JP2737296B2 - Processing method of cellulosic fabric - Google Patents

Description

The present invention has a good whiteness of a cellulosic fabric,
The present invention also relates to a shrink-prevention processing method free from chlorine damage.

2. Description of the Related Art Shrink-preventing processing of a cellulosic fabric using a phosphorus amide compound is disclosed in Japanese Patent Application Laid-Open No. 63-20173. The phosphoramide compound is produced, for example, by the following formulas (1) and (2). In any of the methods, POCl ₃ + 6NH ₃ → PO (NH ₂ ) ₃ + 3NH ₄ Cl (1) (PNCl ₂ ) _N + 4 _n NH ₃ → (PN (NH ₂ ) ₂ ) _n + 2 _n NH ₄ Cl (2) Contains a large amount of ammonium chloride as a by-product.
Since there is no method for economically separating the ammonium chloride, a phosphorus amide-based compound containing a large amount of ammonium chloride is used as a processing agent. When an aqueous solution of a phosphoramide-based compound containing a large amount of ammonium chloride and / or an aged phosphoramide-based compound as a main component is adhered to a cellulose-based fabric and then heat-treated, ammonium chloride is dissociated and generated during the heat treatment. There is a problem that the fabric is yellowed by hydrogen chloride. Further, when a cellulose-based fabric processed using a processing agent containing a phosphorus-amide compound and / or an aged phosphorus-amide compound as a main component is treated with an aqueous solution containing chlorine such as a chlorine bleach, chlorine is adsorbed. However, there is a problem of chlorine damage such as discoloration due to high temperature such as ironing later.

Means for Solving the Problems The present inventors have conducted intensive studies to solve the above problems, and as a result, have found that a phosphorus amide compound and / or an aged phosphorus amide compound are combined with a cyclic urea cellulose reaction type resin or polyamine. It has been found that the above problems can be solved by combining them, and based on this, the present invention has been completed.

The present invention is characterized in that an aqueous solution of a processing agent mainly containing a phosphorus amide compound and / or an aged phosphorus amide compound and a cyclic urea cellulose-reactive resin or a polyamine is attached to a cellulosic fabric, and then heat-treated. The gist of the present invention is a method for processing a cellulosic fabric.

 Hereinafter, the present invention will be described in detail.

Examples of the phosphorus amide compound of the present invention include amide phosphazene compounds and phosphoric amide compounds,
Of these, the amidophosphazene compound has the general formula (Where x is an integer of 3 or more) a cyclic amidophosphazene compound, or a compound represented by the general formulas P _n N _n (NH ₂ ) _2n (2) and P _n N _n-1 (N
H ₂ ) _{2n + 3} (3) (where n is a positive integer), such as a linear amidophosphazene-based compound. In the formulas (1), (2) and (3), part of the amide group is an unsubstituted chloro group, a hydroxyl group by hydrolysis, an alkoxy group such as a methoxy group or an ethoxy group, a phenoxy group, a mono-lower alkylamino group, Those substituted with a di-lower alkylamino group and the like are also included.

Further, the phosphoric amide compound is one or two of phosphoric triamide (OP (NH ₂ ) ₃ ), phosphoric acid triamide condensate, and amide-substituted derivatives in which the amide group is substituted with another substituent. Consists of more than species. Examples of the phosphoric acid triamide condensate include two molecules of phosphoric acid triamide,
NH ₃ to release the fused imide diphosphate tetra-amide NH molecules _{(PO) 2 (NH 2)} 4, 3 diimide fused to release of NH ₃ 2 molecules from triamide molecular triphosphate pentaamide ( NH) ₂ (PO) ₃ (NH ₂ ) ₅ , similarly, a four-molecule condensate of phosphoric triamide, a five-molecule condensate of phosphoric triamide, and a six-molecule condensate of phosphoric triamide.

As the amide-substituted derivative, one part of the amide group of phosphoric acid triamide and phosphoric acid triamide condensate is There is a form that has been replaced with the like.

In addition, those in which a small amount of unreacted -Cl groups remain or those in which the remaining -Cl has been converted to OH by hydrolysis also constitute amide-substituted derivatives.

