JPH02216267A - Modifying processing of protein fiber product - Google Patents

Abstract

PURPOSE:To provide protein fiber product with excellent shrink-resistance without damaging luster, flexibility and water-vapor resistance of the characteristic fiber by supplying protein fiber product with an aminated substance of phosphorus and heat-treating the product. CONSTITUTION:A protein fiber product is provided with a solution of an aminated substance of phosphorus as a main component in an aprotic polar solvent (e.g. acetonitrile or dimethylformamide) by permeation method, etc., to provide the protein fiber product with excellent shrink-resistance without damaging luster, flexibility and water-vapor resistance of the fiber. An aminophosphazene-based compound shown by the formula (n is 2-10, preferably 3-4) or phosphoric amide compound may be cited as the aminated compound of phosphorus.

Description

DETAILED DESCRIPTION OF THE INVENTION Field of Industrial Application The present invention relates to a method for processing protein fiber products using an aminated product of phosphorus.

BACKGROUND OF THE INVENTION Fiber products made of protein fibers such as silk, wool, mohair, and cashmere have excellent gloss, flexibility, hygroscopicity, dyeability, etc., but have the disadvantage of poor shrink resistance when washed. Therefore, various methods have been tried in the past to improve these drawbacks. For example, treatment methods using condensation resins such as melamine resin and urea resin, which are used as wash-and-wear processing agents for cellulose fiber products, and reactive resins such as glyoxal resins have been attempted; Since this method usually uses a catalyst, there is an unavoidable risk of deterioration or alteration of the fibers due to the catalyst, and this method is not a practical method. In addition, methods of treatment with tin chloride or tannic acid, and methods of graft polymerization of vinyl monomers are also known, but these methods tend to impair the unique texture of protein fibers and pose practical problems. Furthermore, a method of treatment with an epoxy compound (Japanese Patent Publication No. 52-3
8131) has also been proposed, but with this method,
Amino groups, carboxyl groups, alcoholic hydroxyl groups, and phenol in protein fiber water test M1. By blocking functional groups such as groups, the shrink resistance during washing can be improved without significantly impairing the dyeability and hygroscopicity inherent to protein fibers, but the effect is not sufficient and the reaction time is long. There were drawbacks.

Invention tries to solve! ! l! The present invention eliminates the drawbacks of the prior art, and provides protein fiber products with excellent shrink resistance during washing without impairing the gloss, flexibility, moisture resistance, dyeability, etc. characteristic of protein fibers. An object of the present invention is to provide a method for modifying protein fiber products that can be applied with high productivity.

Means for Solving the Problems As a result of extensive research, the present inventors have discovered that protein fiber products can be treated with an aprotic polar solvent solution (including suspension) containing an aminated product of phosphorus as a main component. The present invention has been achieved based on the discovery that shrink-proofing with excellent washing resistance can be obtained without impairing the original physical properties of the fiber.

That is, the method of the present invention is characterized in that an aprotic polar solvent solution containing an aminated product of phosphorus as a main component is applied to a protein fiber product, and then heat-treated.

As the aminated product of phosphorus, it is preferable to use an aminophosphazene-based compound or a phosphoric acid amide-based compound, and typical examples of the aminophosphazene-based compound include cyclic compounds such as hexaaminocyclotriphosphazene represented by the following formula 1. , and a linear body P represented by the following formula ■2 or m,
N, (NH□Lll-z II formula P, NM-+(N
Hz) zl141Iff formula (where n is the same as formula 1). Note that a part of the amino group of the compound of formula 1-If1 may be substituted with an alkoxy group such as chlorine, hydroxyl group, methoxy group, or ethoxy group, phenoxy group, or alkyl-substituted amino group.

Further, as the phosphoric acid amide compound, it is preferable to use a compound represented by the following formula 8.

