." has the problem that the texture of the processed product becomes hard.

Furthermore, when cellulose fiber products are washed with commercially available detergents, there is a problem of contamination in which the fiber products are dyed by the fluorescent dyes contained in the detergent and the color of the fiber products changes. Especially in the case of light-colored textile products, the color change is significant. In addition, if you wash UA textile products with poor color fastness together, the color of the textile products will leach into the washing liquid and dye other items to be washed, or textile accessories that have come into contact with textile products with poor color fastness. There is also contamination, such as dyeing at the contact area, which often becomes a problem at the consumption stage of textile products. Clothing stains from blood, oil, sauce, ketchup, cola, black tea, etc. are also a common problem in the home and commercial laundry industry. In the linen refill business, we separate items with blood on them before washing them and perform a special washing process.

In order to solve the problem of contamination mentioned above, conventional technology has been developed.
η For methods of preventing staining, and for fluorescent dyes, There is a way to attach it to fibers. However, in the method (2), the cellulose fiber eaves 1 loses its inherent water absorbency, making it unsuitable for applications that require water absorbency, such as comfort. With method ■, the texture becomes hard and there is a problem with transparent formalin, but both ■ and ■!
! ! ! The present invention solves the problems of the prior art, which has a large progressive shrinkage due to repeated washing, and is non-formaldehyde, flexible in use, has extremely low shrinkage when washed repeatedly, and contains fluorescent dyes in detergents. It is an object of the present invention to provide a processing method capable of obtaining cellulosic materials, particularly fabrics thereof, which are extremely less contaminated by contaminants such as dyes, human blood, soybean oil, sauces, and cola that come off from dyed textile products during washing. It is non-formaldehyde, has a flexible 14-layer, and has very little shrinkage when washed repeatedly, and is resistant to contaminants such as fluorescent dyes in detergents, dyes that fall off from dyed textile products when washed, human blood, soybean oil, sauce, and cola. We are working hard to develop processing agents and processing methods for producing cellulose-based materials, especially fabrics, with extremely low contamination. The present inventors have discovered that the above object can be achieved by using an aqueous solution of a carbon-based compound after ripening, and have thus arrived at the present invention. That is, the present invention is characterized by a processing agent for cellulosic materials comprising an aqueous solution of an aged amidophosphazene compound as a main component, and the processing agent is attached to a cellulose fabric j-1 and then heat-treated. This is a novel method for processing cellulose fabrics. The amidophosphazene compound is a cyclic amidophosfavine compound of the general formula (wherein X is an integer of 3 or more) or a general formula of (1), consisting of a linear amide phosphonoagine compound (medium, nn rho 1 2 2n+3 is a positive integer).
(2) and (3) In the formulas, a part of the amide group is unsubstituted chloro M, a hydroxyl group by hydrolysis, a methoxy sphere, an alkoxy group such as 1-toxy, a phenoxy group, a mono-lower fluor 1
b substituted with -ruamino group, di-lower alkylamino group, etc. are also included.

7 Specific examples of midophosphagene compounds include AA-1000AGB-005 and AA-
1000AGC-403, AA-1000ΔG B −
0345, AA-1000AGJ-006, A, 111
000AGJ-007, AA-1000AGJ-008
(Product name) etc. 1゜Aqueous solutions of these amidophosnopine compounds are prepared by dissolving the amidophosnopine compounds in neutral water or F[ammonium, chloride 1-lium, nitric acid] A neutral aqueous solution of an amidophosfavine compound dissolved in an aqueous solution of a neutral compound such as cum, magnesium chloride, or an ammonia aqueous solution, an aqueous sodium carbonate solution, a caustic soda aqueous solution, an aqueous solution of ammonium hydrogen phosphate, a phosphorus Phosphorus water resistant solution of an alkaline aqueous solution of a midophosphazene compound and an amidophosphazene compound dissolved in an alkaline aqueous solution such as an aqueous sodium acid solution, an aqueous calcium hydroxide solution, and an aqueous solution of putrium oxalate. 8 liquid, ammonium chloride aqueous solution, hydrogen phosphate-ammonium aqueous solution, hydrogen phosphate-sodium aqueous solution, M acid aqueous solution, oxalic acid aqueous solution, ``Hycinic acid aqueous solution, etc.'' Ru.

Acidic catalysts such as ammonium phosphate, ammonium chloride, organic amine hydrochloride, zinc chloride, magnesium chloride, zinc nitrate, zinc borofluoride, hydrochloric acid and phosphorus M, and a few conventionally used resin processing agents, A softener, a penetrant, a water repellent, and/or a cell[1-se crosslinking agent] can also be added as auxiliary components to the aqueous solution of the amidophosphazene compound.

