JP2005054342A - Modification of fiber materials using monochlorotriazine chemicals - Google Patents

Abstract

[Problem] Conventionally, a method for imparting functionality by binding sericin or silk fibroin to a fiber includes a method of physicochemically retaining the protein by coating, resinating or insolubilizing these proteins. Although many have been known, since there are many drawbacks in texture and the like, a method using a dichlorotriazine compound has been disclosed as an improved method. However, the cross-linking agent of this method is unstable and easily decomposed, and has a problem that it is difficult to put it to practical use in terms of aging.
[Solution]
The monochlorotriazine-based cross-linking drug mixture obtained by heat-reacting cyanuric chloride and sericin and / or silk fibroin in the presence of an acid binder becomes an extremely stable drug. It is possible to perform processing with excellent wearing comfort such as excellent form stability, moisture retention, texture, etc., that is, to perform form stability / functionality processing with excellent durability to increase the added value of the fiber material. I found it possible.
[Selection figure] None

Description

Detailed Description of the Invention

The present invention uses a monochlorotriazine fiber modifying chemical mixture obtained by heating and reacting cyanuric chloride with water-soluble sericin or / and silk fibroin in the presence of an acid binder. This is a processing method for modifying a synthetic fiber material to provide a fiber material having excellent shape stability and functionality.
More specifically, the present invention provides water-soluble water in the presence of an acid binder using cyanuric chloride as a raw material for imparting functionality such as form stability, moisture retention, deodorant properties, and wearing comfort to the fiber material. Of natural fiber, regenerated fiber or semi-synthetic fiber material using a monochlorotriazine-based fiber modification agent mixture obtained by heat-reacting with sericin and / or silk fibroin. This is a processing method for providing a fiber material with excellent functionality.

In recent years, with the improvement of quality of life and increasing interest in environmental, safety and health issues, shape memory fibers, flame retardant and flame retardant fibers, UV shielding fibers, insect and mite fibers, antibacterial fibers and deodorant fibers High-quality, high-textured fibers, and functional fibers such as UV-shielding fibers have been developed one after another, attracting the attention of the textile industry. On the other hand, in order for the Japanese textile industry, which is being conquered by China, to survive and co-exist with China, it is considered indispensable to develop functional fibers with added value to the fibers. The development and practical application of functional fibers is extremely important for the Japanese textile industry.
Under such circumstances, animal and plant proteins such as sericin, silk fibroin, chitosan, collagen, and soy protein are combined with fiber materials to give the protein characteristics, that is, a feeling of good texture, moisturizing, erasing Processing to impart functions such as odor, antistatic, antioxidant, ultraviolet shielding, and antibacterial properties has been studied, and some have been put into practical use.
However, the conventional processing method is “fiber processing” Vol. 50 No. 7 301 pages, ibid. As described also on page 8358 (1998), animal and plant proteins are bonded simultaneously with resin processing using mainly fiber processing resins such as glyoxal resins and urethane resins, as described in Japanese Patent Publication No. 2588445. As described above, it is possible to insolubilize sericin and silk fibroin using a sticking agent, or to absorb high temperature water-soluble high molecular weight sericin into a fiber at high temperature and cool it as described in JP-A-11-350352. Describes a method of attaching sericin that has become insoluble by the method to fibers.
Examining the processing effects of the fiber materials processed by these known methods, the resin processing method has a problem that the texture of the fibers tends to become coarse and hard, and the proteins fall off by repeating washing. There is also the problem of durability that it is easy and the sustainability of the processing effect is poor.
In addition, the use of chemicals that may cause safety and health problems and environmental problems such as formalin and various monomers for resin processing has been pointed out as a problem.