The terminal of formula 8 is preferably substituted with an amino group, but phosphoric acid amide derivatives in which part of the amino group, including the amine group shown in formula 8, is substituted with an alkoxy group, an alkyl-substituted amino group, etc. is also useful. Examples of this type of compound include phosphoric acid triamide, phosphoric acid diamide, phosphoric acid triamide condensation products, or amino groups thereof such as methoxy groups,
Examples include amide-substituted derivatives substituted with substituents such as alkoxy groups such as ethoxy groups and alkyl-substituted amino groups. The phosphoric acid triamide condensate contains imide 2 which is condensed by releasing one molecule of Nl (,) from two molecules of phosphoric acid triamide.
Phosphoric acid tetraamide, 2 from 3 molecules of phosphoric triamide
Diimidophosphoric acid pentamide condensed by releasing the molecule Nl (3, or a tetramolecular compound of phosphoric acid triamide formed in the same manner, a five-molecule condensate of phosphoric acid triamide,
This includes a hexamolecule ring compound of phosphoric acid triamide.

Such phosphorus aminated products are generally synthesized by reacting phosphorus halides such as chlorphosphazene, phosphorus pentachloride, phosphorus trichloride, and phosphorus oxychloride with ammonia. Therefore, although the phosphorous aminated product contains the by-product ammonium chloride, it is also possible to use a solution of such a crude aminated product in an aprotic polar solvent (which may also be a suspended EJ solution).

Further, in order to promote the reaction of the phosphorous aminated product, a catalyst such as a protonic acid, a Lewis acid, a Lewis base, or an amine may be used in combination.

In the present invention, an aminated product of phosphorus is used as a solution (or suspension) in an aprotic polar solvent. Examples of the aprotic polar solvent include acetonitrile, dimethylformamide, dimethyl sulfoxide, methyl ethyl sulfoxide, and hexamethyl phosphoric acid. amide, dimethylacetamide,
Sulfolane, N-methylpyrrolidone, etc. can all be used.

The aprotic polar solvent solution containing the phosphorous aminated product, that is, the processing agent solution, contains a small amount of water, a common resin processing agent,
A softener, a penetrant, etc. may also be included.

As a method for attaching a processing agent solution to protein fiber products,
Dipping methods, banding methods, coating methods, etc. can all be applied.

The amount of phosphorous amine attached to protein fiber products is 0.05 to 7% by weight, especially 0.1% by weight, based on the dry textile product.
It is preferable that the amount is ~3% by weight.Even if the amount of adhesion exceeds 7%, a remarkable anti-shrinkage effect can be obtained, but if the amount of adhesion is too large, the characteristic texture, flexibility, hygroscopicity, etc. of the protein fiber will be affected. In addition, there is a risk that fiber strength may decrease.

For the heat treatment after the treatment with the processing agent solution, any of hot air, infrared rays, microwaves, steam, etc. can be used as a heat source, and the number of heat treatments is not limited to one, but may be performed two or more times.

The preferred heat treatment temperature is 80 to 150°C, and the heat treatment time may be about 1 to 30 minutes.

In addition, since aprotic polar solvents have a high swelling property for fibers, it is preferable to react a phosphorus aminated product with a protein fiber product in the presence of an aprotic polar solvent.The boiling point of the aprotic polar solvent is Generally, the temperature is high, so protein fiber products coated with a processing agent solution may be heat-treated in an open state by appropriately selecting the heat treatment temperature. It is preferable to heat-treat the protein fiber product in a closed system or under conditions of wrapping with a film or the like.

It goes without saying that it is preferable to thoroughly wash the fiber product after the heat treatment to remove components that are not fixed to the textile product.

The textile products processed in the present invention may be made of protein fibers alone, or may be blends of protein fibers with other fibers, inter-knitted fabrics, yarns, woven fabrics, It may be in either a knitted fabric or a nonwoven fabric. In addition, these textile products may be used within the range that does not interfere with the processing of the present invention.
It may be processed in advance with another processing agent, and may be before or after dyeing.

Examples of protein fiber include wool, wool, mohair, cashmere, soybean regenerated protein, etc.
The method of the present invention is particularly suitable for processing textile products containing 30% by weight or more of these protein fibers.