Aqueous solutions of these amide compounds include neutral aqueous solutions of amide compounds dissolved in neutral water or aqueous solutions of neutral compounds such as ammonium acetate, sodium chloride, sodium nitrate, and magnesium chloride. Are dissolved in an alkaline aqueous solution such as an aqueous ammonia solution, an aqueous sodium carbonate solution, an aqueous caustic soda solution, an aqueous diammonium hydrogen phosphate solution, an aqueous sodium phosphate solution, an aqueous calcium hydroxide solution, or an aqueous sodium oxalate solution. It is composed of an acidic aqueous solution of an amide compound dissolved in an acidic aqueous solution such as a phosphoric acid aqueous solution, an ammonium chloride aqueous solution, a monoammonium hydrogen phosphate aqueous solution, a monosodium hydrogen phosphate aqueous solution, an acetic acid aqueous solution, an oxalic acid aqueous solution, and a succinic acid aqueous solution.

Acidic catalysts such as diammonium phosphate, ammonium chloride, organic amine hydrochloride, zinc chloride, magnesium chloride, zinc nitrate, zinc borofluoride, hydrochloric acid and phosphoric acid, and small amounts of resin processing agents conventionally used, Agent, penetrant,
A water repellent and / or a cellulose crosslinking agent may be added to the aqueous solution of the amide compound as an auxiliary component.

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

As a method for producing a processing agent obtained by aging an aqueous solution of an amide compound, for example, as shown in Example 1 of US Pat. No. 2,782,133, ammonia gas is blown into a solution of chlorophosphazene in anhydrous carbon tetrachloride. A method of filtering the mixed precipitate of the obtained amidophosphazene compound and ammonium chloride, drying the obtained crude amidophosphazene compound to an aqueous solution and ripening the mixture, and adding ammonia gas to a monochlorobenzene solution of chlorphosphazene. A method in which an aqueous solution is added to the obtained mixed precipitate of the amidophosphazene compound and ammonium chloride, followed by stirring, and the mixture is aged to ripen the aqueous solution containing the amidophosphazene compound and ammonium chloride as main components. −4563
As shown in Examples 1 to 4 of JP-A No. 6 (1994), a phosphonitrile chloride compound obtained by reacting phosphorus pentachloride and ammonium chloride in an inert solvent such as monochlorobenzene or tetrachloroethane.
l ₂ ) A mixture of a group of compounds represented by _n and (PNCl ₂ ) _m · PCl ₅ is mixed with an aqueous solution of ammonia at a low temperature to amidate and by-produced with the resulting relatively low-molecular-weight amidophosphazene-based compound. As shown in Synthesis Example 1 of Japanese Patent Application No. 62-309373, a method of aging an aqueous solution containing ammonium chloride as a main component, chlorophosphazene produced from phosphorus pentachloride and ammonium chloride is dissolved in monochlorobenzene. By reacting with diethylamine under cooling and blowing in ammonia gas, a mixed precipitate of an amidophosphazene compound synthesized in a monochlorobenzene solution and ammonium chloride produced as a by-product is mixed with the above-mentioned page 7 from the bottom line, lines 6 to 8 Ninth
Aqueous solution containing amide phosphazene-based compound and ammonium chloride as main components obtained by adding and stirring the aqueous solution shown in the row, and aging the phosphorus oxychloride obtained in Example 1 of US Pat. No. 2,661,264. A method in which a crude phosphoric acid amide-based compound, which is a mixture of a reaction product with anhydrous ammonia and ammonium chloride as a by-product, is ripened in an aqueous solution, and anhydrous ammonia gas is blown into a monochlorobenzene solution of phosphorus oxychloride. The aqueous solution is added to the mixed precipitate of the phosphoric acid amide compound and ammonium chloride, and the mixture is stirred, and the phosphoric acid amide compound and ammonium chloride obtained by stratifying the aqueous solution in which monochlorobenzene, the phosphoric acid amide compound and ammonium chloride are dissolved are separated. A method of aging an aqueous solution containing the main component, obtained by adding aqueous ammonia to phosphorus oxychloride Various methods such as a method of aging the aqueous solution of phosphoric acid amide compounds can be employed.

