WO2003038181A1 - Method of modification processing cellulose-based functional fiber material with excellent strength - Google Patents

Abstract

A functional cellulose-based fiber material imparting a pleasant feel when used in clothes and an excellent strength can be obtained by, in the modification processing of a fiber material by a covalent bond reaction or a crosslinkage reaction between a cellulose-based fiber material and silk proteins with amines by using a dichlorotriazine compound, carrying out the reaction in the coexistence of four substances, i.e., a water-soluble dichlorotriazine compound, sericin and/or silk fibrorin and diamines and/or alkanolamines and a fiber material, or preliminarily blending or reacting a dichlorotriazine compound with a cellulose-based fiber material, then adding or blending silk proteins and amines followed by the reaction to thereby crosslinking/covalently bonding the silk proteins and the amines to the cellulose-based material via triazine rings.

Description

 Description Modification method for cellulosic functional fiber material with excellent strength

 In the present invention, when modifying a cellulosic fiber material using a water-soluble dichlorotriazine-based compound, sericin and / or silk fibroin and water-soluble amines and Z or alkanolamines coexist. A method of modifying cellulose-based functional fiber material with excellent strength, characterized in that these silk proteins and amines are bonded to the fiber via a triazine ring to modify the cellulosic fiber material. is there. '' Background technology

In recent years, along with the improvement of quality of life and increasing interest in environmental, safety and health issues, shape memory fibers, flameproof fibers, UV shielding fibers, insect-proof fibers, antibacterial fibers, antibacterial fibers, deodorant fibers, and high texture Functional fibers such as fibers have been developed and are attracting the attention of the industry. Among them, silk fiber mouth or sericin is attached to fiber materials other than silk to give it the characteristics of silk, that is, it has good texture, moisturizing properties, deodorant properties, and antistatic properties. Processing methods that impart functions such as antioxidant properties, ultraviolet shielding properties, and antibacterial properties have been studied. However, conventional processing methods using resins and adhesives have the problem that the texture of the fiber tends to become rough and hard against the processing purpose, and the sericin-silk fibrin tends to fall off by repeating washing several times. . Further, such formalin and various processed resin monomers have a problem in that using an agent that causes toxicity and environmental issues _t Another important problem is that, in the case of a modified processing method involving a chemical reaction between a fiber and a drug, there is a problem in that the strength such as tear strength, burst strength, and tensile strength generally decreases. For example, according to known literature, it is shown that fibers processed using a daryozar or formalin-based agent have a significantly lower strength than unprocessed products. A number of patents have been published to improve the strength.However, these documents show that when the cellulosic fiber is subjected to morphological stabilization or functional processing, the strength is significantly reduced by about 20 to 50%. Therefore, a solution is desired as a new issue.

 The present invention relates to the above-mentioned known processing methods using sericin or silk fibroin, which have the disadvantages of poor texture, insufficient durability of processing effects, use of dangerous and harmful substances for processing chemicals, and remarkable. Focusing on the fact that strength reduction occurs, we studied strength improvement processing methods that are excellent in economic efficiency, environmental adaptability, and safety. '

 In addition, despite the fact that silk sericin protein accounts for one-quarter of expensive silk fibers, at present it is often discarded as contained in wastewater discharged during silk scouring. , Has become an environmental pollutant.

Our goal is to use sericin aqueous solution obtained by collecting silk smelting waste liquid or dry sericin powder as a raw material for high value-added processing of cellulosic fiber materials, Is to promote a strong cross-linking reaction by using soluble diamines and Z or alkanolamines to develop a new functional cellulose fiber material with excellent strength. It is also an important aim to reduce wastewater loads by achieving resource recycling and to develop environmentally friendly processing methods. In addition, water produced as part of the recycling of silk that is emitted as fiber waste It is also an object of the present invention to contribute to environmental problems by effectively using soluble silk fibroin by a durable and strong processing method. Disclosure of the invention

 The present inventors have solved the above-mentioned problems and promoted the research and development of functional fibers that are environmentally friendly.As a result, cellulosic fibers and sericin and z or silk fibroin and water-soluble dichlorotriazine compounds were used. It has been found that a functional cellulose fiber material having excellent strength can be produced by covalently bonding or cross-linking a diamine and / or alkanolamine having a property in the presence of an acid binder. BEST MODE FOR CARRYING OUT THE INVENTION

 In the method of the present invention, processing methods such as a so-called immersion method and a pad-dry-steaming method are applied. One method comprises, as a first step, one of a fiber and a water-soluble dichlorotriazine compound. The chlorine in the eyes is allowed to react as much as possible, and as a second step, the remaining chlorine is reacted with the silk proteins and amines to share the silk proteins and amines with the fiber via the triazine ring. -A method of cross-linking. At this time, the amines are assumed to act as agents for promoting cross-linking and improve the strength.