Furthermore, in the case of a modified processing method in which the fiber material and the processing agent involve a chemical reaction, there is a problem that the strength such as tear strength, burst strength, and tensile strength is generally lowered. For example, “Fiber processing” Vol. 50 No. 8 As described in page 358 (1998), fibers processed using glyoxal-based or butanetetracarboxylic acid show that the tear strength is significantly lower than that of unprocessed products.
In addition, as seen in JP-A-5-59664, in the case of the formalin processing method, both the tear strength and the burst strength are greatly reduced as compared with the unprocessed product, so a patent as a strength improvement method has been filed and published. Yes.
The improved patents issued in view of the strength reduction are disclosed in JP-A-6-158550, JP-A-7-279042, JP-A-7-324281, JP-A-8-302567, and JP-A-8-. No. 144176, Japanese Patent Laid-Open No. 2000-96442, etc.
As seen in these examples, the fiber material is subjected to functional processing such as shape stabilization processing, thereby closing up a new problem of reducing strength by about 30 to 50%, and a solution is desired.

As a method for solving these problems, Japanese Patent No. 3366000 using a dichlorotriazine-based crosslinking agent has been published. Although this patent method certainly solves many of the above problems, the biggest drawback of this patent is that the dichlorotriazine compound is an unstable compound and cannot withstand long-term storage. .
In other words, the dichlorotriazine compound is an unstable compound in an aqueous solution and has a change with time. Hydrolysis progresses with time, and the liquidity gradually shifts to the acidic side. However, since the hydrolysis proceeds to a triazine compound having no reactive group, the crosslinking reaction becomes impossible and the processing effect disappears.
The reactivity of the three chlorines of cyanuric chloride is replaced by an electron-providing substituent, so that the reactivity of the second, second, and third chlorines is lower and more stabilized. For example, when the time-dependent change of 2,6-dichloro-4-hydroxy-S-triazine Na salt as a dichlorotriazine compound in which one chlorine of cyanuric chloride is substituted with a hydroxyl group is examined, 25 of an aqueous solution adjusted to PH = 8 is obtained. The change over time at ± 5 ° C. was initially 95%, but the content decreased to 75% in 2 weeks by about 20%, and the liquidity approaches neutrality. Further, as the change with time progresses, the liquidity changes to acidity, the decomposition rate is accelerated, and it is completely hydrolyzed within a few days to become a strongly acidic aqueous solution.
Hydrolysis proceeds in a similar manner for 2,6-dichloro-4- (2,5-disulfoanilino) -S-triazine Na salt. When refrigerated at 5 to 10 ° C., the hydrolysis rate is slightly improved and slightly slowed down, but the change with time cannot be completely prevented. This problem becomes a practically fatal problem such as the distribution and storage management of the cross-linking drug.

Problems to be solved by the invention

In the present invention, the above-mentioned known processing methods using animal and vegetable proteins, especially sericin and / or silk fibroin, are inferior in texture, inadequate in durability of processing effects, and dangerous for processing chemicals. Focusing on the use of harmful substances, strength reduction and instability of processing chemicals, it is excellent in economic efficiency, excellent in environmental problem adaptability and safety, and has an effect of maintaining and improving the strength. We conducted a research on the practical application of screening and processing methods for drugs that have both washability and functionality with high practical value without any change in the drugs.
In addition, by using sericin aqueous solution obtained by collecting and concentrating silk scouring waste fluid or dried sericin in animal and plant proteins as a raw material for high-value processing of fiber materials, If we can develop a new method for processing functional fiber materials with high form stability and high practical value, we will be able to recycle waste and reduce drainage load, and develop processing methods that are friendly to the global environment. It also leads to things. In addition, the water-soluble silk fibroin produced as part of the recycling of recycled clothing or silk waste can be used to contribute to environmental problems by effectively using durable and strong processing methods. It is an object of the invention.

Means for solving the problem

The present inventor has solved such economics, environment / safety, especially the aging of processing chemicals, and has promoted development research on processing methods for functional fibers that are friendly to the global environment. Modification processing of natural fiber, regenerated fiber or semi-synthetic fiber material using monochlorotriazine fiber modification processing chemical mixture obtained by heat reaction with water-soluble sericin and / or silk fibroin in the presence of binder As a result, it was found that a fiber material excellent in form stability and functionality can be obtained.
In particular, the drug mixture of the present invention has improved stability and can be stored at room temperature, so that its practical value has been remarkably increased.

The present invention is a processing method characterized by modifying fibers using a drug mixture obtained by reacting cyanuric chloride and sericin and / or silk fibroin by heating in the presence of an acid binder. Is a very complex multi-component mixture.
The reason is that water-soluble sericin or silk fibroin can be obtained by scouring or hydrolyzing raw silk. As described on page 6, page 36, the molecular weight is distributed from several hundreds to several hundreds of thousands, and the binding state of amino acids is a very complicated and diverse multicomponent mixture.
The monochlorotriazinyl group that binds to one molecule of sericin or silk fibroin (hereinafter sometimes collectively referred to as a high molecular protein) is not limited to one, and many triazinyl groups may be bound at random. . Furthermore, when considering the reaction form at the molecular level, one molecule of cyanuric chloride is bonded to two molecules of a polymer protein by cross-linking, and one molecule of cyanuric chloride reacts with one molecule of cyanuric chloride. Cross-linking is conceivable, but in any case, one reactive chlorine atom in cyanuric chloride is left, that is, a large number of monochlorotriazinyl groups are bound to one or more macromolecular proteins. A monochlorotriazine-based drug mixture is synthesized.

Patent No. 3366000 describes a method for processing a functional fiber using a dichlorotriazine-based drug. Among them, (1) as a drug synthesis method, when cyanuric chloride is used to react with sericin, -5 is used. It is described that a dichlorotriazine-based compound can be obtained by reacting at -5 ° C. When a dichlorotriazine-based compound is used as a starting material, a monochlorotriazine-based compound is obtained by reacting at 0-30 ° C. It is described that the form stabilizing effect cannot be expected unless it is a dichlorotriazine-based compound.
However, the description of the monochlorotriazine-based drug in this patent specification was written by imagination, and at the time of this patent application, the monochlorotriazine-based compound was synthesized or processed into a fiber and not verified. Wrong description. In other words, this patent limits the claims to the dichlorotriazine compounds, because the monochlorotriazine system does not cause a crosslinking reaction, and therefore it is determined that a form stabilizing effect cannot be expected. The point is wrong as described below.
In view of the fact that the monochlorotriazine compound is not included in the claims, the method for synthesizing the monochlorotriazine compound from cyanuric chloride is not described, and the examples are all dichlorotriazine compounds. It is clear that at the time of filing, the practical value of monochlorotriazine compounds derived from cyanuric chloride was not recognized.

However, according to our research after that, the synthesis of monochlorotriazine compounds obtained by reacting macromolecular proteins with cyanuric chloride cannot be achieved sufficiently when reacted at room temperature, and the reaction is carried out at room temperature. The chemicals were still unstable, and when stored in a sealed container, it was found that the container may be deformed by the pressure generated by the gas generated by the chemical change over time. On the other hand, a monochlorotriazine compound obtained by reacting a high molecular protein with cyanuric chloride at a heated temperature is stabilized, and at the same time imparts a form stabilizing effect and functionality equivalent to or higher than that of a dichlorotriazine compound. I found the surprising fact that it was effective.
That is, in the case of a monochlorotriazine compound, a monochlorotriazine monomolecular compound does not undergo a crosslinking reaction, but a compound in which a plurality of monochlorotriazinyl groups are bonded to a polymer protein undergoes a crosslinking reaction via the polymer protein, resulting in form stability. It was found that an effect can be obtained.
As a result, the problem of change with time of the drug, which is a fatal defect of Japanese Patent No. 3366000, was solved, and the practical value of using the drug of this system was remarkably improved, and the prospect of practical use was obtained.
The drug used in the present invention, ie, a compound obtained by reacting and binding cyanuric chloride to a high molecular protein at a heated temperature is a very complex and multi-component mixture, and it is impossible to simply specify the structure of the compound. However, it is a water-soluble cross-linking drug mixture that does not contain an unstable dichlorotriazinyl group that changes with time at least at room temperature, and is stabilized by binding a large number of monochlorotriazinyl groups to a polymer protein.
Considering the case of a triazine monomolecular compound, dichlorotriazine is an essential condition for the crosslinking reaction. However, when a plurality of triazines are bonded to a polymer protein, it is not necessary to use dichlorotriazine, and it has been found that even monochlorotriazine exhibits a form stabilizing effect by a crosslinking reaction.

An example of the pharmaceutical synthesis method of the present invention is as follows. First, sericin and / or silk fibroin is dissolved in ice water, and then a small amount of penetrant is added for the purpose of increasing the water compatibility of cyanuric chloride, and then added and suspended with cyanuric chloride. After that, an alkaline acid binder such as sodium carbonate is added in a theoretical amount, that is, in the case of sodium carbonate, 2 mole ratio is added little by little at 0 to 5 ° C. with respect to 1 mole of cyanuric chloride. After stirring for several tens of minutes to several hours at 0 to 10 ° C., the mixture is heated to 40 to 80 ° C. and stirred for several tens of minutes to several hours.
The method of processing fibers using the monochlorotriazine compound to which this high molecular protein is bound is based on the so-called reactive dye dyeing method, the pad-dry-steaming method, the pad-steaming method, the pad-dry-cure method. Can be carried out by the method of dyeing or dyeing.

The embodiment of the present invention will be described in more detail.
A polymer protein such as sericin or silk fibroin, alone or a mixture thereof, is added to ice water to room temperature water to a concentration of 0.1 to 10% and dissolved by stirring, and then cyanuric chloride is equivalent to the polymer protein in an amount of 20 to 20%. Add alkaline substances such as sodium carbonate, potassium carbonate, sodium bicarbonate, sodium silicate, etc. little by little while stirring and add little by little over 10 minutes to 2 hours so that the pH is within the range of 7-10. Go. After adding cyanuric chloride, the mixture is stirred for several hours at a temperature of 10 ° C. or lower, and then heated and heated to 40 to 80 ° C. Stir at the same temperature for several tens of minutes to several hours. The end point of the reaction is the point where the dichlorotriazine compound disappeared. Naturally, when the heating temperature is low, heating and stirring may be performed for a long time, and when the temperature is high, heating and stirring may be performed for a short time. However, practical reaction rates cannot be obtained at 0 to 30 ° C. The reaction mixture thus obtained is a compound that is stable at room temperature, and is a crosslinkable drug mixture for fiber modification processing that can be stored at room temperature for one month to several months.
In the case of the dip dyeing method, the method of processing the fiber material using the reaction mixture chemical is carried out in water having a bath ratio of 1: 2 to 1:50 in a concentration of 0.01 to 1:50 depending on the processing purpose. In addition to adding 10%, an acid binder such as sodium carbonate or sodium bicarbonate is added in an amount of 0.1 to 5%, and the pH is raised to alkalinity. During the heating, 0 to 150 g / l of sodium nitrate is added. The temperature may be raised stepwise or may reach a high processing temperature at once, but the mixture is kept warm at 60 to 130 ° C. for several hours to several minutes. After washing with water, it is finished by soaping, washing with water and drying at 50 to 100 ° C. A softening treatment may be performed as necessary, or a softening agent or a penetrating agent may coexist during processing.
In the case of the padding method or the printing method, a penetrating agent or a paste is added to the above-described dyeing bath as necessary and the cloth is padded and squeezed, and then dried up once, or remains in a semi-dry or wet state. Steam at 130 ° C for several minutes to several hours, or squeeze pad and pre-dry, then cure and cure at 100-180 ° C for several seconds to several minutes, then washed with water, soaped, washed with water Dry and finish. Also in this case, it may be treated with a soft finish during processing or in the last step.

The high molecular weight protein that can be used in the present invention is an aqueous solution containing a slightly low molecular weight sericin recovered from a silk alkali refining waste liquid, or a slightly large molecular weight sericin recovered by chemical-free high temperature high pressure method refining. I can do it. Silk fibroin is preferably hydrolyzed and previously water-soluble.
A good result is often obtained when a high molecular weight protein having a molecular weight peak in the range of 1 to 20,000 is used. These high molecular weight proteins may be concentrated by an ultrafiltration concentration method or the like, or may be further dried by a spray drying method or the like to form a powder.
Silk protein is a natural material and is a polycondensation polymer protein of many kinds of amino acids, which has a difference between wild silkworms and rabbits, and has large variations in molecular weight and molecular weight distribution. In addition, these values vary depending on the hydrolysis conditions and the recovery method. Therefore, it is necessary to check the analysis value and physical properties of the molecular weight distribution and to examine the water solubility and to reflect them in the synthesis or processing conditions. Furthermore, it is also important to make effective use of hydrolyzed silk fibroin produced as part of the recycling of recycled clothing or silk waste discharged as fiber waste. As described in Fragrance Journal, April 2000, p. 23, hydrolyzed silk having an appropriately adjusted molecular weight can be used, and hydrolyzed silk derivatives can also be used.

The fiber material to be processed of the present invention is a cellulosic fiber material such as cotton, hemp, viscose rayon, cupra rayon, lyocell, cellulose acetate, or the like, or a protein type such as wool, mohair, Angola, alpaca, cashmere, animal hair, silk, etc. Any fiber containing a fiber material and having a reactive substituent such as an amino group, a hydroxyl group, or a thiol group may be used. For example, a fiber material called natural fiber, regenerated fiber, semi-synthetic fiber, etc. can be mentioned, but it is only necessary to have a reactive group such as polyvinyl alcohol, and it is limited to these specific examples. It is not something.
These fiber materials may be used alone, or may be a blended or woven fiber with other natural fibers or synthetic fiber materials. Further, the present invention can be applied to all forms of fiber materials such as yarn, woven fabric, knitted fabric, and non-woven fabric.
The fiber material processed and modified by the method of the present invention is excellent in form stability, becomes a functional fiber excellent in moisture absorption / moisture absorption and wearing comfort, and various characteristics of silk such as unique luster, A functional fiber having a warm texture, moisture retention, deodorant property, antioxidant property, ultraviolet absorption property, antibacterial property and the like, and excellent in strength and durability can be obtained.
In particular, the method of the present invention that can utilize sericin, which is a silk protein contained in waste liquid generated in the scouring process of silk, in a method with high practical value has the effect of two birds with one stone of reducing wastewater load and recycling waste. It is a new technology that responds to environmental problems in the 21st century and can be said to be an eco-friendly fiber processing method.

  Hereinafter, the present invention will be described in detail by way of examples. However, the present invention is not limited to these examples. In the examples, parts and% mean parts by weight and% by weight.

Example 1
150 parts of water-soluble sericin powder is stirred and dissolved in 7500 parts of ice water. Next, 12 parts of a penetrant (Meisei Chemical Industry Co., Ltd .: Mynex SO) is added, 500 parts of cyanuric chloride is added, stirred and suspended, and 576 parts of sodium carbonate is gradually added over about 1 hour. During this time, sodium carbonate is added so that the temperature is kept at 0 to 5 ° C. and the pH is kept at 7 to 10. Next, after stirring at the same temperature for 1 hour, if the temperature is gradually raised to 45 ° C., the temperature is maintained at 45-50 ° C. for several hours so that the final PH falls within the range of 8.0-8.3. A small amount of sodium carbonate is added and the reaction is terminated when the dichlorotriazine-based compound has almost disappeared.
Next, 284 parts of water is added to 316 parts of the drug reaction mixture and mixed. Next, 16 parts of sodium carbonate is added and dissolved, 1.2 parts of penetrant Minex SO is added, and 150 parts of urea is further added to form a padding bath.
The bath is padded with 100% cotton paddle and squeezed and pre-dried at 105-110 ° C. for 5-10 minutes in a warm air dryer. Subsequently, it is cured at 145 to 155 ° C. for 4 to 5 minutes. Next, after washing with water, it is poured into hot water, pH is adjusted to weak acidity, soaped at 90-98 ° C. for 10 minutes, washed with water, dried and finished.
The dimensional change rate of the fabric processed under such conditions according to the washing test of JIS-L-0217 103 method was 0.0% for both vertical and horizontal, indicating a good washability.
When the equilibrium moisture content at 20 ± 2 ° C. and 65 ± 5% RH was measured, the moisture retention was 8.33%, which was improved and improved by 20% compared to the unprocessed product. When the same dough was processed, the improvement rate was more than 18%. As for the burst strength, the unprocessed product and the processed product of this example showed almost the same value. Moreover, the dimensional change rate of the unfinished product was vertical -4.5% and horizontal -2.0%.
The equilibrium moisture content of 3.21% of the raw cotton yarn described in Example 1 of Japanese Patent No. 3366000 is lower than the equilibrium moisture content of nylon of 4%, which is an abnormal value. The equilibrium moisture content of cotton under this condition should generally be a value of around 7%, and it is considered that cotton yarn that had undergone some pre-processing was used.

Example 2
When processed in the same manner as Example 1 except that 18 parts of nitric oxide was added instead of urea and 100% cotton knit was used instead of 100% cotton for the fiber to be processed, JIS-L-0217 of the processed fabric was used. The dimensional change rate according to the 103 method washing test was vertical, -1.0%, and horizontal -0.5%, indicating good form stability.
When the equilibrium moisture content at 20 ± 2 ° C. and 65 ± 5% RH was measured, the moisture retention was improved by 23% compared to the unprocessed product, which was superior to the improvement rate when processed in Patent No. 3366000 Example 2. The value is shown. The dimensional change rate of the unprocessed product was vertical 5.5% and horizontal 2.0%.

Example 3
When processed in the same manner as in Example 2 except that silk 100% decyne was used as the fiber to be processed and sodium bicarbonate was used as an acid binder in a 2.5 molar ratio to cyanuric chloride instead of sodium carbonate, The dimensional change rate by the washing test of JIS-L-0217 103 method was vertical, -1.2%, horizontal -0.5%, and showed good shape stability. The moisture retention was measured by measuring the equilibrium moisture content at 20 ± 2 ° C. and 65 ± 5% RH, and was improved by 12% compared to the unprocessed product. The dimensional change rate of the unfinished product was vertical-8.5% and horizontal-7.0%.

The invention's effect

According to the present invention, animal protein such as sericin and silk fibroin can be firmly bound to a fiber material by a crosslinking agent having excellent stability, and morphological stability having excellent texture, moisture retention, durability and strength. And you can get a fiber material with excellent wearing comfort. The most important factor of the present invention is that the use of a stabilized cross-linking agent mixture with little change over time can be used in place of the unstable water-soluble dichlorotriazine-based cross-linking agent. .
In addition, sericin, which has attracted attention in recent years as one of the important proteins, is disposed of as a scouring waste liquid of silk. It also leads to. In addition, the establishment of a recycling system for garments is an urgent issue, but since it is thought to contribute to the construction of such a recycling society, it is an important element of the present invention that it is an environmental measure for two birds with one stone.
Accordingly, the present invention is an invention that leads to the development of eco-friendly textile processed products that are friendly to the global environment and at the same time to foster eco-business.

Claims (7)

A monochlorotriazine fiber-modifying agent obtained by heating and reacting cyanuric chloride with water-soluble sericin or / and silk fibroin in the presence of an acid binder. A fiber material characterized by modifying a fiber material using a monochlorotriazine-based reaction mixture obtained by heat-reacting cyanuric chloride and water-soluble sericin or / and silk fibroin in the presence of an acid binder. Modification processing method. A functional fiber material modified by using a monochlorotriazine-based reaction mixture obtained by heating and reacting cyanuric chloride with water-soluble sericin or / and silk fibroin in the presence of an acid binder. As the sericin or / and silk fibroin according to claim 1, claim 2 or claim 3, water-soluble sericin or / and water-soluble silk fibroin obtained by scouring or hydrolyzing silk is used. Quality processing chemical mixture, processing method and processed functional fiber material. Alkaline substances such as alkali metal and / or alkaline earth metal carbonates, bicarbonates, phosphates, acetates, silicates and hydroxides as acid binders in claim 1, claim 2 and claim 3 A fiber modification processing chemical mixture, processing method and processed functional fiber material characterized by using Cellulosic fibers such as cotton, hemp, viscose rayon, cupra rayon, lyocell, cellulose acetate, etc. as the fiber material to be modified in claim 1, claim 2 and claim 3, wool, mohair, Angola, alpaca, cashmere, A method for modifying natural fibers, regenerated fibers and / or semi-synthetic fiber materials, characterized by using protein fiber materials such as animal hair and silk. Natural fiber material, regenerated fiber material, or semi-synthetic material characterized in that sericin and / or silk fibroin is covalently bonded to fiber via 1,3,5-triazine-2,4,6-triyl group Fiber material.