Here, aging means giving a chemical change to an aqueous solution of a phosphorus amide compound. The pH of the aqueous solution may be acidic, neutral or alkaline. The aqueous solution may contain an organic compound such as an organic solvent and an inorganic compound such as an acid, an alkali and a salt. An aqueous solution containing ammonia and ammonium ions gives particularly favorable results. The aging temperature is preferably from 10 to 70 ° C, and the aging time varies depending on the aging temperature, but is preferably 1 hour or more, particularly preferably 5 hours or more.

The phosphorus amide compound undergoes a chemical change during ripening, which is due to the ³¹ P
This is supported by the change in the NMR curve.

FIG. 1 shows an NMR curve of ³¹ P before aging of an amidophosphazene compound (lot No. GB-003, manufactured by Nippon Soda Co., Ltd., pure content: 41.4%, ammonium chloride: about 58%).
Is the peak of the main component.

FIG. 2 shows that the amidophosphazene-based compound having the NMR curve of ³¹ P shown in FIG.
FIG. 2 shows an NMR curve of ³¹ P after aging an aqueous solution having an amidophosphazene-based compound concentration of / at 50 ° C. for 12 hours.
According to FIG. 2, the peak C shown in FIG. 1 disappears, while the peaks A and B not shown in FIG. 1 are generated.

FIG. 3 shows a phosphoric acid amide compound (Nippon Soda Co., Ltd., Lot No.GL-08, pure content 36.6%, ammonium chloride 63).
%) Shows the NMR curve of ³¹ P before aging. Peaks D and E are the main component peaks.

FIG. 4 shows that the phosphoric acid amide-based compound having the ³¹ P NMR curve shown in FIG.
3 shows an NMR curve of ³¹ P after aging an aqueous solution having a concentration of a phosphoric acid amide-based compound at 50 ° C. for 50 hours. According to FIG. 4, the peaks D and E seen in FIG.
The components almost completely changed to those shown by peaks F and G, which were not seen in the figure. The peaks F and G in FIG.
Have almost the same ppm values as the peaks A and B in FIG. 2, respectively, and are presumed to be the same substance.

In the present invention, a cyclic urea-based fibrin-reactive resin such as dimethylol alkyltriazone, dimethylol ethylene urea, dimethylol glyoxal monourein, urone resin and propylene urea resin as a chloride ion adsorbent; or dicyandiamide Polyamines such as condensates of dimethyldiallylammonium chloride, copolymers of dimethyldiallylammonium chloride and sulfur dioxide, diallylamine hydrochloride, and monoallylamine hydrochloride are used.

These chlorine ion adsorbents absorb chloride ions generated during heat treatment of the fabric to reduce yellowing of the fabric and reduce chlorine damage of the fabric after processing. The chlorine ion adsorbent is added to the aqueous solution of the phosphorus amide compound and / or the aged phosphorus amide compound, and the amount of addition is preferably 0.01 to 100 g /, particularly preferably 0.1 to 50 g /, as the concentration of the aqueous solution. If the concentration is too low, the effect is small, and if it is too high, it is economically undesirable.

The base material, which is the fiber base material of the fabric used in the present invention, is a cellulosic fiber, and includes both natural fibers such as cotton, ramie, and linen, and regenerated cellulose fibers such as viscose rayon, polynosit, and kyupura. In addition, a small amount of fibers other than the base material, such as polyamide, polyester, polyacrylonitrile, organic synthetic fibers such as spandex, glass fibers, carbon fibers, and inorganic fibers such as silicon carbide fibers are mixed with the base material. The fabric may be in any form such as a woven fabric, a knitted fabric, a nonwoven fabric, a resin-treated cloth, and a sewn product.

The present invention provides an aqueous solution processing agent (hereinafter abbreviated as an aqueous solution processing agent) obtained by adding a cyclic urea-based fibrin reactive resin or a polyamine to an aqueous solution of a phosphorus amide compound described above and / or an aged aqueous solution of a phosphorus amide compound. Is attached to the fabric, the aqueous solution processing agent of the present invention may be used alone as an aqueous solution processing agent, diammonium phosphate, ammonium chloride, organic amine hydrochloride, zinc chloride, magnesium oxide, zinc nitrate, Addition of acidic catalysts such as zinc borofluoride, hydrochloric acid and phosphoric acid, and small amounts of resin processing agents, softening agents, penetrants, water repellents and / or cellulose crosslinking agents conventionally used as auxiliary components thereof Can also. The pH of the aqueous solution processing agent is preferably 9.5 or less. pH
If it is higher than 9.5, the immobilization of the phosphorus amide compound on the fabric may be impaired.

