JP2517993B2 - Fabric shrink-proofing composition and shrink-proofing method - Google Patents

Description

TECHNICAL FIELD The present invention relates to a shrink-proofing composition for a cloth and a method for shrink-proofing a cloth containing a cellulosic fiber using the composition.

[Conventional technology]

A processing agent such as aminoplast resin is commercially available as a processing agent that prevents the shrinkage that occurs during repeated washing of a fabric containing cellulosic fibers. However, the fabric processed with these processing agents may release formaldehyde when worn and cause skin damage. In recent years, non-formaldehyde-based resins have been marketed in order to avoid the above-mentioned skin disorders, but they have little effect of preventing shrinkage that occurs during repeated washing. That is, a composition which is non-formaldehyde-based, has a soft texture, and has a very small shrinkage factor upon repeated washing, and a composition which can give a fabric containing the cellulosic fiber, and a shrink-proofing treatment of the fabric containing the cellulosic fiber by the composition. No way has been found.

[Problems to be solved by the invention]

The present invention solves the above-mentioned problems of the prior art, that is, it is possible to obtain a fabric containing a cellulosic fiber which is a non-formaldehyde type, has a soft texture, and has a very small shrinkage factor when repeatedly washed. A possible composition and a method of processing said fabric with such a composition are aimed at.

[Means for solving problems]

The present inventor is keen to develop a composition which is non-formaldehyde-based, has a soft texture, and has a very small shrinkage factor upon repeated washing, and a method for processing the composition by using such a composition. As a result of the research, the above object was achieved by treating a fabric with a composition comprising an acid catalyst and an amide phosphazene derivative in which a part of the acid group of the amide phosphazene compound was substituted with another substituent. The present invention has been discovered and the present invention has been reached.

That is, the present invention provides: (1) Formula N = P) _n (NH ₂ ) _a R _b (wherein R is a lower alkoxy group which may have a substituent or a phenoxy group which may have a substituent). A mono-lower alkylamino group or a di-lower alkylamino group, n is an integer of 3 or more, b is an integer of 1 or more, a + b = 2n, and a / b ≧ 1 One or two of the amidophosphazene derivatives represented by
A composition for shrink-proofing fabric, containing at least one species and an acidic catalyst; and (2) Formula N = P) _n (NH ₂ ) _a R _b (wherein R is a lower group which may have a substituent). An alkoxy group, a phenoxy group which may have a substituent, a mono-lower alkylamino group, or a di-lower alkylamino group, n is an integer of 3 or more, and b is an integer of 1 or more. , A + b = 2n, and a / b ≧ 1) one or two of the amidophosphazene derivatives represented by
The present invention relates to a method for shrink-proofing a fabric, which comprises depositing an aqueous solution containing one or more species and an acidic catalyst on a fabric containing cellulosic fibers, and then heat treating the fabric.

As used in the present invention, the formula N = P) _n (NH ₂ ) _a R _b (In the formula, R is a lower alkoxy group which may have a substituent, a phenoxy group which may have a substituent, or mono. A lower alkylamino group or a di-lower alkylamino group, n is an integer of 3 or more, b is an integer of 1 or more, a + b = 2n, and a / b ≧ 1) The amidophosphazene derivative represented by the formula is obtained by a reaction of phosphorus pentachloride and ammonium chloride, A chlorophosphazene oligomer represented by the formula (wherein n is the same as defined above) and a lower aliphatic alcohol, a phenol, a mono-lower alkylamine or a di-lower alkylamine which gives a group R, And by reacting with ammonia.

The chlorophosphazene oligomer has the formula A cyclic trimer having It is obtained as a mixture of a cyclic tetramer having, and a high molecular cyclic body and a chain body. To prepare the amide phosphazene derivative used in the present invention, this mixture can be used as it is. Well, or a cyclic trimer or cyclic tetramer purified and separated from the mixture may be used.

Examples of the lower aliphatic alcohols to be reacted with these chlorophosphazene oligomers include methanol,
There are ethanol, propanol, butanol, pentanol, and isomers thereof, and these alcohols may have a halogen atom, a lower alkoxy group, a nitro group, a cyano group or the like as a substituent, and as a phenol, Is a phenol derivative having a phenol atom and a halogen atom, a lower alkyl group, a nitro group, a cyano group, or an alkoxycarbonyl group as a substituent, and as an alkyl group of mono-lower alkylamines or di-lower alkylamines, , Methyl, ethyl, propyl, butyl, and pentyl groups, and their isomers.

