JP2018035070A - Terrestrial gastropod repellant composition and terrestrial gastropod repellant sheet using the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a composition that contains a chitosan-copper complex as an active ingredient, excels in coatability, film deposition properties and water resistance, and shows excellent repellent effect on terrestrial gastropods.SOLUTION: A terrestrial gastropod repellant composition contains a chitosan-copper complex and an aqueous resin. The aqueous resin is one or more resin selected from the group consisting of a cationic acrylic resin, a nonionic acrylic resin, a cationic urethane resin and a nonionic urethane resin.SELECTED DRAWING: Figure 3

Description

  The present invention relates to a composition for repelling terrestrial gastropods such as snails and slugs, and more specifically, chitosan-copper complex as an active ingredient, and has a high repellency effect on terrestrial gastropods and is excellent in sustainability of the effect. Relates to the composition.

  Terrestrial gastropods such as snails and slugs prefer humid conditions, and are active during the rainy season, increasing their habitat density and injuring various crops. Terrestrial gastropods lurk in the soil and in the shade during the day and are active at night and on rainy days, leaving vegetation shoots, flowers, leaves, fruits, etc., and leaving traces of eating damage.

  It is known that copper ions have a controlling effect on these land-gastropods. For example, it has been reported that a suspension of copper compounds such as cupric hydroxide and copper sulfate exhibits a lethal action on slugs (Patent Document 1). However, in the form of such a liquid agent, there is a concern that copper ions may flow out due to watering or raining, adversely affecting the environment, or reducing the sustainability of the effect. Therefore, it has been attempted to fix a copper compound to a substrate such as a nonwoven fabric or a plastic film. For example, a composition in which copper gluconate is dispersed in a specific water-soluble resin and a water-insoluble resin is formed on a PET film. A sheet coated on the surface has been proposed (Patent Document 2).

  On the other hand, a complex of chitosan and copper is known as a copper compound having a repellent effect against such pests. It has been reported that this compound is used as an acidic aqueous solution and exhibits repellent effects on slugs when applied to textile products (Patent Document 3). However, as described above, in the form of such a liquid agent, there is a concern that chitosan-copper complex may flow out due to rain or the like, resulting in a decrease in sustainability or an adverse effect on the ecosystem. Therefore, it is desirable to fix it to a solid carrier so that it can be recovered after use.

JP 63-162608 A JP 2001-354502 A Japanese Patent No. 5513863

  However, when the present inventors tried to make a solid formulation by mixing a chitosan-copper complex with a resin, the compatibility was low and it did not become a uniform composition in the first place. There may be a problem with formability. Further, even when a film is formed, the water resistance is low and the repelling effect may not be sufficiently maintained.

  Therefore, the present invention provides a composition comprising a chitosan-copper complex as an active ingredient, having good coating properties and film-forming properties, excellent water resistance, and a long-lasting repellent effect on terrestrial gastropods. Let it be an issue.

  As a result of diligent research, the present inventors have obtained a highly compatible and uniform composition by combining a specific resin with a chitosan-copper complex, and this composition has coating properties and film-forming properties. It is excellent in water resistance by forming a strong and stable film, and when a snail or slug comes into contact with this film, the surface of the film is dissolved appropriately by the mucus and comes into contact with copper ions. The present invention has been completed by finding that it exhibits excellent repellent behavior and is excellent in sustainability of the effect.

  That is, the present invention includes a chitosan-copper complex and an aqueous resin, and the aqueous resin is selected from the group consisting of a cationic acrylic resin, a nonionic acrylic resin, a cationic urethane resin, and a nonionic urethane resin. It is a land or gastropod repellent composition characterized by being a seed or two or more kinds of resins.

  Further, the present invention is a land and gastropod repellent sheet in which a repellent layer comprising the above composition is formed on at least one surface of a substrate.

  The terrestrial gastropod repellent composition of the present invention has good coating properties and film-forming properties, and the formed film stably retains the chitosan-copper complex and has a property of being gradually dissolved by mucus of the terrestrial gastropod. Have. Moreover, since the formed film has high water resistance, it is excellent in the repellent effect on the land and gastropod and the sustainability of the effect, and can prevent the outflow of copper ions into the environment.

External view showing watering test of the present invention External view showing the water immersion test of the present invention External view showing the land and gastropod repellent test of the present invention

  In the present invention, a chitosan-copper complex is used as an active ingredient. Chitosan-copper complex is a known compound and can be produced, for example, according to the description in Japanese Patent No. 5513863. The specific manufacturing method is illustrated below.

  The chitosan used for the production of the chitosan-copper complex can be used without particular limitation, but preferably has a degree of deacetylation of 70 to 90 and a weight average molecular weight of 10,000 or more, and a degree of deacetylation of 80 to 90 and weight. Those having an average molecular weight of 500,000 or less are desirable, and those having an average molecular weight of 10,000 or more and 200,000 or less are suitable.