The method of attaching the aqueous solution processing agent to the fabric can be carried out by immersing the fabric in the aqueous solution and then squeezing the fabric as it is or by using a roll or mangle, or by spraying and applying the aqueous solution to the fabric.

The amount of the aqueous solution processing agent adhering to the fabric is as follows.
Preferably, it adheres. If the amount of adhesion is small, the shrinkage-preventing effect is reduced, and if the amount of adhesion is large, the strength and whiteness may be reduced depending on the material.

Heat treatment is performed after attaching the aqueous solution processing agent to the fabric,
As a heat treatment method, any heat source such as hot air, infrared rays, microwaves, and steam can be used. One heat treatment may be performed, or two or more heat treatments may be performed. The preferred heat treatment temperature is 50 to 190 ° C., and the preferred heat treatment time is 1 to 30 minutes. The temperature and the time may be appropriately selected so as not to damage the cloth. By the heat treatment, the aqueous solution processing agent becomes hardly soluble in water and is fixed to the cloth. After the heat treatment, it is preferable to remove the water-soluble components in the fabric by washing with hot water or the like.

In the cloth obtained by the processing method of the present invention, phosphorus in the aqueous solution processing agent adhering to the processed cloth is preferably 0.3 to 2.0% by weight based on the weight of the original cloth, and is excellent in whiteness and / or chlorine damage. However, on the other hand, the original gloss, flexibility, moisture resistance, dyeability, etc. are not impaired at all.

In addition, the measuring method of phosphorus content weight%, shrinkage ratio to wash, whiteness, and chlorine damage is as follows.

(1) Method of Measuring Phosphorus-Containing Weight% Phosphorus-containing weight% in a fabric was determined by a sulfuric acid decomposition-colorimetric method shown below.

Sulfuric acid decomposition-colorimetric method for determination of phosphorus content weight% in fabric Reagent 1. Sulfuric acid for precision analysis (reagent grade, 98%) 2. 60% perchloric acid 3. Ammonium molybdate solution: ammonium molybdate (primary reagent) ) Dissolve 17.7g in water to make 500ml.

4. Ammonium metavanadate solution: Dissolve 0.6 g of ammonium metavanadate (first-class reagent) in water and add 60%
Add 100 ml of perchloric acid and dilute to 500 ml with water.

Measuring equipment Analytical balance, 50 ml Kjeldahl flask, 10 ml hole pipet, 5 ml hole pipet, Kjeldahl pyrolysis table, 25 ml volumetric flask, 50 ml volumetric flask, 50 ml volumetric cylinder, 500 ml volumetric flask, 100 ml volumetric cylinder,
Zeolite, spectrophotometer Operation 1.Decomposition of sample 200 to 300 mg of absolutely dry material is precisely weighed using an analytical balance, and 50 ml
Take in a Kjeldahl flask. 5 ml of water, 5 ml of sulfuric acid and 2-3 grains of zeolite (made of glass) are added, and the mixture is set on a Kehldahl pyrolysis table and pyrolyzed. When the sample is carbonized and dissolved in sulfuric acid to give a brown color (about 30 minutes after the start of heating), stop heating, allow to cool for 5 minutes, add 3 drops of 60% perchloric acid, and heat decompose again.
The heat decomposition-cooling-perchloric acid addition operation is repeated until the decomposition solution becomes colorless and transparent, thereby completely decomposing. After cooling to room temperature, the decomposed solution is washed with water in a 25 ml volumetric flask and diluted to the scale line.

2.Measurement Decomposed 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 weighing level. At the same time, the Blank test is performed by the same operation. After standing for 30 minutes, the absorbance at 400 nm is measured using Blank as a control solution.