For example, at a concentration by weight of 0.5% to 20% of the purity of a dichlorotriazine-based compound, 0% to 10% of sodium sulfate, 0.5% to 2% of sodium carbonate and / or bicarbonate soda. 0%, urea 0-20%, penetrant 0.1-1.0 ° /. Mix and dissolve in water to make padding bath. Pad the cloth in this bath, squeeze it and heat it to 50 to 150 ° C for several seconds to several hours to dry or semi-dry. Pad the cloth with 5 to 20% sericin and / or silk fiber mouth and 0.1 to 10% aqueous solution of amines and dry it again or leave it alone for 80 to 150 seconds for several hours to several seconds. Steaming. Then wash with water, wash at 60-100 ° C, wash with water, and dry to finish.

 As mentioned above, it is also possible to process in one step without dividing the process into two.In this case, a padding bath containing a mixture of drug, silk protein, amines, acid binder, urea, bowel nitrate and wetting agent After the padding and squeezing and drying the cloth, steaming may be performed for several hours to several seconds at 60 to 150 ° C while keeping it wet.

 Specific examples of water-soluble dichlorotriazine compounds that can be advantageously used as a cross-linking agent between cellulosic fiber materials and silk proteins and amines include the following compounds. May be any water-soluble dichlorotriazine compound having two or more reactive chlorine atoms, and is not limited to these specific examples.

 2,6-dichloro-1- (3-carboxyethylamino) S-triazine

 2,6-dichloro-1-4-("y-carboxypropinoleamino) -S-triazine

 2,6-Dichloro-1-41- (3-sulfoalinelino) -1 S-triazine 2,6-dichloro-14-1,4- (4-sulfoalinelino) -1 S-triazine 2,6-dichloro-1 One 4— (3,5-disulfoalinerino) One S—Triazine

2,6-dichloro-1-4- (2,5-disulfoalinelino) -S-triazine 2, 6 — Zykrol 1-Peridot S — Triadine

 2, 6-dichloro-1-4-thiocarbamoylamino-S-triazine

2, 6 —Dichloro-1-oxoxy S — Triazine Na salt

 2,6-dichloro-1-4-thio-S-triazine Na salt

 2,6-dichloro-1-41 (3-carboxanilino) -S-triazine

4,4'-bis (4,6-dichloro-S-triazine-1-2-ylamino) stilbene-1,2,2'-disulfonic acid Na salt.

 Sericin that can be used in the present invention may be an aqueous solution containing a slightly low molecular weight silk protein obtained by recovering a waste solution of Arikari refining, or a silk protein having a relatively large molecular weight recovered by high temperature method refining. It may be used. Molecular weight distributions generally include those in the thousands to hundreds of thousands. Further, a product concentrated by an ultrafiltration concentration method or the like may be used, or a product obtained by further drying the powder by a spray drying method or the like may be used. It is also possible to use hydrolyzed silk whose molecular weight is adjusted appropriately, and it is also possible to use hydrolyzed silk derivatives.

The water-soluble diamines or alkanolamines which can be used in the present invention include aliphatic straight-chain, branched-chain or cyclic alkylenediamines, alkylenetriamines, alkylenetriamines and the like. Specifically, the following compounds can be mentioned, but it is essential that the amines have at least two reactive groups such as amino group, imino group, hydroxyl group and thiol group in total. Is not limited to the specific example. For example, ethylenediamine, triethylenetetrathamine, arginine, ethanolamine, jetanolamine, triethanolamine, isopropanolamine, 1-1 (2 Amines such as monoaminoethyl) piperazine. In some cases, a polyhydric alcohol or urea may be added to the amine to produce a better effect.

 The fiber material to be processed in the present invention is a cellulosic fiber material such as cotton, hemp, viscose rayon, cupra rayon, lyocell, and cellulose acetate. In essence, it is a natural fiber material having a hydroxyl group that can be covalently bonded to a dichlortriazine compound. These fiber materials may be used alone, or may be blended with other natural fibers or synthetic fibers, or woven fibers. Further, the present invention can be applied to any form of fiber material such as yarn, woven fabric, knitted fabric or non-woven fabric.