The order of reacting the chlorophosphazene oligomer with these alcohols, phenols or amines and ammonia may be any order, but in order to facilitate controlling the amount of the group R in the product to the desired amount. Advantageously, the alcohols, phenols or amines are reacted first.

To react alcohols with a chlorophosphazene oligomer, tertiary amines such as pyridine, picoline, quinoline and triethylamine, or potassium hydroxide, sodium hydroxide, potassium carbonate, sodium carbonate, etc. can be used in an inert organic solvent. Is used as a deoxidizing agent. In order to react the phenols, they are converted into potassium or sodium phenolate, and the reaction is also carried out in an inert organic solvent. Even when reacting amines, double the calculated amount of amines to be reacted in an inert organic solvent to serve as a deoxidizing agent, or as in the case of phenols. The reaction is carried out using a tertiary amine or an inorganic base as a deoxidizing agent.

In these reactions, the reaction temperature does not need to be particularly limited, but in the products reacted at a high temperature, for example, P-
Polymers due to intermolecular cross-linking such as OP are mixed and produced, and the mixture of such polymers impairs the texture of the final treated fabric (however, there is no adverse effect on the shrinkproof effect).
A reaction at 60 ° C or lower is preferable.

In these reactions, the amount of alcohols, phenols or amines used is determined based on the structure of the desired amidophosphazene derivative.

After completion of these reactions, the reaction solution is filtered to remove by-produced tertiary amine hydrochloride or inorganic salts, and then reacted with ammonia. That is, the reaction liquid from which the by-products have been removed is transferred into an autoclave, and 2 equivalents or more of ammonia gas is blown into the chlorine atom remaining in the phosphazene while stirring. The temperature at this time is also preferably 60 ° C. or lower as above. After completion of blowing, the autoclave is closed, and stirring is continued under pressure at a temperature of 60 ° C. or lower for a while to complete the reaction. Then, excess ammonia is degassed, and the produced white crystals are collected by filtration and dried under reduced pressure at a temperature of 60 ° C. or less to obtain a mixture of the desired amidophosphazene derivative and ammonium chloride.

By treating this mixture with liquid ammonia, ammonium chloride soluble in it can be removed to obtain a pure amidophosphazene derivative, but in the present invention, it is not necessary to specifically remove this ammonium chloride. Rather, this ammonium chloride serves as an acidic catalyst in the shrinkproofing process of the present invention.

The amide phosphazene derivative thus obtained is a substance that is easily hydrolyzed, and is not affected by moisture in the air not only in the aqueous solution used for shrink-proofing but also in the post-treatment of the manufacturing process. I may receive it.
However, if the degree of hydrolysis is not significant, it does not significantly affect the shrinkproof effect.

The shrinkproof fabric obtained by the present invention is superior in mechanical properties such as tensile strength and frictional strength to the shrinkproof fabric obtained by treating with an aqueous solution of an amide phosphazene compound. This effect is presumed to be due to the substituent R. Regarding b representing the degree of substitution of the substituent R, a / b <
In the case of 1, the amide phosphazene derivative becomes difficult to dissolve in water, and when a / b is large, the effect of the substituent is small, and the preferable degree of substitution is 2 <a / b <5.

Examples of the base material, which is the fiber base material of the cloth used in the present invention, include cellulosic natural fibers such as cotton and hemp, and regenerated fibers such as rayon, kyupura, sufu, and polynodic. In addition, a small amount of fibers other than the base material, for example, organic synthetic fibers such as polyamide, polyester, polyacrylonitrile, polypropylene and spandex, glass fibers, carbon fibers, and inorganic synthetic fibers such as silicon carbide fibers. May be mixed, and the cloth may be woven, knitted,
It may be in any form such as non-woven fabric, resin-processed fabric, and sewn products.

The acidic catalyst used in the present invention is all effective as long as it is an acidic catalyst used for resin processing of cloth,
For example, catalysts such as diammonium phosphate, ammonium chloride, organic amine hydrochloride, zinc chloride, magnesium chloride, zinc nitrate, zinc tetrafluoride, hydrochloric acid and phosphoric acid are preferable.

In the shrink-proofing method of the present invention, the fabric is treated with an aqueous solution in which at least one of the above-mentioned amidophosphazene derivative and at least one of the acidic catalyst are dissolved. To this aqueous solution, a small amount of a resin processing agent, a softening agent, a penetrating agent, a water repellent, and / or a cellulose cross-linking agent may be added. The concentration of the amide phosphazene derivative in the aqueous solution is preferably 50-250 g /, particularly preferably 55
It is ~ 70g /. The concentration of the acidic catalyst is preferably 1-140 g /, particularly preferably 5-100 g /.
Is.