Estimated phosphorus content Decomposed liquid collection volume 0.5-15% 0.5ml 0.1-3% 2.5ml 3. Calculation Since the phosphorus content of the work cloth is 3% or less, the amount of the decomposed liquid collected is 2.5 ml, and is calculated by the following calculation.

(2) Whiteness Measured according to JIS L 1013-1981, 7, item 20 B method.

(3) Chlorine injury JIS L 1041-1983 Section 5.4 (4) Shrinkage ratio to be washed Determined by the JIS L 0217103 method.

Example 1 Phosphoric amide (Lot No. IC-2703, manufactured by Nippon Soda Co., Ltd., about 37% pure, about 63% ammonium chloride) as a phosphoramide compound and dimethylol ethylene urea (Dainippon Ink) as a chlorine adsorbent (Betcamine E, manufactured by Co., Ltd.) dissolved in water (a concentration of the phosphoric amide of 110 g /
The urea concentration of 30 g /) is impregnated with a fluorescent rise under cotton nit sheeting (30 count 30 inch x 28 GG), squeezed with a mangle to 100% pick-up, dried at 110 ° C, and dried at 150 ° C for 1.75 minutes. It was quenched, then washed with hot water and dried. The processing conditions are shown in Table 1, and the whiteness, chlorine damage, phosphorus content, and shrinkage after washing of the processed cotton nit are shown in Table 2, respectively.

Example 2 Phosphoramide (Lot No. IC-2703, manufactured by Nippon Soda Co., Ltd., about 37% pure, about 63% ammonium chloride) as a phosphoramide compound and dimethylol ethylene urea (Dainippon Ink) as a chlorine adsorbent A processing solution (concentration of the above-mentioned phosphoric acid amide: 110 g /, concentration of the above-mentioned urea: 30 g /) prepared by dissolving Beccamin E manufactured by Co., Ltd.
Aged at 24 ° C for 24 hours, immersed in the resulting aging solution under a cotton nit sheeting (30 count 30 inch x 28GG) under fluorescent light, squeezed with a mangle to a 103% pick-up, dried at 100 ° C, and dried at 100 ° C.
It was cured at 8 ° C. for 2 minutes, then washed with hot water and dried. Table 1 shows the processing conditions, and Table 2 shows the whiteness, chlorine damage, phosphorus content, and shrinkage after washing once of the processed cotton nit.
These are shown in the table.

Example 3 Amidophosphazene (manufactured by Nippon Soda Co., Ltd., Lot No. GH-605, pure content: about 42%, ammonium chloride: about 58%) as a phosphorus amide compound and polyamine (manufactured by Nitto Boseki Co., Ltd.) as a chlorine adsorbent Danfix 202 was dissolved in water to a processing fluid (concentration of the amidophosphazene of 120 g / concentration of the polyamine of 30 g /), and cotton nit sheeting (30th count)
Immerse the fluorescent light in the lower part of 30 inches x 28GG), squeeze it to 110% pick-up with mangle, dry at 105 ° C, and dry at 145 ° C.
I spent a minute. The processing conditions are shown in Table 1, and the whiteness, chlorine damage, phosphorus content, and shrinkage after washing of the processed cotton nit are shown in Table 2, respectively.

Example 4 Amidophosphazene (manufactured by Nippon Soda Co., Ltd., Lot No. GH-605, pure content: about 42%, ammonium chloride: about 58%) as a phosphorus amide compound and polyamine (manufactured by Nitto Boseki Co., Ltd.) as a chlorine adsorbent A working fluid (concentration of the amidophosphazene of 120 g /, concentration of the polyamine of 30 g /) obtained by dissolving Danficus 202) in water was aged at 20 ° C. for 72 hours,
Into the obtained aging solution, immerse the fluorescent up under cotton nit Kanoko (30 count 26 inch x 28GG), squeeze it with a mangle to 90% pick-up, dry at 100 ° C, and cure at 150 ° C for 1.75 minutes, Then, it was washed with hot water and dried. The processing conditions are shown in Table 1, and the whiteness, chlorine damage, phosphorus content, and shrinkage after washing of the processed cotton nit are shown in Table 2, respectively.