  Copper (II) acetate can be used as a compound that forms a copper complex with chitosan. Chitosan is added to an aqueous solution in which copper (II) acetate is dissolved, and copper acetate is reacted with chitosan. Then, acetic acid is further added to dissolve the reaction product. An aqueous solution of a copper complex can be obtained.

  First, an organic acid such as acetic acid and lactic acid and an inorganic acid such as hydrochloric acid are dissolved in water to prepare an acid aqueous solution. After adding chitosan to the acid aqueous solution and dissolving it, copper acetate ( By introducing II) or cupric sulfate (II) cupric chloride, an aqueous solution of a chitosan-copper complex can be obtained in the same manner. At this time, the acid aqueous solution is preferably prepared by dissolving an organic acid or an inorganic acid in a hot water of 45 to 60 ° C. so as to have a concentration of 2 to 15% by mass (hereinafter simply referred to as “%”). The amount of chitosan introduced into the aqueous acid solution is preferably about 2 to 8%, and it is preferable to completely dissolve chitosan while maintaining 45 to 60 ° C. Further, copper (II) acetate, copper (II) sulfate, cupric chloride and the like may be hydrates, and are preferably added to a chitosan aqueous solution so as to have a salt concentration of 2 to 12%. By reacting while maintaining the temperature, a solution of chitosan-copper complex can be obtained. The time required for the reaction between chitosan and copper ions is about 2 to 6 hours, more preferably 3 to 5 hours.

In the chitosan-copper complex obtained as described above, the copper ion is chelate-bonded to the amino group (—NH ₂ ) bonded to C _{2 of the} chitosan unit structure as the binding mode of the copper ion to chitosan. On average, it is considered that 2 to 6 chitosan single molecules are randomly coordinated at a ratio of one copper ion. The obtained aqueous solution of chitosan-copper complex can be easily diluted with water at an arbitrary ratio.

  On the other hand, the aqueous resin used in the present invention is a group in which a resin component is dispersed in a solvent containing water, and is composed of a cationic acrylic resin, a nonionic acrylic resin, a cationic urethane resin, and a nonionic urethane resin. 1 type or 2 types or more selected from. Among these, from the viewpoint of compatibility with the chitosan-copper complex, film formation, and water resistance, a cationic acrylic resin and a nonionic urethane resin are preferable. For example, a water-soluble cationic acrylic resin and a cationic acrylic resin are preferable. A resin emulsion, a water-soluble nonionic urethane resin, a nonionic urethane resin emulsion, and the like are suitable. From the viewpoint of compatibility with the chitosan-copper complex, the resin emulsion is preferably a forced emulsification type with an external emulsifier rather than a self-emulsification type having a reactive group, a non-reactive hydrophilic group or a non-reactive hydrophilic segment. Moreover, you may use the thermosetting resin which a crosslinking reaction produces between polymers by thermosetting reaction. The acrylic resin refers to a resin containing at least acrylic acid or an acrylic ester as a monomer unit, and includes homopolymers thereof or copolymers with other copolymerizable monomers. From the viewpoint of compatibility with the chitosan-copper complex, film-forming property, water resistance, and the like, styrene-acrylic polymers such as styrene-acrylic acid ester copolymers are preferred.

  Commercially available products of the above cationic acrylic resins include N-Nicazole RX-672A (manufactured by Nippon Carbide), Polysol AP-1350 ((meth) acrylic acid ester), and Polysol AE-821 (styrene / acrylic acid ester copolymer). ) (Made by Showa Denko KK). Examples of commercially available nonionic acrylic resins include Polysol AP-1700N (styrene / acrylic acid ester copolymer). Examples of commercially available nonionic urethane resins include Adekabon titer HUX-895, HUX-830 (ADEKA), Superflex E-2000 (Daiichi Kogyo Seiyaku).

  The average particle size of these water-based resins is not particularly limited, but is preferably 0.01 μm to 10 μm, and preferably 0.1 μm to 2 μm from the viewpoints of compatibility with the chitosan-copper complex and film formation. 0.0 μm is more preferable.

  The content of the resin component (solid content) in the aqueous resin used in the present invention is preferably 5 to 60%, more preferably 10 to 55%. In addition, from the viewpoint of compatibility with the chitosan-copper complex, film formation, and the like, the viscosity is preferably in the range of 10 to 5000 mPa · s, and more preferably 20 to 4000 mPa · s. The water-based resin may contain a surfactant, a crosslinking agent, an ultraviolet absorber, an antioxidant, a pigment, a filler and the like in addition to water. In the present invention, the viscosity and average particle diameter of the water-based resin mean values measured by the following measuring method.

(Measurement method of viscosity)
A vibration type, a rotary type, a thin tube type, a falling body type, a cup type viscometer, etc. can be used. In particular, a single cylindrical rotary viscometer (B type) is preferably used, and measurement at 20 to 25 ° C. Value can be adopted.

(Measuring method of average particle size)
A particle size distribution measuring apparatus based on the dynamic light scattering method is preferably used.

