JP4132165B2 - Insect repellent processing method of fiber - Google Patents

Description

[0001]
BACKGROUND OF THE INVENTION
The present invention relates to an insecticidal processing method for protein fibers, and more particularly to an insecticide for protein fibers, and an insecticidal processing method for protein fibers treated with the insecticide. More particularly cells of Bacillus thuringiensis (Bacillus t huringiensis) (hereinafter, sometimes abbreviated as BT cells.) Or fungus protein fiber protectant agents and insecticidal protein active ingredient to produce and The present invention relates to an insect repellent processing method for protein fibers treated with the insect repellent.
[0002]
[Prior art]
Protein-based fibers, especially wool and animal hair, have the characteristics that they are more resistant to wrinkling, do not lose shape, are porous, flexible, light and warm. The fibers are also used in felt products because they absorb and diverge moisture gradually and have a compaction property.
However, since it is a protein fiber, it has a drawback that it is susceptible to insect damage, and is a typical fiber that needs an insect repellent treatment along with silk.
[0003]
Known insect pests that damage protein fibers include moths, moths, mosenga, cicadas, and larvae, which are harmful to the fibers during the larval stage. Among these pests, the Himekatsuobushimushi has been established in Japan for a long time, and Himemarukabushimushishi are widely distributed throughout the world, both of which are seriously damaging to the wool and animal hair industry.
[0004]
Pesticides that feed on these protein fibers can be broadly classified as follows: Do not give pests a growing environment by cleaning, etc., or use storage conditions such as CA (Controlled Atmosphere) or low-temperature storage methods, or high-temperature treatment methods. There are a method to pay attention to and a method using a control agent.
Pesticides include preventives and pesticides. Specific examples of preventives include sublimable insecticides (paradichlorobenzene, naphthalene, camphor, etc.), transpiration agents (empensulin, allethrin, dichlorvos, etc.), insecticide processed paper ( Arelesrin, permethrin, diazinon, fenitrothion, etc.) and insect repellents (mitine FF, Eulan U33, Gardna, allesrin, permethrin, etc.).
In addition, fumigants (methyl bromide, hydrogen phosphide, ethylene oxide, etc.), fumigants (fenitrothion, permethrin, etc.), contact insecticides (fenitrothion, fenthion, chlorpyrifosmethyl, dichlorvos, diazinon, permethrin, etc. )It has been known.
[0005]
Among the above-mentioned preventive agents, the insect repellent is used as one of the insect repellent measures for protein fiber products such as clothes and carpets, at the product manufacturing stage and after washing and cleaning of the products. As this insect repellent, a dieldrin-based compound has been conventionally used, but its use is practically prohibited due to toxicity to humans and fish. Therefore, at present, halogenated diphenylurea derivatives (mitine FF), phosphonium compounds (eulan U33), phenyl phosphate compounds (Gardner), pyrethroid compounds (aresulin) and the like are mainly used.
However, there is a demand for the development of insecticides that are less toxic to human livestock and superior in durability than the insecticides described above, and bromine-containing organic compounds, silicon-containing organic compounds, surfactants, etc. have been studied. However, in particular, from the viewpoint of low toxicity to the human body, a satisfactory one has not been obtained.
[0006]
On the other hand, the insect repellent treatment of wool and animal hair is performed in a dyeing process, a scouring (washing) process, a yarn felting process, a batch solvent process, and the like. Among these, the insect repellent processing in the dyeing step is to add an insect repellent (control agent) to the dye bath and to give the insect repellent to wool and animal hair together with the dye. The treatment in the scouring step is a method in which an insect repellent is introduced at the final stage of the continuous washing step and adhered to wool or the like. The application of insect repellents in these processes is most often carried out because it is economically superior.
In these methods, in order to use an insect repellent having a small fixing force in the above-mentioned process, it is necessary to use it mixed with an appropriate fixing agent. However, in view of the fact that there are no adverse effects on human livestock and the environment, there are no known drugs and methods that are sufficiently satisfactory.
[0007]
In addition, the insect repellent treatment in the yarn felting process may result in non-uniform adsorption of the repellent and may require special processing containers. Moreover, this method is a special process that is applied only during felting.