Example 5 Phosphoric acid amide (manufactured by Nippon Soda Co., Ltd., Lot No. HK009, pure content: about 37%, ammonium chloride: about 63%) as a phosphoramide-based compound and uronic resin (manufactured by Dainippon Ink Co., Ltd.) as a chlorine adsorbent Processing fluid (concentration of 10% of the above-mentioned phosphoric amide) in which betcamine N-55) is dissolved in aqueous ammonia having a concentration of 0.7%.
0 g /, the above-mentioned uron resin concentration of 20 g /) was aged at 20 ° C. for 35 hours.
(Up to 26 inch count x 1512 lines) Soak the fluorescent light up, squeeze it into a pick-up 110% with a mangle, dry at 120 ° C,
The mixture was cured at 1.degree. C. for 1.75 minutes, then washed with hot water and dried. Table 1 shows the processing conditions, and Table 3 shows the whiteness, chlorine damage, phosphorus content, and shrinkage after washing once of the processed cotton nit.
These are shown in the table.

Example 6 Phosphorus amide (Lot No. HK009, manufactured by Nippon Soda Co., Ltd., about 37% pure, about 63% ammonium chloride) as a phosphoramide compound and dimethylol glyoxal monourein (Dainippon Ink Co., Ltd.) as a chlorine adsorbent A processing solution (concentration of the phosphoric acid amide: 100 g /, concentration of the dimethylol glyoxal monourein: 30 g /) obtained by dissolving Beccamin DCW (manufactured by Corporation) in 1% aqueous ammonia was aged at 20 ° C. for 5 hours. Then, immerse the fluorescent rise under cotton knit milling (40 count 26 inch x 1512 pcs) under the obtained aging solution, squeeze it into 110% pick-up with a mangle, dry at 120 ° C,
It was cured at 150 ° C. for 1.75 minutes, then washed with hot water and dried. The processing conditions are shown in Table 1, and the whiteness, chlorine damage, phosphorus content, and shrinkage after washing of the processed cotton nit are shown in Table 2, respectively.

Comparative example 1 It carried out similarly to Example 1 except not adding betcamine E.

Comparative Example 2 The procedure of Example 4 was repeated except that Danficks 202 was not added.

Effects of the Invention The fabrics processed by the processing method of the present invention have a whiteness of 116 and 118, respectively, in Comparative Examples 1 and 2 processed with a processing liquid containing no chlorine adsorbent of the present invention. Examples 1 to 6 of the present invention containing a chlorine adsorbent
Have excellent whiteness of 121 to 124. This indicates that the chlorine adsorbent of the present invention adsorbs hydrogen chloride generated by the thermal decomposition of ammonium chloride in quenching, thereby effectively preventing the test cloth from yellowing. In the case of chlorine damage, Comparative Examples 1 and 2 were tertiary, whereas Examples 1 to 6 were all tertiary, and chlorine contained in the test cloth due to chlorination was scorched. Shows that there is an effect of hardly coloring the test cloth. As described above, the fabric processed by the processing method of the present invention rarely yellows even during processing, adsorbs chlorine after processing, and is exposed to high temperatures such as ironing. Also, there is an effect that coloring is extremely small.

[Brief description of the drawings]

FIG. 1 shows the results of ³¹ P before aging of the amidophosphazene compound.
2 shows an NMR curve of the sample. FIG. 2 shows that the amidophosphazene compound of FIG.
Dissolved in aqueous ammonia to a concentration of 400 g /
3 shows the NMR curve of ³¹ P after aging at 0 ° C. for 12 hours. FIG. 3 shows a ³¹ P NMR curve of the phosphoric acid amide compound before ripening. FIG. 4 shows a solution obtained by dissolving the phosphoric acid amide compound of FIG. 3 in 10% aqueous ammonia to a concentration of 400 g / ml at 50 ° C.
1 shows an NMR curve of ³¹ P after aging for 0 hours.

Claims (1)

(57) [Claims] An aqueous solution of a processing agent mainly comprising a phosphorus amide compound and / or an aged phosphorus amide compound and a cyclic urea fiber-reactive resin or a polyamine is attached to a cellulosic cloth, followed by heat treatment. A method for shrink-proofing a cellulosic fabric, which is characterized in that: