JPH0565623B2 - - Google Patents

Description

[Detailed description of the invention]

[Industrial Application Field] The present invention is directed to knitted fabrics containing cellulose fibers,
An aqueous solution containing at least an amidophosphazene compound and an acidic catalyst is applied to the knitted fabric in an amount of 3 to 7% by weight of the amidophosphazene compound, followed by drying, curing, and subsequent soaping. The present invention relates to a method for processing knitted fabrics containing cellulose fibers. [Prior Art] U.S. Patent No. 2,782,133 discloses a method for flameproofing cellulosic products using a water-soluble substance obtained by reacting chlorphosphazene with anhydrous ammonia. There is no description of improving the progressive shrinkage rate of knitted fabrics containing cellulose fibers using an amidophosphazene compound. On the other hand, in order to improve the progressive shrinkage rate of knitted fabrics containing cellulose fibers, urea-formaldehyde, melamine-formaldehyde, methylated methylol melamine, dimethylol ethylene urea, dimethylol uron, tetramethylol acetylene diurea, dimethylol trichloride, Methods using aminoplast resin finishing agents such as azone and trimethylolmelamine, and glyoxal resin finishing agents have been carried out. However, these methods are not satisfactory, and it is desired to improve the progressive shrinkage rate of knitted fabrics made of recycled cellulose, such as viscose rayon, strong viscose rayon, polynosic, and kyupra. [Problems to be Solved by the Invention] Woven fabrics containing cellulose fibers have the disadvantage of so-called progressive shrinkage, in which the shrinkage rate gradually increases as the number of washings increases. Contractibility is large. [Means for Solving the Invention] According to the present invention, the above-mentioned disadvantages of knitted fabrics containing cellulose fibers can be solved by applying an aqueous solution containing at least an amidophosphazene compound and an acidic catalyst to the knitted fabrics containing cellulosic fibers. This can be prevented by adhering the phosphazene compound to the knitted fabric in an amount of 3 to 7% by weight, followed by drying, curing, and subsequent soaping. Woven fabrics containing cellulose fibers have progressive shrinkage properties, and their uses have been limited. In particular, recycled cellulose-based knitted fabrics have a high progressive shrinkage rate;
Knitted fabrics containing 65% or more are rarely used in fields where dimensional stability is required. The present inventors have conducted research on a method for flameproofing textiles containing cellulose fibers using amidophosphazene compounds, and have already applied for patents regarding the flameproofing method (Japanese Patent Application No. 60-103388,
103389, 60-219611 and 61-34799)
I'm running the number. In these patent applications, in order to achieve flame retardant performance, greater than about 10% by weight of an amidophosphazene compound is applied to the fabric, followed by drying, curing and subsequent soaping. However, during this research process,
The present inventors have discovered that the amidophosphazene compound 3-
The present inventors have discovered that when 7% by weight is attached to knitted fabrics, the progressive shrinkage rate of knitted fabrics containing cellulose fibers is significantly improved, and the present invention has been achieved. Further, according to the method of the present invention, in addition to improving the progressive shrinkage rate, wrinkles and fluffing after washing are also improved. That is, the present invention applies an aqueous solution containing at least an amidophosphazene compound and an acidic catalyst to a knitted fabric containing cellulose fibers so that the amount of the amidophosphazene compound adhering to the knitted fabric is 3 to 7% by weight. let me,
The present invention then relates to a method for processing a knitted fabric containing cellulose fibers, which is characterized by drying, curing, and subsequent soaping. Examples of cellulose fibers include viscose rayon filament, viscose rayon staple, strong viscose rayon filament, strong viscose rayon staple, polynosic,
Examples include Kyupra filament, Kyupra staple, acetate filament, and cotton. As for knitted fabrics containing cellulose fibers,
Examples include knitted fabrics made of 100% cellulose fibers, knitted fabrics obtained from yarns made by blending cellulose fibers with other fibers, and knitted fabrics obtained by blending cellulose fibers with other fibers. . Examples of knitted fabrics containing cellulose fibers for which the effects of the present invention are most noticeable include knitted fabrics containing 65% or more of viscose rayon, strong viscose rayon, polynosic, and kyupra. Woven fabrics containing prominent cellulosic fibers include knitted fabrics of viscose rayon, high strength viscose rayon, polynosic and 100% cupora. As the amidophosphazene compound used in the present invention, any water-soluble compound can be used. For example, general formula

Cyclic amidophosphazene compounds of [formula] (where x is a positive integer) or general formulas P _o N _o (NH ₂ ) _2o (2) and P _o N _o-1 (NH ₂ ) _2o+3
Linear amidophosphazene compounds of (3) (wherein n is a positive integer) can be used, and preferred cyclic amidophosphazene compounds include the following: 6-membered ring shown in , other 8-membered ring, 10-membered ring and
Examples include 12-membered rings. Preferred linear amidophosphazene compounds include those represented by the following formulas (5) to (9), but higher polymers can also be used. As the degree of polymerization of the amidophosphazene compound increases, the texture of the processed knitted fabric tends to become harder, but it is better in terms of progressive shrinkage. A 6-membered ring represented by formula (4) is a particularly preferable amidophosphazene compound in terms of the feel of processed knitted fabrics. The amide group of the amidophosphazene compound (-
A small amount of NH ₂ ) is added to other substituents e.g. -Cl, -
Although substituted with OCH ₃ , -OC ₂ H ₅ , -OC ₃ H ₇ and -OH, etc., compounds that are water-soluble as a whole and provide effects similar to those of the above-mentioned amidophosphazene compounds are naturally also included in the present invention. Contained in amidophosphazene compounds. As the acidic catalyst used in the present invention, all acidic catalysts used for resin processing of knitted fabrics are effective, such as urea-formaldehyde, melamine-formaldehyde, methylated methylolmelamine, dimethylolethylene urea, dimethylol Diammonium phosphate, ammonium chloride, organic amine hydrochloride, zinc chloride, chloride used in aminoplast resin finishing agents such as uron, tetramethylol acetylene diurea, dimethylol triazone and trimethylol melamine, and glyoxal resin finishing agents. Catalysts such as magnesium, zinc nitrate, zinc borofluoride, hydrochloric acid and phosphoric acid are preferred. The liquid for processing the knitted fabric containing cellulose fibers of the present invention contains at least one kind of amidophosphazene compound and at least one kind of acidic catalyst, but contains two or more kinds of amidophosphazene compounds and/or two kinds of acidic catalyst. The above acidic catalysts can also be used. Also,
In addition to amidophosphazene compounds and acidic catalysts,
If the effects of the present invention are not lost even if small amounts of resin processing agents, softeners, penetrants, water repellents, and/or cellulose crosslinking agents are added, processing fluids in which these other components are mixed are also included within the scope of the present invention. . In addition, the present inventors have proposed a method for flameproofing an amidophosphazene compound with the aim of improving wash resistance.
No. 103388, No. 60-103389, No. 60-219611, and No. 61-34799 have been filed for patent, but the processing agent used to improve wash resistance in these applications is not included in the processing fluid of the present invention. It can also be effectively used by adding it further. The concentration of amidophosphazene compound in the processing liquid is preferably 0.5 to 15
% by weight, particularly preferably from 1 to 10% by weight. In addition, the concentration of the acidic catalyst is preferably 0.01~
14% by weight, particularly preferably 0.1-10% by weight. A knitted fabric containing cellulose fibers has a processing liquid attached thereto, and the amount of the amidophosphazene compound adhering to the knitted fabric after compression is 3 to 7% by weight. If the deposited amount is lower than 1% by weight, no effective effect on the progressive shrinkage rate can be obtained. In addition, when the amount of adhesion is more than 10% by weight, there is almost no increase in the effect on progressive shrinkage and wrinkles, and on the contrary, there is a decrease in abrasion strength,
Problems such as yellowing and increased drug costs occur. In particular, in the case of knitted fabrics made of recycled cellulose, if the adhesion amount exceeds 10% by weight, the abrasion strength will decrease and yellowing will be significant, making commercialization difficult. The preferred range of the adhesion amount is 2 to 9% by weight,
A particularly preferred range is 3 to 7% by weight. The knitted fabric coated with the processing liquid is dried and then cured. Preferred curing temperature is 150-200℃
and the preferred curing time is 2 to 6 minutes. By curing, a portion of the amidophosphazene compound becomes insoluble in water and is filled into the cellulosic fibers, providing the effect of the present invention. When the amount of the amidophosphazene compound of the present invention applied to the knitted fabric after compression is 1 to 10% by weight, the phosphorus content in the processed knitted fabric of the present invention is approximately
It ranges from 0.15 to 3%. It is believed that the acidic catalyst makes the insolubilization in water and filling into the fiber more efficient, and improves the progressive shrinkage rate. The cured post-knitted fabric is soaped, that is, immersed in a weakly alkaline solution, washed with hot water and/or water, and then dried, or after washed with hot water and/or water, a softener or the like is applied and dried. Next, the measurement method used in the present invention will be described. (1) Progressive shrinkage rate (a) Sample collection and test piece preparation A 40 x 40 cm test piece was prepared according to the sample collection and test piece preparation methods described in JIS L-1042-1983: Section 7. (b) Washing The test was carried out in accordance with the water washing test method of the Fire and Disaster Management Agency Notification No. 11 dated June 1, 1970, "Standards for Washing Resistance Performance Related to Flame Retardant Performance (hereinafter referred to as "Notification No. 11")". Ivy. (i) Wash continuously for 75 minutes with a 60°C solution. In addition, in the method of Notification No. 11, the washing time is 15 minutes, but in this method, the washing time is 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 ×
6 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 6 times, which corresponds to a total of 30 repetitions. (c) Measurement After washing, measurement was performed 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 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) (2) Wrinkles after washing JIS L1096-1979 :Drying was measured by tumble drying according to method A in Section 6.23.1. (3) Abrasion strength Measured according to JIS L1096-1979: Section 6.17.1 (2) A-2 method (bending). (4) Amount of amidophosphazene compound adhering to knitted fabric after pressing Amount of amidophosphazene compound adhering (%) = [Weight of knitted fabric after adhesion of processing liquid (g) - Knitting fabric before adhesion of processing liquid/processing liquid Weight of knitted fabric before adhesion (g)* *Weight of fabric (g)] x Weight of amidophosphazene compound in processing fluid (%)/ (5) Carbonized area A-1 method specified in JIS L1091 (45° micro It was determined by a combustion test using a burner (heated for 1 minute). (6) Phosphorus content Phosphorus content was measured by sulfuric acid decomposition-colorimetric method. Reagent 1 Sulfuric acid for precise analysis (special grade reagent, 98%) 2 60% perchloric acid 3 Ammonium molybdate solution: Dissolve 17.7 g of ammonium molybdate (first grade reagent) 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 dissolve with water.
Dilute to 500ml. Measuring equipment Chemical balance, 50ml Köldahl flask, 10ml whole pipette, 5ml whole pipette, Kjeldahl thermal decomposition table, 25ml volumetric flask, 50ml volumetric flask, 50ml graduated cylinder, 500ml volumetric flask,
100 ml graduated cylinder, zeolite, spectrophotometer Operation 1 Sample decomposition treatment Accurately weigh 200 to 300 mg of the bone-dried sample using an analytical balance and transfer it to a 50 ml 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 0.5-15% 0.5ml 0.1-3% 2.5ml 3 Calculation P (%) = 25 / Decomposition fluid collection amount x 50 / 1000 x 11.65 x absorbance x 100 / Sample collection amount (mg) (11.65 mg/= Ab1.0) = 125/amount of sample collected x 11.65 x absorbance/amount of sample 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 x 11.65 x 50 / Sample collection amount (m
g) (7) Shrinkage rate F-2 method JIS L1042-1983: Determined according to Section 8.2.2 F-2 method. (8) Shrinkage rate D method Determined according to JIS L1042-1983: Section 8.1.4 D method. (9) Whiteness Determined according to JIS L1013-1981: Section 7.20 B method (two-wavelength method). [Effects of the present invention] The knitted fabric obtained by the present invention hardly undergoes the hardening of the knitted fabric, which often occurs in conventional resin processing. That is, the hardness of the knitted fabric before and after processing hardly changes, and the progressive shrinkage rate is significantly improved. Therefore, the processed knitted fabric of the present invention can be used in fields where dimensional stability is required. In particular, the effect on recycled cellulose-based knitted fabrics is great. In addition to improving the progressive shrinkage rate, wrinkles and fuzzing are also improved. Additionally, processed fabrics substantially free of free formaldehyde can be obtained when processed with preferred processing fluids of the present invention containing an amidophosphazene compound, an acidic catalyst, a softener, and a penetrant. Example 1 The refined muslin (30 x 30/68 threads/inch x 60 threads/inch, basis weight: 117 g/m ² ) woven using viscose rayon staple spun yarn was treated with amide phosphide having about 100% 6-membered rings. Azene compound 5% by weight, ammonium chloride 6.9
% by weight, and 0.2% by weight of a nonionic penetrant, and compressed so that the amount of the amidophosphazene compound adhering to the fabric after pressing was 5% by weight. Subsequently, it was dried and cured at 160° C. for 4 minutes, then immersed in an aqueous solution containing 2% by weight of soda carbonate and 0.2% by weight of a nonionic penetrant, washed with hot water, washed with water, and dried. The obtained processed product of the present invention is designated as A, the unprocessed product after scouring is designated as B, and the product processed with resin by the conventional method [glyoxal resin (trade name LFK: adhesion amount 10% by weight]) is designated as C. It is shown in Table 1.

[Table] Example 2 Consisting of 0.2% by weight of nonionic penetrant, about 60% of a 6-membered ring amidophosphazene compound, about 20% of a cyclic amidophosphazene compound of 8 or more members, and about 20% of a linear amidophosphazene compound. The amidophosphazene compound was added at varying weight percentages. The same refined muslin as in Example 1 was immersed in a pad solution to which ammonium chloride was added in an amount of 1.38 times the weight of the changed amide phosphazene compound, and the amide was applied to the fabric by squeezing. Varying the amount of phosphazene compound attached after squeezing, followed by drying and curing at 160°C for 4 minutes, followed by 3% by weight of soda carbonate and a nonionic penetrant.
Immerse in an aqueous solution containing 0.2% by weight, rinse with hot water, rinse with water,
Table 2 shows the relationship between the amount of the amidophosphazene compound adhering after pressing and various properties of the processed product of the present invention obtained by subsequent drying. According to the results of this example,
The vertical shrinkage rate (%) hardly changed when the amount of the amidophosphazene compound attached after compression was 4% or more. When the amount of adhesion exceeds 9.9% by weight, the abrasion strength decreases and the whiteness decreases significantly due to yellowing.
The level of performance has reached a level that does not meet the desired performance of consumers.
Incidentally, the complete burnout described in Table 2 refers to "a state in which the flame reaches the highest position of the test cloth and almost the entire test cloth is burned and carbonized."

[Table] Example 3 Scouring of a fabric woven using spun yarn consisting of 70% viscose rayon staples and 30% polyester (30 x 30/68 pieces/inch x 68 pieces/inch, basis weight 128 g/m ² ) was immersed in a padding solution prepared in the same manner as in Example 2 and squeezed to change the amount of the amidophosphazene compound attached to the fabric after squeezing, followed by drying and curing at 170°C for 3 minutes. After that, 0.5% by weight of soda carbonate and 0.2% by weight of nonionic penetrant.
Table 3 shows the relationship between the amount of the amidophosphazene compound adhering after squeezing and various properties of the processed product of the present invention obtained by immersing the product in an aqueous solution containing , washing with hot water, washing with water, and then drying. The vertical shrinkage rate (%) hardly changed when the amount of the amidophosphazene compound attached after compression was 3.3% or more. A deposition amount of around 3% is most preferable in consideration of abrasion strength and whiteness. There was no flame retardant effect when the adhesion amount was around 3%.

[Table] Example 4 A gray fabric (120D x 150D/107 pieces/inch x 72 pieces/inch) produced using viscose rayon filament was treated with about 60% of a 6-membered ring amidophosphazene compound.
%, about 20% of cyclic amidophosphazene compounds with 8 or more members and about 20% of linear amidophosphazene compounds
and approximately 30 of the amide groups of the amidophosphazene compound are substituted with methoxy groups (-OCH ₃ ). 4% by weight of the amidophosphazene compound, 5% by weight of ammonium chloride, 2% by weight of 85% phosphoric acid, and nonionic permeation. immersed in a pad solution containing 0.2% by weight of
After squeezing the amidophosphazene compound onto the fabric so that the amount of the compound after squeezing becomes 4% by weight, followed by drying and curing at 170°C for 3 minutes,
The processed product of the present invention obtained by immersing it in an aqueous solution containing 4% by weight of soda carbonate and 0.3% by weight of a nonionic penetrant, washing with hot water, washing with water, and then drying is called A, and the unprocessed product before processing is called B. do. These progressive shrinkage rates are calculated as
Shown in the table.

[Table] Example 5 The scouring of a broad fabric (product number 7420, basis weight 118 g/m ² ) woven using 100 spun cotton yarn was treated with 0.3% by weight of nonionic penetrant, 2% by weight of 85% phosphoric acid, and 6-membered rings. The addition weight percentage of an amidophosphazene compound consisting of about 60% of an amidophosphazene compound, about 20% of a cyclic amidophosphazene compound with 8 or more members and about 20% of a linear amidophosphazene compound was added, and this change The fabric was immersed in a pad bath to which ammonium chloride was added in an amount of 1.38 times the amount by weight of the amidophosphazene compound added and squeezed to change the amount of the amidophosphazene compound attached to the fabric after squeezing. After drying and curing at 170°C for 4 minutes, the amide of the processed product of the present invention was immersed in an aqueous solution containing 6% by weight of soda carbonate and 0.2% by weight of a nonionic penetrant, washed with hot water, washed with water, and then dried. Table 5 shows the relationship between the amount of phosphazene compound deposited after compression and various properties. According to the results of this example, the vertical shrinkage rate (%) is approximately 4% when the amount of amidophosphazene compound attached after compression is
% or more, there was almost no change. A coverage of about 4% is best considering abrasion strength and whiteness.

[Table] Example 6 The finished twill weave (20/1 x 20/2/154 threads/inch x 48 threads/inch) woven using viscose rayon staple spun yarn was scoured with the same composition as in Example 2. Amidophosphazene compound 7.0% by weight, ammonium chloride
The fabric was immersed in an aqueous solution containing 9.7% by weight and 0.2% by weight of a nonionic penetrant, and compressed so that the amount of amidophosphazene compound adhering to the fabric was 7.0% by weight, followed by drying and curing at 160°C for 3 minutes. ,
The present invention obtained by immersing in a solution containing 3% by weight of soda carbonate and 0.2% by weight of a nonionic penetrant, washing with hot water, washing with water, immersing in a 3% aqueous solution of high-density polyethylene softener, squeezing, and subsequently drying. The processed product is designated as A, the processed product obtained in the same manner except that ammonium chloride is not added is designated as B, and the unprocessed product after scouring is designated as C. These various performances are shown in Table 6.

[Table] Example 7 0.2% by weight of a nonionic penetrating agent and 0.2% by weight of a 6-membered ring amidophosphazene compound were added while varying the added weight%. 100% cotton nit smooth (40s'/16 inches x 1600 pieces (25G ), the scouring material with a basis weight of 216 g/m) is soaked,
The amount of the amidophosphazene compound attached to the knitted fabric after squeezing was varied by squeezing, followed by drying and curing at 160° C. for 1.5 minutes. Next, the processed product of the present invention was immersed in an aqueous solution containing 2% by weight of soda carbonate and 0.2% by weight of a nonionic penetrant, washed with hot water, washed with water, and then dried. The relationship between
Shown in the table.

[Table] As is clear from Table 7, it showed extremely excellent shrink-proofing properties in cotton knitted fabrics. In addition, practical flame retardant performance was not exhibited at these adhesion levels. Example 8 0.2% by weight of a nonionic penetrating agent and 0.2% by weight of a 6-membered ring amidophosphazene compound were added while varying the added weight%. 100% rayon staple nitsmooth (30s'/20 inches x 1500 pieces, fabric weight The scouring product (210 g/m) was soaked and pressed to change the amount of the amidophosphazene compound attached to the knitted fabric after pressing, followed by drying and curing at 160° C. for 1.5 minutes. Next, the processed product of the present invention was immersed in an aqueous solution containing 2% by weight of soda carbonate and 0.2% by weight of a nonionic penetrant, washed with hot water, washed with water, and then dried. Table 8 shows the relationship with various properties.

[Table] As is clear from Table 8, it showed an excellent reduction in warp shrinkage in staple knitted fabrics. Furthermore, flame retardant performance was not exhibited at these adhesion levels. After measuring the progressive shrinkage rate of the processed product of the present invention (washing 30
The surface (which had been washed several times) was smooth and shiny, and was almost unchanged from before washing. On the other hand, the surface of the unprocessed product after scouring had an extremely large amount of fuzz, a so-called "blurring" phenomenon, and the product lost its luster and had no commercial value.
This phenomenon was the same for Examples 1 to 8.

Claims (1)

[Scope of Claims] 1. An aqueous solution containing at least an amidophosphazene compound and an acidic catalyst is applied to a knitted fabric containing cellulose fibers such that the amount of the amidophosphazene compound attached to the knitted fabric is 3 to 7% by weight. 1. A method for processing a knitted fabric containing cellulose fibers, the method comprising: adhering the fibers so that the fibers are formed, followed by drying, curing, and subsequent soaping. 2. The method according to claim 1, wherein the knitted fabric containing cellulose fibers is a knitted fabric containing 65% or more of viscose rayon, strong viscose rayon, polynosic, and kyupra.