 The fiber material processed and modified by the method of the present invention becomes silk-like and has various characteristics of silk, such as unique luster, warm texture, moisture retention, deodorant, antioxidant, ultraviolet absorption, and antibacterial. Properties, etc., and excellent strength and durability.

 In particular, the method of the present invention, in which sericin contained in the waste liquid generated in the silk scouring process can be utilized in a highly practical way, has the effect of reducing wastewater load and recycling waste as one bird and two birds per stone. This is a new technology that responds to environmental problems in the 21st century, and it can be said that it is Eco and Fendri single fiber processing.

 Hereinafter, the present invention will be described in detail with reference to Examples, but the present invention is not limited to these Examples. In the examples, parts and% mean parts by weight and% by weight.

Example 1

Water 32 2 parts, sodium carbonate 1.35 parts, 2,6-dichloro-14-oxy-S-triazine Na salt 10% aqueous solution 8 parts, water-soluble with molecular weight distribution of 10,000 to 20,000 0.8 parts of sericin powder, 0.8 parts of diethanolamine, 0.04 parts of penetrant, and 4 parts of urea are mixed well at room temperature to form a padding bath. Next, 100% cotton broad is padded and squeezed into this bath, and dried in a warm air dryer at 120 ° C for about 3 minutes. Then steam with humidification at 105 ° C for 20 minutes and finally dry out.

After rinsing, wash in hot water for 10 minutes, rinse with water, dry and finish.

 The dimensional change rate of the cotton broad processed under such conditions was 0.3% in the vertical direction and 0.2% in the horizontal direction, indicating good washability. The tensile strength (N) of the unprocessed product was vertical 683 and horizontal 523, but the processed product had a vertical length of 775 and horizontal 530, and the strength was improved. When sericin was added alone without adding amines, the tensile strength decreased by about 20%. The moisture retention was measured at 20 ± 2 ° C and 65 ± 5% RH, which was 8.1%, which was superior to the unprocessed product. Both moisture retention and feeling were improved.

Example 2

 As a result of performing similar processing using Tencel bit instead of the cotton broad in Example 1 described above, the dimensional change rate was 0.5% in the vertical direction and 0.3% in the horizontal direction, showing good pushability. The abrasion strength was 100 times by the Mandale method, and the unprocessed product was fibrillated, but the processed product did not produce fibrillation at all.

The burst strength of the unprocessed product was 212 KPa, and that of the product processed with sericin alone was 180 KPa, and that of the processed product of this example was 23.5 KPa, indicating improved strength and moisture retention. The texture was better than unprocessed products. Industrial applicability

 According to the present invention, silk proteins such as sericin and / or silk fibroin and amines such as diamines and / or alkanolamines can be firmly bound to a cellulosic fiber material by covalent bonds. Therefore, compared to the conventional method of simply coating sericin on the fiber, converting it to resin, or insolubilizing it, physically retaining the sericin in the fiber, it has excellent texture, durability and strength. A silk-like fiber material with good form stability can be obtained. As a result, any cellulosic fiber material that has a substituent capable of reacting with a dichlorotriazine-based derivative can be converted into a skin that has good texture, reduced skin damage such as rough skin, rash, and atopy. It can be modified to a cellulose-based functional fiber material with excellent properties.

 In addition, silk is an excellent fiber material that is gentle on the skin, but its production is limited and expensive, and it is easy to cause shrinkage due to repeated washing, causing many problems. It is significant that the field which can be replaced with silk by the cellulosic fiber of the method of the present invention which can be processed is widened in terms of cost and expansion of demand.

 Although silk sericin is disposed of as a waste liquid after scouring, this waste will be used effectively as a resource, which will lead to a reduction in drainage load. Therefore, it is not an exaggeration to say that the present invention is not only a development of eco-friendly eco-fiber products, but also an invention that fosters eco-business.

Claims

The scope of the claims 1. In modifying a cellulosic fibrous material with a water-soluble dichlorotriazine compound, sericin and Z or silk fibrin and water-soluble diamines and Z or alkanolamines are allowed to coexist. Of high-strength cellulose-based functional fiber material, characterized by modifying cellulosic fiber material by covalently bonding the silk protein and amines of the present invention to the fiber material through a triazine ring by covalent bond. Law.  2. In modifying a cellulosic fiber material with a water-soluble dichlorotriazine-based compound, sericin and Z or silk fibroin and water-soluble diamines and Z or alkanolamines coexist, and these silks are used. A cellulose-based functional fiber material with excellent strength that has been modified by binding proteins and amines to the fiber material via a triazine ring via a covalent bond.