The batch solvent process is a special method that uses a dry cleaning solvent because a special insect repellent is used. In addition, since a solvent is used in this method, there are concerns about adverse effects on livestock and the environment.
[0008]
[Problems to be solved by the invention]
Therefore, an object of the present invention is to develop a means for imparting insect repellency to protein fibers without adversely affecting human livestock and the environment. That is, to develop an insecticide for protein fiber that can effectively control the pests without adversely affecting human livestock and the environment, and a method for imparting insecticide to protein fiber using the insecticide. .
[0009]
In the present invention, BT cells or insecticidal proteins produced by the bacteria are used as insect repellents. BT cells were first isolated as a pathogen against silkworms in 1901 and are known to produce crystalline insecticidal proteins. The protein is non-toxic even when inoculated into the body fluid of insects, and only exhibits toxicity when eaten and digested by insects. In addition, BT cells and insecticidal proteins are very specific, exhibiting insecticidal activity against specific insects, and are therefore highly safe for human livestock.
Since it has such characteristics, BT cells are used as a kind of biological pesticide, and it is approved to use the live fungus for raw food vegetables such as cruciferous vegetables.
However, no BT cells or insecticidal proteins that are effective against cutworms that damage protein fiber have been found.
As a result of intensive studies, the present inventors have found that Bacillus thuringiensis SSK-10 strain (FERM BP-6162) has a strong insecticidal activity against cutworms, insecticidal proteins produced by the fungus Have the same action, and by mixing them with a substance (binder) used for proper fixation, they can be effectively fixed to protein fibers. Based on this, the present invention has been completed.
[0010]
[Means for Solving the Problems]
The present invention described in claim 1 contains a microbial cell of Bacillus thuringiensis SSK-10 strain (FERM BP-6162) or an insecticidal protein produced by the bacterium as an active ingredient, and has an insecticidal effect against cutworms An insect repellent for protein fibers having The present invention according to claim 2 comprises, as an active ingredient, a bacterial cell of Bacillus thuringiensis SSK-10 strain (FERM BP-6162) or an insecticidal protein produced by the fungus mixed or dispersed in a natural protein. It is an insect repellent for protein fibers that contains and has an insect repellent effect against cutworms. The present invention according to claim 3 is the insect repellent according to claim 2, wherein the natural protein is at least one of wool keratin, silk fibroin and collagen. The present invention according to claim 4 is the insect repellent according to claim 2, wherein the natural protein has an average molecular weight of 5000 to 30000 obtained by subjecting at least one of wool keratin, silk fibroin and collagen to protease treatment. is there. The present invention according to claim 5 is an insect repellent processing method for protein fibers, characterized by treating protein fibers with the insect repellent according to claim 1 or 2. The invention according to claim 6 is the method according to claim 5, wherein the protein fiber is pretreated with protease. The invention according to claim 7 is a method for producing a protein fiber, which comprises blending an insect repellent for protein fiber with an insect repellent effect against the cuticle beetle according to claim 1 or 2. The invention according to claim 8 is the method according to claim 7, wherein the cutlet worm is a chickworm worm and / or a dipworm. The invention according to claim 9 is a protein-based fiber having an insect repellent effect against cutworms treated with the insect repellent according to claim 1 or 2. The invention according to claim 10 is a processed fiber product using the protein fiber according to claim 9 as a raw material.
[0011]
DETAILED DESCRIPTION OF THE INVENTION
The insect repellent for protein fiber of the present invention comprises BT cells or an insecticidal protein produced by the cells as an active ingredient. Among BT cells, Bacillus thuringiensis SSK-10 strain (FERM BP-6162) is particularly preferable.
BT cells can be obtained by culturing by a conventional method using a medium in which the present bacteria can sufficiently grow. BT cells are usually dried and used as a powder. Moreover, an insecticidal protein can be obtained by separating from the cells by an appropriate means.
[0012]
The amount of BT cells or the insecticidal protein produced by the cells may be appropriately determined in consideration of the purpose of use, the type of the target protein fiber, etc., but generally BT cells are used. In this case, 50 to 50000 mg per kg of protein fiber, preferably about 200 to 10000 mg, and when using an insecticidal protein, 5 to 12500 mg per kg of protein fiber, preferably about 20 to 2500 mg may be used as a guide.