Although the crude amidophosphazene compound contains a large amount of ammonium chloride as a by-product, an aqueous solution of the crude amidophosphazene compound is one of the preferred embodiments.

The processing agent of the present invention can be prepared by aging an aqueous solution of an amidobosphazene compound. Ammonia gas was blown into an anhydrous carbon tetrachloride solution, and the mixed precipitate of the amidophosnoapine compound and ammonium chloride was filtered and dried, and the resulting crude amidophosfavine compound was made into an aqueous solution. In the aging method, ammonia gas was blown into a solution of chlorphosphagen in t-chlorobenzene, and an aqueous solution was added to the mixed precipitate of an amidophosnopine compound and ammonium chloride. Method for aging an aqueous solution containing an amidophosphazene compound and ammonium chloride as main components, Japanese Patent Publication No. 47-1963
As described in Examples 1 to 4 of Publication No. 6, a phosphonitrile chloride compound prepared by reacting phosphorus pentachloride and ammonium chloride in an inert solvent such as monochlorobenzene or tetrachloroethane. % Formula %) (PNcJ!) ・A mixture of a group of compounds represented by PCl5 is annealed at a low temperature, mixed with an aqueous solution of Nia, and amidated. ) A method of aging an aqueous solution mainly containing the amidophosphazene compound of 4 and ammonium chloride as a by-product, as shown in Synthesis Example 1 of Japanese Patent Application No. 62-309373, from phosphorus pentachloride and ammonium chloride. The produced chlorobosphazene is dissolved in chlorobenzene, reacted with diethylamine under cooling, and ammonia gas is blown into the solution.
A method for aging an aqueous solution containing an amidophosfavine compound and ammonium chloride as main components obtained by stratifying the itch;
Various methods can be adopted.

31 of the aqueous solution of amidophosphazene compound by aging.
The N M 8 curve of P changes. Examples of typical changes in the aqueous solution of amidophosphazene compounds are shown in Figures 1 to 5.
It's not in the picture.

Figure 1 shows crude amidobosphazene compounds (Lot N
o, GL3-003. The NMR 11II line of unripened 3IP (purity 41.4%, ammonium chloride approximately 58%) is shown, and the peak C4 is the peak of the -F component of the compound.

Figure 2 shows the same amidophosfavine compound as in Figure 1.
*11 of crude amidophosphazene compound dissolved in 4% aqueous ammonia and 400 g/o! Figure 3 shows the NMRI line of 31P obtained by aging an aqueous solution of a bound 7 midophosphavine compound at 0°C for 1 hour; NMR of 31P after aging the same aqueous solution of amidophosphazene compound used in Figure 2 at 50°C for 6 hours.
A curve is shown, and it can be seen that beaks 8 and B have grown, and beak C has almost disappeared. No. 414 is 1 at 50℃
The NMR curve of 31P after aging for 2 hours is shown, and it can be seen that beaks A and 8 have grown roughly and beak C has disappeared. Figure 5 shows the sample aged at 50°C for 24 hours, and it can be seen that the composition has almost changed to the compositions shown in beaks A and B'c.

FIG. 6 shows a lot number of crude 7 midophosphavine compound (Lot No., FC-028, purity 42%, different from the amidobosphazene compound used in FIG. 1).
NMR of unaged 3IP of ammonium chloride (approximately 58%)
The dh line is shown, and the peak C is the peak of the main component of the compound.

Are Figures 7 to 15 the same as those used for Figure 6? Midophosphazene compound was dissolved in each aqueous solution and
"j/I crude amidophosphazene compound aiii1
There is an NMR curve C of 31P after aging under various conditions.

Figure 7 shows an amidophosphazene compound dissolved in 10% aqueous ammonia and aged at 50°C for 24 hours. FIG. 8 shows an amidophosphazene compound dissolved in 5% aqueous ammonia and aged at 50° C. for 85 hours. FIG. 9 shows an amidophosphazene compound dissolved in 1% 7 mp water and aged at 50° C. for 23 hours. , Figure 10 shows a sample in which an amidophosphazene compound was dissolved in 1% ammonia water and aged at 50°C for 69 hours. Figure 11 shows the amount of amidophosphazene compound.
It was dissolved in 1% aqueous ammonia and aged at 50°C for 85 hours. FIG. 12 shows an amidophosphazene compound dissolved in a 1% aqueous phosphoric acid solution and aged at 50° C. for 60 hours.

Figure 13 shows the solution of amidophosphazene compound in water.
It was aged for 36 hours at 0°C.

FIG. 14 shows a product in which an amidophosphazene compound was dissolved in 1% aqueous ammonia, aged at 60°C for 15 hours, and then gently aged at 20°C for 10 minutes. , Figure 15 shows the result of dissolving an amidophosphazene compound in 0% ammonia water and aging it at 20°C for 20[-1°]. NMR curve of unripened 31P of the crude amidophosphazene compound (Lot No. GH-605, purity 41.7%, ammonium chloride about 58%) from tot NO. The peak CG is the peak of the main component of the compound.

Figures 17 to 19 show the results obtained by dissolving the same amidophosphazene compounds used in Figure 16 in the respective aqueous solutions.
This was used as 81 degrees of an amidophosphazene compound of 00Sj/1. FIG. 17 shows an amidophosphazene compound dissolved in a 1% aqueous ammonium phosphate solution and aged at 40° C. for 16 hours. Figure 18 shows an amidophosphazene compound dissolved in a 1% 1-lium hydroxide aqueous solution, aged at 40°C for 16 hours, and then further heated at 20°C.
It is aged for 3 times. Figure 19 shows an amidophosphazene compound dissolved in a 1% oxalic acid aqueous solution at 45°C.
There is a C that has been aged for 20 hours.

The ripening conditions are such that beak A and/or beak B form a
Although the field is different from the one that is not converted, there is no difference in effect. ) Preferred aging 11Jt is 10-60
It is °C.

In the present invention, a processing agent (hereinafter abbreviated as "processing agent") mainly composed of the aged amidophosphazene compound described above is applied to a fabric. Acidic catalysts such as ammonium phosphate, ammonium chloride, tll amine hydrochloride, zinc chloride, magnesium chloride, zinc nitrate, zinc borofluoride, hydrochloric acid and phosphoric acid, and traditionally used beef tallow They can also be added as auxiliary components such as resin processing agents, softeners, penetrants, water repellents and/or cellulose cross-linking agents.

The processing agent can be applied to the fabric by immersing the fabric in an aqueous solution and then squeezing it directly or with a roll or mangle, or by spraying or applying the aqueous solution onto the fabric.

Regarding the number of times the finishing agent is applied to the fabric, it is preferable that 2 to 7 percent of the active ingredient adheres to the fabric at one time of drying.

If there is less adhesion, the shrinkage effect will also be smaller, and 14 pieces i'11
This is because if there is too much, the strength may be low depending on the material.

The base material according to the invention is a cellulosic material, in particular a fiber, such as viscose rayon filament, viscose slay constable, strong viscose rayon filament, strong viscose rayon stable, polynosic, cupro filament, cupro daple,
Examples include cotton, ramie and linen. In addition, this base material includes a small amount of lj & miscellaneous other than the base material.
For example, organic synthetic fibers such as polyamide, polyester, polyacrylonitrile, polypropylene, and spandex, glass fibers, carbon fibers, and silicon carbide fibers. (1) Any synthetic fiber 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.

After the finishing agent is attached to the fabric, heat treatment is performed, and any heat source such as hot air, infrared rays, microwaves, steam, etc. can be used for this heat treatment. The heat treatment may be performed once or twice or more. 1. The preferred heat treatment temperature is 50 to 190"C, and the preferred heat treatment time is 1 to 30 minutes. Conditions may be appropriately selected so as not to damage the fabric.

Due to heat treatment, the processing agent becomes refractory to water and becomes fixed to the fabric. It is preferable to perform dry washing or the like after the heat treatment to remove water-soluble components in the fabric.

The fabric obtained by the processing method of the present invention is such that the phosphorus in the aqueous processing agent adhering to the processed fabric is preferably 0.3 to 2.0% by weight based on the soaked original fabric. The amount of TI-free formaldehyde in the product is 10μ97g or more, and the MI yield after washing is 4% or less.

The methods for measuring phosphorus content (wt%), free formaldehyde, abrasion strength, shrinkage rate of 45 recovery after washing, white melon, bending resistance, and bending properties are as follows.

(1) Method for measuring phosphorus content weight % The phosphorus content of 11% in the fabric was determined by the sulfuric acid decomposition-colorimetric method shown below.

@Measurement reagent for weight % phosphorus content in fabric by acid decomposition-colorimetric method 1. Precise analysis Kawasulfur M (special reagent grade, 98%) 2.60
% perchloric acid 3, ammonium molybdate solution: Dissolve 17.7 J of ammonium molybdate (reagent grade) in water to make 500 d.

4. Ammonium metavanadate solution Dissolve 0.69 ammonium dimetavanadate (reagent grade) in water, add 60% per-'Am100Id, and dilute to 500ml with water! It is diluted.

Measuring equipment (chemistry)? , 50-Kjeldahl flask, 10d hole pipette, 5d ball pipette, Kjeldahl thermal decomposition table, 25-volume flask, 5] Od volumetric flask, 50
d graduated cylinder, bo 0- volumetric flask, 100-
Graduated cylinder zeolite, spectrophotometer operation 1 Sample decomposition treatment: Precisely weigh 200 to 300 η of an absolutely dry sample using a chemical balance.
Take 50 quarts into a Coeur d'Art flask. 5ml of water! , sulfur F
l! 25m1! , add 2 to 3 grains of zeolite (glass),
Set on Kjeldahl thermal decomposition table and thermally decompose. When the sample carbonizes and dissolves in sulfuric acid and turns brown (approximately 3 minutes after starting heating)
0 minutes) Stop heating and leave to cool for 5 minutes until 60% has passed! ! element 1
Add 3 drops and heat decompose again. Heat decomposition=-Cold 2JI-Perchlorine ilI until the decomposition solution becomes colorless and transparent! i Repeat the addition operation to ensure complete decomposition.

Cool MIL until room wet, wash the decomposition solution into a 25 d volumetric flask with water, and dilute to balance. .

2. Measurement 111 According to the constant phosphorus content 1゛D, the decomposed solution was weighed into a 50af volumetric flask, and after adding 30ml of water, ammonium molybdate solution 5I! ! i! , metavanazine awakening [
Nium solution 5III! Add and dilute to the scale with water.

In parallel, a blank test is performed in the same manner. Immediately after incubation for 30 minutes, the absorbance at 4000... is measured using Blank as a control solution.

IW constant concentration 1 Decomposition liquid collection amount 0.5~
15% 0.5M10.1~3%
2.5d3 xll, 65X Absorption 1 The phosphorus content ITtti of the processed fabric is less than 3%, so the amount of decomposed liquid collected is 2.5d! Applying this, we obtain the result using the following calculation.

Absorbance X 11.65X 50 (2) Free formaldehyde measurement method JIS L
1096-1979 6.39゜Term 1.2 + 1) B
-1 method was used.

+31 K Measuring method of abrasion strength JIS L 1096-1979.6.17゜1
It was determined by the A-2 method.

(4) Method for measuring shrinkage rate after 45 washes (a)
How to collect samples and prepare test pieces JIS l--101
A 40×40c111 test piece was prepared according to the sample collection and test piece preparation methods described in Section 2-1983.

(In accordance with the water washing test method of the IIN #Washing performance standards t1g (hereinafter referred to as "F1 Notification No. 11"), dated June 1, 1970, Fire Department , carried out by the following.

(i) Washing time is carried out continuously for 75 minutes with a solution at 60°C. In addition, in the method of Koshimizu No. 11, the washing time is 15 minutes, but in the case of water spray, it is 15 minutes x 5 (times) = 75 minutes.

The washing test method other than the washing time is the same as in Notification No. 11. However, when using detergent, use the powder method.
Type 1 specified in JIS K3303), water 11
1 g was used per sample.

(ill) Washing method (i) (60℃ water supply → Add detergent → Add test specimen → Wash with 60℃ solution for 75 minutes → 1
7 + water, water supply, rinsing with 40°C water for 5 minutes x 3 times → draining → dehydration for 2 minutes → drying at 60°C) was repeated 9 times. In addition,
Since the washing test (i) corresponds to 5 repetitions, this is repeated 9 times, which corresponds to a total of 45 repetitions.

1) Measurement After washing, JIS L-1042-1983: Section 9;
The measurement was carried out using the method described in Section 2. .

0 Calculation The calculation was carried out using the method described in JIS L-1042-1083:10. In other words, 3 each for vertical and horizontal
The average value of the length of the line was determined, and the shrinkage rate was calculated using the following formula, and was expressed as the average value of three times each in the vertical and horizontal directions.

Here, L: Length before washing (#R) L': Length after washing (an) (5) Measuring method for home use JIS L 1013-1981.7. 20
It was determined by the 1-negative B method.

(6) Measuring method of bending properties JIS L 1096-1979 6.19゜ Section 3 C method (Clark method) (1) Measuring method of bending properties 1 Standardization and analysis of fit evaluation 2nd edition (Incorporated Association Textile Machinery Society of Japan, texture measurement and standardization ω1 research committee) No. 2
7-28 According to the true method, B(a, f, υ2/α) and 2HB(gf・rttr
/ c 屓) was calculated.

()1) Stain resistance evaluation method Based on Japanese Standards Association color fastness test stain gray scale determination method.

1 Example 1 Hereinafter, the present invention will be explained in more detail with reference to Examples.

Example 1 Crude amidophosphazene compound [AΔ manufactured by Nippon Soda Co., Ltd.
-1000ALotNO, GB-005, amidophosnoagene compound approximately 42%, ammonium chloride approximately 58%]
An aqueous solution containing 120 g/l of nonionic penetrant 39/1 was prepared, aged at 35°C for 3 hours, and the pick-up after squeezing the aqueous solution with a 4x74 piece of 100% Polynosic fabric was 120%.

Next, after drying at 100°C for 5 minutes, heat treatment was performed at 150°C for 3 minutes, followed by washing and drying. Table 1 shows the various qualities of the fabric of the present invention.

Example 2 Crude amidophosphazene compound [Nippon Yosso Co., Ltd.
-1000ALotNo, GC-403 amidophosphazene compound approximately 42%, ammonium chloride approximately 58%] 1
70=, i/1, an aqueous solution containing 3 g/l of a nonionic penetrant was prepared, and the aqueous solution aged during SILI at 30° C. was squeezed with 6.1×60 ml of sfumos, and the pickup was 100%.

Next, it was dried at 100°C for 5 minutes and heat treated at 150°C for 4 minutes. Afterwards, it was washed and dried. Table 1 shows the various [j] of the fabrics of this defense that have been subjected to iFJ.In addition, we investigated the effect of aging time on bending resistance by changing the aging time from 3 to 8 hours, but the aging time Q: What is the difference in bending resistance due to shortening? I
I was not placed in dormitory A.

Example 3 Crude amidophosphazene compound 1 Hehe-1000ALotNO, GB-0345 manufactured by Nippon Kaida Co., Ltd., 42% of amidophosphazene compound, about 58% ammonium chloride 1
An aqueous solution containing 130 g/l of nonionic penetrant 2'j/1 was prepared, and the aqueous solution was aged at 15° C. for 9 hours, and the pick-up after squeezing the aqueous solution with a 5×68 piece of Polynosic 100% fabric was 115%.

Next, after drying at 100°C for 7 minutes, drying at 155°C for 2.
Heat treatment was performed for 5 minutes. It was then washed with hot water and dried. Table 1 shows the various properties γ1 of the fabric of the present invention.

Example 4 Crude amidophosphazene compound [A manufactured by Japan fIdatsu Co., Ltd.
A-3000ALOtNO, GB-025, amidophosfavine compound 97.1%, ammonium chloride approx. 29
%] An aqueous solution containing 10'lJ/1 of 55g/l phosphoric acid was prepared and aged at 45°C for 21J6 hours.
It was 11%. Next, after drying at 105°C for 5 minutes, heat treatment was performed at 160°C for 2 minutes. It was then washed with hot water and dried. Table 1 shows the various properties of the obtained fabric of the present invention.

Comparative Example 1 The same method as in Example 1 was carried out except that no aging was performed. The first person to purchase the fabric was Nagisatake.

Comparison 12 The same method as in Example 2 was carried out except that ripening was not performed. 4.14 The properties of the fabrics obtained are shown in Table 1.

Comparative Example 3 Commercially available non-formalin resin processing agent Beckamine NF-5 (manufactured by Dainippon Ink & Chemicals Co., Ltd.) 100 g/l, Ki17
Talist GT (manufactured by Jinjiki Ink Chemical Industry Co., Ltd.) 40
After brewing the same sfumos as in Example 2 in an aqueous solution containing g/l and 3 g/l of a nonionic penetrant and squeezing it with a mangle, the pick-up was 95%. Table 1 shows the properties of the fabrics obtained by drying at 100°C for 5 minutes and heat treating at 155°C for 2 minutes.

Comparative PA4 Table 1 shows the properties of the fabric obtained in the same manner as in Example 3 except that aging was not performed.

Comparative pA5 Table 1 shows the properties of the fabric obtained in the same manner as in Example 4 except that aging was not performed.

Table 1 Example 5 Crude amidophosphazene compound [Lot No. FC-028, manufactured by J Kokudatsu Co., Ltd., 42% of phosphoric acid amide compound, ammonium chloride [approximately 58% of chives]] An aqueous solution of an aqueous solution of an amidophosphazene compound dissolved in an aqueous ammonia solution with a concentration of 400 g/β of a crude amidophosphazene compound and aged at 50°C for 23 hours - the NMR curve of 311 of this aqueous solution is the 9th As shown in the figure -
Dilute it 4.42 times with water, and add 70% polynosic 100% fabric weight 70J/7FL2 scouring J-ri fabric to the diluted solution.
M The pickup after squeezing with the crushing mangle is 11.2
%Met. Next, after drying, it was heat-treated (cured) at 150° C. for 4 minutes. Then, it was washed with hot water and dried. Table 2 shows the properties of the obtained fabric of the present invention.

Example 6 Crude? Midophosphagen compound [manufactured by Hiki Kodatsu Co., Ltd. L
0.1% of FC-028, 42% of amidophosphazene compounds, about 58% of ammonium chloride
An aqueous solution of an amidophosphazene compound dissolved in an ammonia aqueous solution and made up of 400 g/1 crude amidophosphazene compound was aged at 50°C for 24 hours, and the aqueous solution was diluted 4.42 times with water. In the liquid, Pola 19fu 9
The pickup after narrowing down to 100 angles was 11.4%. Next, after drying, heat treatment (cure) at 150℃ for 3 minutes
did. After that, it was washed with hot water and dried. Table 2 shows the properties of the obtained fabric of the present invention.

Example 7 Japanese amidophosphazene compound [Japanese version 1 'I: (
Co., Ltd. Lot No. FC-028, amitoposph 7-pin compound approx. 42%, ammonium chloride approx. 58%1
was dissolved in 1% thorium carbonate aqueous solution and 400Sl/
An aqueous solution of 1 ift of the crude amidophosphazene compound of 1 was added at 50°C to 2.
The aqueous solution aged for 4 hours was diluted with water to 4.42-8, and the diluted solution was added with polynosic 100% fabric weight approximately 70 sh/Tr.
The pick-up after the L2 hot wire fabric was dipped and squeezed with a mangle was 11.1%. Next, after drying, 155℃
It was cured for 3 minutes. After that, I washed it in place and dried it.7. The properties of the obtained fabric of the present invention are shown in Table M2.
.

Example 8 Crude amidophosphagen compound [L manufactured by Nippon Soda Co., Ltd.
ot No. FC-028, amide small spphapine compound 42%, ammonium chloride approximately 58% 1 dissolved in water and 400! 7/1 crude amidophosfapine compound in water. An aqueous solution obtained by aging RA liquid at 50°C for 48 hours was mixed with water for 4.4 hours. -12 times diluted, Pola 19F 9100 live wire up fabric was immersed in the diluted solution and squeezed with a mangle, the pickup was 11.5%. Next, after drying, it was heat-treated (cured) at 145° C. for 5 minutes. Then, it was washed and dried.

Table 2 shows the properties of the obtained cloth of the present invention.

Comparative Example 6 Crude amidophosphazene compound [manufactured by Nippon Soda Co., Ltd. 1]
．． ot No. FC-028] was used, no aging was performed - the N M l of 31P of this aqueous solution < curve t is shown in Figure 6 - and the same as Example 8 except that it was diluted 3.36 times with water. This was done using the h method.

Table 2 shows the properties of the fabric obtained.

Example 9 Crude amidophosphazene compound [1-1 Lot No. manufactured by Honsoda Co., Ltd. GB-003, amidophosphazene compound 42%, ammonium chloride approximately 58% 1 to 1
Of the crude amidophosphan-based compound dissolved in a 4% ammonia aqueous solution at a concentration of 400 l/1! ! Aqueous solution of amidophosfavine compound at 50"C x 2 4 rfI
Aqueous solution aged for 31 p o]N M of this aqueous solution
The R db line is obtained by diluting the gas shown in Figure 5 4.80 times with water, and adding Pola 19F Fii! to the diluted solution. The pickup after narrowing down with i Simangle was 11.2%. Next, after drying, heat treatment (cure) was performed at 150°C for 4 minutes.
，After that, it was fried, washed and dried. The properties of the obtained fabric of the present invention are shown in Table 2/B4.

Example 10 Crude amidophosphazene compound 1 day L manufactured by Kishitatsu Co., Ltd.
4. Ot No., GB-003, 42% of amidophosphazene compound, about 58% of ammonium chloride] was dissolved in 0.5% phosphoric acid aqueous solution. An aqueous solution of an amidophosphazene compound, which was used as an affl of 0 0 9 /l of a crude amidophosphazene compound, was aged at 45°0 for 16 hours. The aqueous solution was diluted 4.31 times with water, and a positive solution was added to the diluted solution. The pick-up after soaking the live wire up fabric of 19ft 0100t1 about 70g/rrL2 and squeezing it with a mangle is 11.
It was 3%. Next, after drying, heat treatment at 150℃ for 4 minutes for 11J
F (cured).Then, it was washed and dried.The properties of the obtained fabric of the present invention are shown in Table 2.

Example 11 Crude amidophosphazene compound L manufactured by Nippon Soda Co., Ltd.
ot No. GB-003, amide phosphazene compound 42%, ammonium chloride approx. 58% 1 was dissolved in water to give a crude amidophosphazene compound concentration of 400 y/i, and an aqueous solution of amide 11\suphagene compound 2
The aqueous solution aged at 0°C for 330 days was diluted 4.67 times with water, and the diluted solution was added with polynosic 100% fabric weight approximately 7.
0: t/m2 scouring", the pick-up after soaking the fabric and squeezing it with a mangle was 11.5%. Next, after drying, it was heat-treated (cured) at 150° C. for 4 minutes. Afterwards, it was washed and dried. (Table 2 shows the properties of the smoothed fabric of the present invention.

Comparison 1917 Crude amidophosphagen compound 1 day tut-ot No. G B OO3] was used and no ripening was carried out.The NMR curve of 31P of this aqueous solution is shown in Fig. 11. and tj by the same tj method as in Example 11, except that it was diluted 3.29 times with water.

The properties of the fabric obtained are not shown in Table 2.

Example 12 Amidophosphazene compound 1 Lot manufactured by Japan Yosso Co., Ltd.
No. FB-03, 94% amidophosphagen compound, about 6% ammonium j-chloride 1 was dissolved in 1% ammonia + 5% magnesium chloride aqueous solution,
An aqueous solution of an amidobosphazene compound with a 1:1 concentration of 7 midophosphagene compounds was aged at 10°C for 80 days, and the aqueous solution was diluted 9.4 times with water, and polynosic was added to the diluted solution. 100% A1 A live wire fabric of about 70 g/TrL2 was soaked and squeezed with a mangle. Next, after drying, 1
Heat treatment at 55℃ for 3 minutes II! (cure). Afterwards, it was washed and dried. The properties of the obtained fabric of the present invention were
Shown in the table.

Comparative Example 8 The same method as in Example 12 was carried out except that aging was not performed. Table 2 shows the properties of the fabric obtained.

Example 13 Crude amidophosphagen compound [L manufactured by Usuki Daitatsu Co., Ltd.
Amidophosphazene was prepared by dissolving 42% of the amidophosphazene compound and about 58% of ammonium chloride in a 2% ammonium acetate aqueous solution to give a concentration of the crude amidophosphazene compound of 35) Ov/Il. The aqueous solution of the compound was aged at 5°C with Cl2O for 420 times, and the diluted solution was added with 10% hemp.
0% fl approx. 200! The pick-up after f/TrL2 dyed fabric was dipped and squeezed with a mangle was 80%. Next, after drying, heat treatment was performed at 145° C. for 6 minutes (J-17>).

Afterwards, it was washed and dried. Table 2 shows the properties of the obtained fabric of the present invention.

Comparative Example 9 The same method as in Example 13 was carried out except that no aging was performed and the mixture was diluted 2.94 times with water.

V) Properties of the resulting fabric are shown in Table 2.

Example 14 Crude amidophosphazene compound 1 day L manufactured by Kiso Tatsu Co., Ltd.
ot No, EL-20, about 58% amidophosphazene compound, about 42% ammonium chloride 1 was dissolved in 1% diammonium hydrogen phosphate aqueous solution to give a crude concentration of 200 g/l of amidophosphazene compound. An aqueous solution of a phosphazene compound aged at 15°C for 60 days was diluted 1.66 times with water, and a 100% cotton fabric with a fabric weight of approximately 170 y/y/L2 was immersed in the diluted solution. The pick-up rate for the mangled manga was 8.5%. Next, after drying, it was heat treated at 155° C. for 3 minutes (Kikoa). Then, it was fried, washed and dried.

1! Table 2 shows the properties of the 4II fabric of the present invention.

Comparative Example 10 The same method as in Example 14 was carried out except that no aging was performed and the mixture was diluted 1.36 times with water.

(!The various qualities of the fabrics obtained are shown in Table 2.

Example 15 The processed fabrics of Examples 5 to 9 and the processed fabrics were
Page 1 Q-bu [The cloth to be washed 30 times by the method described in Washing 1 is used as the test cloth, and a part of the test cloth is washed with human blood,
It was contaminated by soaking it in sauce, soybean oil, ketchup, and fluorescent dye R1, and then it was taken out and hung to dry for 12 hours at room temperature.

Method for washing contaminated processed cloth at home JIS L 021
7. Washing was carried out using a home washing machine according to method 103 under the following conditions.

Bath ratio 1:30 Kao Seki [)n Co., Ltd. commercial product "New Beads 1"
0.1%, 2 times at a temperature of 40℃ (5 minutes), rinsed at room temperature for 2 minutes), dehydrated and dried for 1℃. The 11゛P value determined by the gray scale determination method is shown in Table 3.

(If the dyed material is a fluorescent dye, the test cloth was washed 30 times in accordance with the home washing method JIS 1.0217 103 using a home washing machine under the following conditions; Ratio: 1:30, fluorescent agent-containing detergent (Flower)-6 commercially available crystals manufactured by Ken Co., Ltd. 1-New Beads 1): 0.2%, temperature 40
°C (5 minutes), ) V: Dehydrated and dried twice at room temperature (2 minutes).

The processed fabric after washing was evaluated using the Japanese Standards Association's color fastness test and gray scale judgment method for staining.
were processed and evaluated. The results are shown in Table 3.

3k [Effect of the invention] First, the shrinkage rate in the warp direction after dyeing and washing 45 times for fabric L fabric is 14% Pillf, but when this is added with a commercially available specific formalin resin finishing agent, it becomes 6% Pillf. % (Table 1 Comparative Example 3 @ Teru).

However, in the present invention, by adopting the above configuration,
This will further reduce the shrinkage rate to around 2% (
(See Example 2 in Table 1), the processing agent of the present invention is clearly superior1, and in this case, the processing agent of the present invention has a low bending resistance (the smaller the value is, the more flexible it is) and is flexible. 11Next, in a comparison of cases in which an amidophosphagen compound is used and is aged (Examples 5 to 14 in Table 2) and cases in which it is not aged (Comparative Examples 6 to 10 in Table 2), after 45 washes, Although there is no particular difference in shrinkage rate, there is a considerable difference in abrasion strength and bending properties, and the present invention is superior.

Inventive C is also improved in varus. Furthermore, as can be seen from the conclusion of Table 3, the processed fabric of the present invention has excellent stain resistance against stains such as fluorescent dyes, human blood, and sauces.
, equipped with bamboo. Thus, the properties are improved and the non-formalin fit is flexible, especially for infants and children's clothing.

It can be said to be extremely useful for use in clothing that comes directly onto the skin, such as pajamas, lingerie, bed sheets, blouses, and dress shirts.

[Brief explanation of drawings]

Figure 1 shows 3 unripened crude amidobosphazene compounds.
Figure 2 shows the NMR curve of 1P. Figure 2 shows the same amidophosphazene compound as in Figure 1 dissolved in 14% aqueous ammonia to give a concentration of 400 g/l of the crude amidophosphazene compound. 5 aqueous solution
3IP NMR+lt aged at 0°C for 1 hour
＋I! iI is a dimensional diagram, Figure 3 is a diagram showing the NMR curve of 3IP after aging the same aqueous solution of the amidophosphazene compound used in Figure 2 for 6 hours, and Figure 4 is a diagram showing the NMR curve of 5.
Figures showing the NMR curve of 31P after aging at 0°C for 12 hours and Figure 5 show the results after aging at 50°C for 241 hours. Next, FIG. 6 is a diagram showing an unripened 31P(7) NMR curve of a crude amidophosphazene compound of a different Lot No. from the amidophosnoapine compound used in FIG. 1, Figures 7 to 15 show the same amidophosnoapinic compounds used in Figure 6 in each water. Figure 7 shows the NMR curves of 31P obtained by dissolving the crude 7 midophosnoane compound in a solution of 400 g/1 and aging under the respective conditions. An amidophosphazene compound was dissolved in 10% aqueous ammonia and aged at 5) 0°C for 24 hours. At 8511. Figure 9 is a diagram of an amidophosfavine compound dissolved in 1% 7N water and aged at 50°C for 231 hours, and Figure 10 is a diagram of an amidophosnopine. Fig. 11 (jAmidophosphazene compound dissolved in 0.1% ammonia solution and aged at 50°C for 69 hours) 851jJ lff1 Figure 12 is a diagram of an amidophosphazene-based IL'1 compound dissolved in a 1% phosphoric acid aqueous solution and aged at 50°C for 60 hours, and Figure 13 is a diagram of an amidophosphazene-based IL'1 compound dissolved in water. Dissolve at 5
It is a diagram of the product aged at 0° C. for 36 hours. Also, the first
Figure 4 shows the amide/1\sphazene compound with 1% acetic acid [
7% 'C was dissolved in Nia water and aged at 60°C for 15 hours, and then further aged at 20°C for 10 days. 45th
The figure shows 10% of a 7-midobosphazene compound dissolved in near water and aged at 20° C. for 201 hours. FIG. 16 shows Lot N different from the amidophosfabine compound used in FIGS. 1 and 6.

Claims (3)

[Claims] (1) A processing agent for cellulose-based materials whose main component is an aqueous solution of an aged amidophosphazene compound. (2) A method for processing a cellulose fabric, which comprises adhering an aqueous solution of an aged amidophosphazene compound as a main component to a cellulose fabric, and then heat-treating the fabric. (3) A soft, stain-resistant, shrink-proof cellulose fabric treated with a processing agent whose main component is an aqueous solution of an aged amidophosphazene compound.