As a method for attaching the aqueous solution to the cloth, it can be carried out by immersing the cloth in the aqueous solution and then squeezing the cloth as it is or by squeezing it with a roll or mangle, spraying the aqueous solution onto the cloth, or the like.

The aqueous solution is attached to the cloth, and then heat treatment is performed.
As the heat treatment method, any heat source such as hot air, infrared rays, micro-webs, and steam can be used. 1
The heat treatment may be performed once, or the heat treatment may be performed twice or more. The temperature of the heat treatment is preferably 50 to 190 ° C, particularly preferably 120 ° to 160 ° C. The preferred heat treatment time is 1
~ 30 minutes, particularly preferably 2-10 minutes. Regarding the temperature and the time, conditions that do not damage the fabric may be appropriately selected. The heat treatment makes the composition sparingly soluble in water and fixes it on the fabric. After the heat treatment, it is preferable to remove the water-soluble components in the cloth by washing with hot water or the like. The preferable phosphorus content in the cloth is 0.05 to 4.0% by weight,
It is particularly preferably 1 to 2% by weight.

The phosphorus content weight% measurement method, the free formaldehyde measurement method, the shrinkage rate measurement method after 45 times of washing, and the bending resistance measurement method are as follows.

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

Sulfuric Acid Decomposition-Measurement of Phosphorus Content in Cloth by Colorimetric Method Reagents 1. Sulfuric acid for precision analysis (reagent grade 98%) 2.60% Perchloric acid 3. Ammonium molybdate solution: Ammonium molybdate (reagent grade 1) 17.7 Dissolve g in water to make 500 ml.

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 instruments Chemical balance, 50 ml Kjeldahl flask, 10 ml hall pipette, 5 ml hall pipette, Kjeldahl thermal decomposition table, 2
5ml volumetric flask, 50ml volumetric flask, 50ml volumetric cylinder, 500ml volumetric flask, 100ml volumetric cylinder, zeolite, spectrophotometer.

Operation 1. Decomposition treatment of sample 200-300 mg of absolutely dry sample is precisely weighed using an analytical balance and 50 ml.
Collect in a Kjeldahl flask. Add 5 ml of water, 5 ml of sulfuric acid, and 2 to 3 grains of zeolite (glass), and set on a Kjeldahl thermal decomposition table to decompose by heating. When the sample carbonizes and dissolves in sulfuric acid to give a brown color (for about 30 minutes after the start of heating), the heating is stopped, the mixture is allowed to cool for 5 minutes, 3 drops of 60% perchloric acid are added, and it is again decomposed by heating.
Repeat the heating decomposition-cooling perchloric acid addition operation until the decomposition liquid becomes colorless and transparent, and completely decompose. After cooling to room temperature, the decomposition solution is washed with water in a 25 ml volumetric flask and diluted to the balance line.

2.Measurement Decomposition solution is weighed in a 50 ml volumetric flask according to the estimated phosphorus content, and after adding 30 ml of water, 5 ml of ammonium molybdate solution and 5 ml of ammonium metavanadate solution are added,
Dilute with water to the balance line. Perform the Blank test in the same way in parallel. After standing for 30 minutes, the absorbance at 400 nm is measured using Blank as a control solution.

Estimated phosphorus content Decomposition solution collection amount 0.5 to 15% 0.5 ml 0.1 to 3% 2.5 ml 3.Calculation The phosphorus content of the work cloth is 3% or less, so 2.5 ml of the decomposition solution is applied and calculated by the following calculation.

(2) Measurement method of free formaldehyde JIS L-1096-1979 6.3.9.1.2 (1) The measurement was carried out by the B-1 method.

(3) Method of measuring shrinkage after 45 times of washing (a) How to collect a sample and make a test piece 40 x 40 cm test piece depending on how to make a sample and a test piece described in JIS L-1042-1988: 7 It was created.

(B) Washing: Fire Service Notification No. 11 dated June 1, 1973, "Standards for anti-washing performance related to flameproof performance (hereinafter referred to as" Notification No. 11 ")
According to the test method of washing with water, the procedure was as follows.

(I) The washing time is continuous with the liquid at 60 ° C for 75 minutes. In addition, in the method of Notification No. 11, the washing time is 15 minutes, but in this method, 15 minutes x 5 (times) = 75 minutes.

Except for the washing time, the washing test method is the same as in Notification No. 11. However, the detergent should be powder-washed (JIS
1 type specified in K 3303), and 1 g per 1 water was used.