[0013]
A sufficient amount of BT cells and insecticidal protein cannot be fixed to protein fibers. Therefore, it is preferable to use it together with a fixing agent in order to fix a sufficient amount of BT cells and insecticidal protein to protein fibers without adversely affecting human livestock and the environment.
Natural protein is effective as a fixing agent for fixing BT cells and insecticidal proteins to protein fibers. There are no particular restrictions on the natural protein that can be used, and various proteins can be used. For example, wool keratin, silk fibroin, collagen and the like are preferable. In particular, a natural protein treated with a protease and having an average molecular weight of 5000 to 30000 is effective. If the average molecular weight exceeds 30000, the fixing efficiency to the fiber will be low, and if the average molecular weight is less than 5000, the protein fiber will penetrate into the inside of the protein fiber. Is not preferable because it cannot be efficiently fixed to the fiber.
[0014]
By making these natural proteins coexist with BT cells and insecticidal proteins during various processing of protein fibers, insect processing is performed without deteriorating the texture of the protein fibers and without adversely affecting human livestock and the environment. Can be implemented. When BT cells that are insect repellents or insecticidal proteins produced by the fungi are used in combination with natural proteins, the method is not particularly limited. For example, both are mixed, preferably BT cells are used as natural proteins. The dispersion can be carried out by adhering to the protein fiber by the exhaust method or the pad method. Here, there is no particular limitation on the amount of the natural protein used as the fixing agent. For example, in the exhaust method (dyeing industry, 43 (4), 20 (1995)), 5-50% owf, pad method (dyeing industry) 43 (4), 20 (1995)) is suitably 0.1 to 10% (w / w). In addition, the amount of natural protein can be increased by subjecting the protein fiber to an enzyme treatment with a protease or the like in advance.
[0015]
When carrying out the above insect-repellent processing on protein fibers, there is no restriction on the process, and it can be carried out at any stage such as a scouring process, a dyeing process, and a finishing process. Furthermore, there are no restrictions on the form of protein fiber that provides insect repellent properties, from fibrous loose hair, tops, yarns such as rovings, weaving yarns, knitting yarns, and nonwoven fabrics such as felt to woven fabrics and knitted fabrics. In addition to processing, it can also be processed into sewing products. When insecticidal processing is carried out on such a fiber processed product, it is fixed to the fiber processed product by spraying or immersing BT cells, etc., preferably mixed or dispersed with a fixing agent. That's fine.
Furthermore, at the time of dry cleaning of the above-mentioned fiber processed product, it is possible to carry out insect repellent processing by adding a trace amount of the insect repellent of the present invention to the dry cleaning liquid.
[0016]
The protein-based fiber imparted with insect repellent properties by the method of the present invention can remarkably reduce the damage caused by cutworms such as Himekaobushimushi and Himemarukabushimushi, and is harmless to humans and the environment. In addition, since both the insect repellent and the fixing agent of the present invention are proteins, there is little change in the appearance and texture of the protein fiber before and after fixing them. Further, the fiber after fixing has a characteristic that the strength and elongation become large.
In addition, when producing processed fiber products such as sewn products with protein-based fibers that have been subjected to insect repellent treatment according to the present invention, it is possible to suppress the occurrence of puckering, which is a wrinkle generated in the vicinity of the seam, and to recover wrinkles. In addition, it is possible to produce a fiber product having high dimensional stability and excellent shape stability.
[0017]
【Example】
Next, although an example etc. explain the present invention in detail, the present invention is not limited to these.
Production Example 1
Bacillus thuringiensis SSK-10 (FERM BP-6162) with 2.25% peptone, 0.3% glucose, 1.2% monopotassium phosphate, 1.5% dipotassium phosphate, magnesium sulfate heptahydrate 0.0123%, manganese sulfate heptahydrate 0.002%, zinc sulfate heptahydrate 0.00014%, ferrous sulfate heptahydrate 0.002% and calcium chloride dihydrate 0.0184% For 2 days at 30 ° C. After confirming the presence of the crystal protein in the BT cells collected from the culture by microscopic observation, the cells were collected by centrifugation according to a conventional method. The bacterial cells thus obtained were dried with a spray dryer to obtain powdered BT bacterial cells (hereinafter referred to as BT dried product).
[0018]
Example 1
JIS Dye Fastness Test Attached White Cloth (Wool) is cut into 25 mm x 12.5 mm, and BT dried product obtained in Production Example 1 or various commercially available insect repellent water dilutions 0.50.ml Was sprayed with a spray gun (0.8 kg / m ² ). The commercially available insect repellents used are chlornicotil (trade name: Admeier wettable powder, manufactured by Bayer Agrochem Japan), synthetic pyrethroid (trade name: agrosulin wettable powder, manufactured by Sumitomo Chemical Co., Ltd.) and organic phosphorus. System (trade name: Ortran wettable powder, manufactured by Takeda Pharmaceutical Company Limited).
The white cloth was air-dried all day and night, and then weighed and placed in a plastic cup having a diameter of 5 cm to release 5 chickworm larvae. Next, the cap was covered and the breeding test was conducted for 18 days in the dark at a temperature of 25 ° C. and a humidity of 65%. After the breeding, the weight of the white cloth was measured, and the weight was reduced compared to the weight of the white cloth at the start of the experiment. The rate was determined and this was taken as the eating damage rate. Also, hole evaluation is performed by the IWS method. A: No detectable damage, B: Partially cut yarn or fiber, C: Some small holes, D: Some large Judged as one of the holes. The results are shown in Table 1.
As is apparent from the table, compared to commercially available insect repellents, the dried BT product was found to have a superior effect on wool damage.
[0019]
[Table 1]
[0020]
Production Example 2
To 1 g of wool, 100 ml of 8M urea solution and 0.5 ml of 2-mercaptoethanol were added, and the pH was adjusted to 10.5 with potassium hydroxide solution. This wool suspension was swirled for 72 hours at 40 ° C. and 100 rpm.
Then, it dialyzed for 72 hours using the dialysis tube (made by a spectrum company) of the molecular weight cut off 3500. After completion of dialysis, the dialysis tube contents were collected, protease N (manufactured by Amano Pharmaceutical Co., Ltd.) was added at 1% per wool weight, and treated at 50 ° C. and 80 rpm for 2 hours. Subsequently, the enzyme was inactivated by treatment at 90 ° C. for 10 minutes to obtain a wool degradation product.
The molecular weight distribution of the obtained wool degradation product was examined with a liquid chromatograph (intelligent HPLC system / Gulliver series, manufactured by JASCO Corporation) and a gel filtration column (Biofine PO-700K-L column, manufactured by JASCO Corporation). The average molecular weight of the wool degradation product was 22,000. This is called wool keratin.
[0021]
Production Example 3
100 ml of 40% calcium chloride solution was added to 20 g of silk and boiled for 5 hours. Then, it dialyzed for 72 hours using the dialysis tube (made by a spectrum company) of the molecular weight cut off 3500. Next, the contents of the dialysis tube were collected, and protease S (Amano Pharmaceutical Co., Ltd.) was added at 1% per silk weight and treated at 50 ° C. and 80 rpm for 2 hours. Subsequently, the enzyme was inactivated by treatment at 90 ° C. for 10 minutes.
When the molecular weight distribution of the obtained silk decomposition product was examined in the same manner as in Production Example 2, the molecular weight distribution had three peaks, and the average molecular weights were 18,000, 12300, and 6000, respectively. These are referred to as silk fibroin.
[0022]
Test example 1
Protease NL (manufactured by Amano Pharmaceutical Co., Ltd.) was added to a woolen fabric (200 mm × 200 mm) at an enzyme addition amount of 10% owf and a bath ratio of 1:30, followed by shaking treatment at 50 ° C. and 80 rpm for 30 minutes. Subsequently, the enzyme was inactivated by treatment at 90 ° C. for 15 minutes. The wool keratin obtained in Production Example 2, silk fibroin obtained in Production Example 3, or commercially available collagen having an average molecular weight of 29000 (trade name: HCP M-15, manufactured by Nitta Gelatin Co., Ltd.) ) Was fixed. The concentrations of the natural protein used were 2.63% wool keratin, 3.85% silk fibroin, and 5.00% collagen.
[0023]
The exhaustion method was carried out using a shaking incubator (120 rpm) under the conditions that the amount of fixing agent used was 50% owf, the bath ratio was 1:30, the treatment temperature was 50 ° C., and the treatment time was 30 minutes.
Further, the pad method was performed with a fixing agent concentration of 5% (w / w) and a pickup rate of 80% (mangle drawing rate).
Subsequently, heat fixation was performed by a dry heat method (90 ° C. for 30 minutes) or a wet heat method (vacuum 6 minutes, steam 80 ° C. for 30 minutes, vacuum 6 minutes).
The amount of natural protein adhering to the wool fabric was determined by measuring the change in the weight of the wool fabric before and after the treatment by the absolutely dry method. That is, it was determined by allowing the sample to stand in a drier at a temperature of 105 ± 2 ° C. to reach a constant temperature.
As a result, as shown in Table 2, fixation of the natural protein to the wool fabric was observed in all test sections. In particular, wool keratin and silk fibroin were found to increase the amount of fixation by performing enzyme treatment with protease NL, and the pad method showed a higher amount of fixation than the exhaust method. In the table, E0 indicates that the enzyme treatment with protease NL is not performed, E10 indicates that the enzyme treatment is performed, Q indicates the exhaust method, and P indicates the pad method.
[0024]
[Table 2]
[0025]
Test example 2
Using the wool keratin obtained in Production Example 2, silk fibroin obtained in Production Example 3 and commercially available collagen having an average molecular weight of 29000 (trade name: HCP M-15, manufactured by Nitta Gelatin Co., Ltd.) as a sticking agent, The degree was measured. First, 20% owf of the fixing agent was added to the worsted yarn (2/60), and fixed by the exhaust method in the same manner as in Test Example 1. Subsequently, it was heat-fixed by a wet heat method (vacuum 6 minutes, steam 80 ° C. for 30 minutes, vacuum 6 minutes).
The high elongation of the wool yarn to which the fixing agent thus obtained was fixed was determined according to JIS L1095 7.5.1 (constant speed extension type). The results are shown in Table 3. As shown in Table 3, the tenacity and elongation of the wool yarn were improved by attaching the natural protein.
[0026]
[Table 3]
[0027]
Test example 3
Using the wool keratin obtained in Production Example 2 as a sticking agent, the same as in Test Example 1, using the pad method (sticking agent concentration 5% (w / w)) and dry heat heating method (90 ° C. for 30 minutes) The dried BT obtained in 1 was attached to an attached white cloth (wool) for JIS dyeing fastness test at a concentration of 8%.
The wool with the dried BT adhered thereto was subjected to a thermal decomposition treatment (JHP-22 type Curie Point Pyrolyzer, manufactured by Nihon Analytical Industrial Co., Ltd.) at 590 ° C. for 3 seconds, and then a gas chromatograph (GC-14APTF, manufactured by Shimadzu Corporation). Was analyzed. As a control, the same analysis was performed on the wool treated with only enzyme treatment and the wool treated with the dried BT without using the fixing agent. The results are shown in FIG. The figure is a pyrolysis gas clopyrogram. In the figure, A and B are the control group, A is the wool treated only with the enzyme treatment, B is the wool treated with the BT dry substance without using the fixing agent, and C is the wool of the test group. In addition, for the wool that had been subjected to the fixing treatment of the dried BT product without using the fixing agent in the control group, the wool after washing 10 times by the JIS L 0217 105 method was similarly analyzed by pyrolysis gas cropyrogram. The results are shown in FIG.
As shown in FIG. 1C, in the case of the test section, it was confirmed that the dried BT was fixed to the wool. Moreover, as shown in FIG. 2, after washing the wool which adhered the BT dry substance without using the fixing agent 10 times, the BT dry substance did not remain. On the other hand, although not shown, in the case of the test section (C), even after washing in the same manner, the same amount of BT dry matter as before washing remains and is firmly fixed. Was confirmed.
[0028]
Example 2
A trial for practical use was carried out in which a woolen woven fabric was prototyped and sewn according to the present invention. The raw fabric is treated with a standard arrangement method such as washing and boiled knitted wool fabric with a Karze structure using eyelash yarn (count: 2/72) for warp and eyelash yarn (count: 1/40) for weft. Then, the enzyme treatment was performed with a liquid dyeing machine at 50 ° C. for 30 minutes using 10% owf of prosthesis NL (Amano Pharmaceutical Co., Ltd.).
Subsequently, anti-dying was carried out with a leveling type acidic dye which also serves as an enzyme deactivation treatment. The dyeing conditions are: 0.037% owf for the sand blue E-HRNL (Sand), 0.253% owf for Sand Yellow E-2GSN (Sand), Sand Red E-HU (Sand) 3.4% owf, 8% owf anhydrous silica (manufactured by Shikoku Kasei Co., Ltd.) as an auxiliary agent, 2.5% owf concentrated sulfuric acid (manufactured by Kanto Chemical Co., Inc.), 1 arabon SCN-150 (manufactured by Bayer) Stained at 100 ° C. for 50 minutes using 0.0% owf.
Furthermore, insecticidal treatment was applied after dyeing. As processing conditions, the 0.5% solution of the dried BT prepared in Production Example 1 was fixed to the fabric by the exhaust method in the same manner as in Test Example 1 using 5% owf. At this time, the wool keratin hydrolyzate (average molecular weight 22,000) obtained in Production Example 2 was added to a 5% owf processing bath for the purpose of increasing the effect of fixing the dried BT to the cloth. After the insect repellent finish, the fabric was dried while also serving as a fixing treatment, and then subjected to arrangement such as shirring and steaming to finish an insect repellent fabric.
[0029]
Next, using the above-described insect-proof protein fiber fabric as a raw material, an upper and lower suit for a woman was prototyped. Since the texture of the fabric is soft and supple, puckering of the seam is unlikely to occur, and as a result, a well-made sewn product with excellent sewability could be created. Furthermore, since the insect repellent processing method of the present invention uses only protein, when producing a fiber product, it is possible to produce a fiber product with high wrinkle recovery and dimensional stability and excellent shape stability. .
[0030]
【The invention's effect】
INDUSTRIAL APPLICABILITY The present invention provides an insect repellent comprising, as an active ingredient, a Bacillus thuringiensis cell or an insecticidal protein produced by the fungus. By treating protein fiber with this insect repellent, an insect repellent effect on cutworms Can be produced. In addition, the appearance and texture of the protein fiber processed with insect repellent is small, and the strength and elongation are increased.
The insect repellent of the present invention exhibits high toxicity only to pests without adversely affecting human livestock and the environment. By using this insect repellent mixed or dispersed with a natural protein having a sticking action, the sticking to fibers is improved.
[Brief description of the drawings]
[Fig. 1] A is wool with enzyme treatment only, B is wool with BT cells fixed without using a fixing agent, and C is wool with BT cells fixed with a fixing agent. This is a pyrolysis gas chromopyrogram.
FIG. 2 is a pyrolysis gas cropyrogram after washing of wool (fixing agent not used) on which BT cells have been fixed.

Claims (10)

Bacillus thuringiensis SSK-10 strain (FERM BP-6162) or an insecticidal protein produced by the fungus as an active ingredient, and an insecticide for protein fibers that has an insecticidal effect against cutworms . Bacillus thuringiensis SSK-10 strain (FERM BP-6162) or an insecticide for protein fibers containing an insecticidal protein produced by the fungus mixed or dispersed in a natural protein as an active ingredient and having an insecticidal effect against cutworms .   The insect repellent according to claim 2, wherein the natural protein is at least one of wool keratin, silk fibroin and collagen.   The insect repellent according to claim 2, wherein the natural protein has an average molecular weight of 5,000 to 30,000 obtained by subjecting at least one of wool keratin, silk fibroin and collagen to a protease treatment. An insect repellent processing method for protein fibers, comprising treating protein fibers with the insect repellent according to claim 1 or 2. 6. The method according to claim 5 , wherein the protein fiber is pretreated with a protease. A method for producing a protein fiber, which comprises blending an insect repellent for protein fiber having an insect repellent effect against the cuticle beetle according to claim 1 or 2. The method according to claim 7 , wherein the cutlet worm is Himekatsu beetle and / or Himemaru cutworm.   A protein fiber having an insect repellent effect on cutworms treated with the insect repellent according to claim 1 or 2. Textile processing products with protein fiber according to claim 9 Symbol mounting as a raw material.