Next, examples of the present invention will be shown. In the examples, unless otherwise specified, parts and percentages indicate parts by weight and percentages by weight.

Example 1 Dimethyl sulfoxide (DMSO) containing 20% by weight of amidophosphazene resin (DFA manufactured by Nippon Soda)
- Special reagent grade - In the solution, add silk-koshirimen (6 out of 27 warps)
The real flat threads and 8 out of 27 weft threads (2,800 t/yard, scoured by a conventional method) were soaked, squeezed to about 110% with a mangle, and then heat-treated at 120° C. for 10 minutes while maintaining a predetermined width. Thereafter, it was soaped with warm water containing a small amount of soda carbonate and a nonionic surfactant, and dried by repeating hot water washing and water washing. Thereafter, it was placed in a predetermined width (36 cm).

Comparative Example I A rope crepe was immersed in an aqueous solution containing 20% by weight of DFA (without DMSO) and treated in the same manner as in Example 1.

Example 2 DMSO as in Example 1? In liquid A, string pares crepe (3 flat threads out of 21 warp threads, 4 threads out of 21 weft threads 3200t/
11, scoured by a conventional method), squeezed to about 1.10% with a mangle, and while maintaining the specified width, 12
Heat treatment was performed at 0°C for 10 minutes. Then, soap with warm water containing a small amount of soda carbonate and nonionic surfactant, wash with hot water,
Repeated washing with water and drying. After that, it was set to a predetermined width.

Example 3 In the same DMSO solution as in Example 1, silk patterned rinds (2 out of 27 warp yarns, 4 out of 27 ground weft yarns, 3600 t/pm) were added.
, 6 out of 21 picture wefts, lower 600 t/pigeon, upper 500 t/
s, refined by a conventional method), squeezed to about 110% with a mangle, and then squeezed to 120% while maintaining the specified width.
Heat treatment was performed at ℃ for 10 minutes. Thereafter, it was soaped with warm water containing a small amount of soda carbonate and a nonionic surfactant, and dried by repeating hot water washing and water washing. After that, it was set to a predetermined width.

Example 4 A woolen fabric (warp 5
2 m count, 68 m weft count, scouring by conventional method) was soaked, squeezed to about 110% with a mangle, and then heat treated at 120° C. for 10 minutes while maintaining a predetermined width. Thereafter, it was soaped with warm water containing a small amount of soda carbonate and a nonionic surfactant, and dried by repeating hot water washing and water washing.

Then, it was cented to the prescribed width.

The physical properties of the products obtained in Examples 1 to 4 and Comparative Example 1 are shown in Table 1 in comparison with the physical properties of the unprocessed products.

In addition, the physical property values in Table 1 indicate the following values.

Adhesion rate The weight of the fabric was calculated as an absolute dry weight using the following formula.

Shrinkage rate X, Y, and Z were determined and calculated using the JIS L-1042B whitening C1, Lab color system.

Bending resistance The KES method bending properties were B and 28B.

As is clear from the results of Examples 1 to 3, the method of the present invention provides highly excellent shrink-proofing effects to highly twisted yarn fabrics at an adhesion rate of around 1%. However, there is no substantial effect on the original whitening of the fabric, bending resistance, etc., and there is no damage to the texture.On the other hand, when DFA is used in an aqueous solution (Comparative Example 1), , almost no shrinkage effect was observed,
The texture also becomes hard.

Note that, as is clear from the results of Example 4, the method of the present invention can impart excellent shrink-proofing effects to woolen fabrics without affecting the feel or the like.

Effects of the Invention The method of the present invention provides protein fiber products with the luster, flexibility, dyeability, etc. characteristic of protein fibers, without sacrificing their properties.
It can provide excellent shrink-proofing properties.

Claims (1)

[Claims] 1. A method for modifying protein fiber products, which comprises applying an aprotic polar solvent solution containing an aminated product of phosphorus as a main component to the protein fiber products and heat-treating the products.