(Ii) Washing method of (i) (water supply at 60 ° C → detergent addition →
Put test sample → Let's wash for 75 minutes with 60 ℃ liquid → Drainage / water supply
Rinse with water at 40 ° C for 5 minutes x 3 times → Drain → Dewater 2 minutes → 60
(° C drying) was repeated 9 times. Since the washing test of (i) corresponds to 5 repetitions, this is repeated 9 times, which corresponds to a total of 45 repetitions.

(C) Measurement A washing machine was used, and the measurement was carried out according to the measurement method described in JIS L-1042-1983: 9.

(D) Calculation The calculation method described in JIS L-1042-1083: 10 was used. That is, the average value of the lengths of three lines for each of the vertical and horizontal lines was calculated, the shrinkage ratio was calculated by the following formula, and the average value of the vertical and horizontal lines was expressed three times.

Where L: length before washing (mm) L ': length after washing (mm) _{1: n = P n (NH} 2) 2 / 3n (n (C 2 H 5) 2) 1/3
n (amino-diethylaminophosphazene oligomer)
Synthesis of Chlorophosphazene (cyclic trimer 53.6) prepared by a conventional method using phosphorus pentachloride and ammonium chloride as raw materials
%, Cyclic tetramer 15.5%, other chlorophosphazene 3
0.9% mixture) 100 g [all chlorophosphazenes (N is an integer greater than or equal to 3) chlorine atom 1.724
Mol.) Was dissolved in 300 ml of monochlorobenzene,
With stirring while cooling with ice water, 84.2 g of diethylamine (1.1
(52 mol) was added dropwise. The temperature of the reaction solution rose to around 20 ° C. After completion of dropping, the mixture was further stirred at room temperature for 2 hours, and then the precipitated crystals of diethylamine hydrochloride were filtered off,
The filtrate was transferred to an autoclave, and ammonia gas was 51.4g.
(3.024 mol) was bubbled in at a temperature below 20 ° C. for 2 hours. The autoclave was closed and aged for 1 hour. The internal pressure at the end of aging was 3.0 kg / cm ² .

The autoclave was opened, ammonia was degassed, and the precipitated crystals were collected by filtration and dried under reduced pressure at a temperature of 50 ° C. to obtain 139 g of a desired mixture of an amidophosphazene derivative and ammonium chloride. The composition of this mixture was 60.5% amidophosphazene derivative and 39.5% ammonium chloride, and the analytical value of amidophosphazene was as follows.

P (%) N (%) C (%) H (%) Analytical value 18.7 28.98 15.71 7.31 Theoretical value 20 32.56 16.93 7.86 That is, the amidophosphazene derivative obtained here was almost the same as the target substance. .

Synthesis Example 2: Synthesis of tetraamino-di-n-propoxycyclotriphosphazene 100 g (0.288 mol) of cyclic chlorotriphosphazene and 39.7 g (0.583 mol) of pyridine are added to 400 ml of monochlorobenzene.
35 g of n-propanol while cooling with ice water
(0.583 mol) was added dropwise with stirring, and the stirring was continued at room temperature for 2 hours. Then, the precipitated crystals of pyridine hydrochloride are removed by filtration, and then the same procedure as in Synthesis Example 1 is carried out to carry out the desired mixture of the amidophosphazene derivative and ammonium chloride.
Obtained 105 g. The composition of this mixture was 45.3% amidophosphazene derivative and 54.7% ammonium chloride, and the analytical values of the amidophosphazene derivative were as follows.

P (%) N (%) C (%) H (%) Analytical value 16.4 28.99 11.36 6.48 Theoretical value 17.5 28.31 10.29 6.48 That is, the amidophosphazene derivative obtained here was almost the same as the target substance. .

Synthesis Example 3: Synthesis of pentaamino-monophenoxycyclotriphosphazene 100 g (0.288 mol) of cyclic chlorotriphosphazene was dissolved in 300 ml of monochlorobenzene, 38.1 g (0.288 mol) of potassium phenolate was added, and 50 ° to 60 ° C. Stirring was continued for 3 hours at the temperature. Then, the precipitated crystals of potassium chloride were filtered off, the filtrate was transferred to an autoclave, and then the reaction with ammonia was carried out according to Synthesis Example 1. The product was collected by filtration and dried to obtain 151.3 g of a mixture of the desired amidophosphazene derivative and ammonium chloride.The composition of this mixture was: amidophosphazene derivative 48.6% ammonium chloride 51.4%. The analytical values of the derivative were as follows.

P (%) N (%) C (%) H (%) Analytical value 15.1 30.54 7.34 5.27 Theoretical value 16.2 31.12 11.36 6.21 That is, the amidophosphazene derivative obtained here was almost the same as the target substance. .

Example 1 170 g of a mixture of the amidophosphazene derivative obtained in Synthesis Example 1 and ammonium chloride and 3.0 g of a nonionic penetrant (Adecatol NP-690 manufactured by Asahi Denka Co., Ltd.) were dissolved in water 1 to prepare an aqueous solution of Sufmos. The pick-up after immersing the dyed swelling and squeezing with the mangle was 100%. Next, after drying at 100 ℃ for 5 minutes, 150
It heat-processed at 3 degreeC for 3 minutes. Then, it was washed with hot water and dried.
The properties of the obtained fabric are shown in Table 1.

Comparative Example 1 Commercially available non-formalin resin finishing agent Betukamin NF-5 (manufactured by Dainippon Ink and Chemicals, Inc.) 130 g, KYATARISTO GT
Example 1 was added to an aqueous solution prepared by dissolving 40 g (manufactured by Dainippon Ink and Chemicals, Inc.) and ADEKATOL NP-6903 g in water 1.
After dipping Sufmos similar to the above and squeezing with mangle, the pickup was 100. Next, various properties of the cloth obtained by drying at 100 ° C. for 6 minutes and then heat-treating at 155 ° C. for 4 minutes are shown in Table 1. It became a little harder due to the processing, and the drape characteristic peculiar to Sufmos was lost.

Example 2 190 g of a mixture of the amidophosphazene derivative obtained in Synthesis Example 2 and ammonium chloride, 10 g of phosphoric acid and 3 g of ADECATOL NP-690 were dissolved in water 1 to prepare an aqueous solution containing 100% cotton.
Katsuragi The pick-up after dipping and squeezing at the angle was 95%. Then, after drying at 100 ℃ for 10 minutes,
Heat treatment was performed at ℃ for 3 minutes, then washed with hot water and dried. The properties of the obtained fabric of the present invention are shown in Table 1.

Comparative Example 2 A non-formalin-based cotton finishing agent (Betcamine NF-8, manufactured by Dainippon Ink and Chemicals, Inc.) 150 g, KYATARIST GT40 g, and ADEKA TOL NP-690 3 g were used to dye the same cotton fabric as in Example 2. The pick-up after dipping in an aqueous solution dissolved in water 1 and squeezing with a mangle was 90%. Then, the properties of the product obtained by the same treatment as in Example 2 are shown in Table 1.

Example 3 180 g of a mixture of the amidophosphazene derivative obtained in Synthesis Example 3 and ammonium chloride, and adecatol NP-
690 Scouring of a woven fabric using a spun yarn consisting of 70% viscose rayon staple and 30% polyester in an aqueous solution prepared by dissolving 3 g of water in 1 of water. After picking up and squeezing with mangle, pickup is 105%
It was. Next, it was dried at 100 ° C. for 3 minutes and then heat-treated at 150 ° C. for 3 minutes. Then, it was washed with hot water and dried. The properties of the obtained fabric of the present invention are shown in Table 1.

Comparative Example 3 Various properties of a fabric obtained by performing the same processing as in Comparative Example 1 using the same fabric as in Example 3 are shown in Table 1.

[Effects of the Invention] As is clear from the above description, the fabric processed with the composition of the present invention has a very small shrinkage factor due to repeated washing, is non-formalin and has a soft texture, and therefore is suitable for infants' clothing and pajyama. Clothes that come into direct contact with the skin, such as skin, lungiery and bet sheets, are extremely versatile.

Claims (2)

(57) [Claims] 1. A compound represented by the formula: N = P) _n (NH ₂ ) _a R _b (wherein R is a lower alkoxy group which may have a substituent, a phenoxy group which may have a substituent, or a mono- A lower alkylamino group or a di-lower alkylamino group, n is an integer of 3 or more, b is an integer of 1 or more, a + b = 2n, and a / b ≧ 1) One or two of the represented amidophosphazene derivatives
A composition for shrink-proofing a fabric, which comprises one or more kinds and an acidic catalyst. 2. A compound represented by the formula: N = P) _n (NH ₂ ) _a R _b (wherein R is a lower alkoxy group which may have a substituent, a phenoxy group which may have a substituent, or a mono- A lower alkylamino group or a di-lower alkylamino group, n is an integer of 3 or more, b is an integer of 1 or more, a + b = 2n, and a / b ≧ 1) One or two of the represented amidophosphazene derivatives
A method for shrink-proofing a fabric, which comprises applying an aqueous solution containing one or more species and an acidic catalyst to a fabric containing cellulosic fibers, and then heat-treating the fabric.