  The content of the chitosan-copper complex in the terrestrial gastropod repellent composition of the present invention (hereinafter sometimes referred to as “repellent composition”) is not particularly limited, but film-forming property, repellent effect, etc. From the viewpoint of, the solid content is 0.5 to 10%, preferably 1 to 5%. On the other hand, the content of the aqueous resin is 0.2 to 55%, preferably 1 to 50% in terms of solid content. The mass ratio of the water-based resin and the chitosan-copper complex (in terms of solids) is preferably 80: 1 to 1:20 (water-based resin: chitosan-copper complex), and is 40: 1 to 2: 1. It is more preferable.

  In addition to the above essential components, a component such as a curing agent can be added to the land and gastropod repellent composition of the present invention as necessary. Examples of the curing agent include isocyanate compounds, zirconyl chloride compounds, and titanium lactate ammonium salts. Examples of commercially available products include Meikanate CX (manufactured by Meisei Chemical Industry Co., Ltd.), Organachix (manufactured by Matsumoto Fine Chemical Co., Ltd.), and the like.

  The terrestrial gastropod repellent composition of the present invention can be prepared by mixing the chitosan-copper complex, an aqueous resin, and optional components such as a curing agent added as necessary according to a conventional method.

  Further, by providing a repellent layer formed from the above-mentioned land and gastropod repellent composition on at least one surface of the base material, the land and gastropod repellent sheet of the present invention can be obtained.

  The substrate is not particularly limited. For example, paper such as wood, Japanese paper, fine paper, natural fibers such as cotton and hemp, and woven fabrics thereof, natural rubber, polyethylene, polyester, polyethylene terephthalate and other plastic plates and films. Examples thereof include fibers, woven fabrics, non-woven fabrics, metals, ceramics, and stones. Among these, paper, plastic and the like are preferable from the viewpoint of convenience in use and economy.

The formation of the repellent layer on the substrate can be performed according to a conventional method. For example, the repellent composition may be coated on the substrate and dried. Examples of the method for coating the repellent composition include a coating method using a knife coater, a rod coater (bar coater), a squeeze coater (two roll coater), a reverse roll coater, a gravure coater and the like. Although the application quantity of a repellent composition is not specifically limited, For example, 10-100 g / m < ² > is preferable and 20-50 g / m < ² > is more preferable. The coating amount can be controlled by the clearance provided on the bar coater wire or the glass coater, the number of times of application, the mesh size and shape of the roll, the clearance of the doctor blade, the number of times of application, and the like. Although the thickness of the repellent layer formed on a base material is not specifically limited, 5-1000 micrometers is preferable from viewpoints, such as the sustainability of a repellent effect, and 10-100 micrometers is more preferable. In coating, the viscosity may be adjusted by appropriately diluting the repellent composition or adding a thickener. The drying conditions are appropriately set according to the amount and type of the solvent so that the solvent is sufficiently removed. Moreover, you may heat-process and heat-harden as needed. Furthermore, in order to improve physical properties such as the strength of the film, it is preferable to age for about 1 to 4 weeks after the drying treatment.

  The repellent sheet of the present invention is one in which the repellent layer formed as described above is laminated on one or both surfaces of a substrate. When the repellent layer is formed on only one of the substrates, an adhesive layer may be provided on the other surface so that it can be fixed to the application site.

  As the land-hog gastropod which is the application object of the repellent composition and the repellent sheet of the present invention, snails such as Onimaimai, Usukawamaimai, Africamaimai, slug, Noharanakugeji, Kouranamakuji, Chakoura Namakuji, Fusujijakuji, Examples include slugs such as the Japanese slug and the reed slug.

  The film formed by the terrestrial gastropod repellent composition of the present invention has the property of being gradually dissolved by the mucus of the terrestrial gastropod. Therefore, when the terrestrial gastropod contacts the membrane, it directly senses the eluted copper ions and exhibits sensitive repellent behavior. On the other hand, this membrane stably retains the chitosan-copper complex, and the elution by mucus remains in a very small amount. Furthermore, this film is excellent in water resistance and suppresses the outflow of copper ions due to rain or the like, so that the influence on the environment is suppressed and the repelling effect is maintained over a long period of time.

  EXAMPLES Hereinafter, although an Example etc. are given and this invention is demonstrated in detail, this invention is not restrict | limited at all by these.

Production Example 1
Preparation of chitosan-copper complex:
803.23g of tap water was taken in a glass beaker with a capacity of 2 liters, heated in a water bath and reached 50-55 ° C, acetic acid (Wako Pure Chemical Industries, Ltd., reagent grade 1, purity) 99%) 80 g was added and dissolved.
Next, 50 g of chitosan (“Chitosan SK-10” manufactured by Koyo Chemical Co., Ltd .: Deacetylation degree 86.9, average molecular weight of about 50000, ash content 0.27%, flake form) is added to this acetic acid aqueous solution. The solution was completely dissolved while maintaining the temperature.
After confirming dissolution, 66.77 g of copper (II) acetate monohydrate (manufactured by Wako Pure Chemical Industries, Ltd., reagent grade 1, purity 98%, calculated copper content 20. 81 g) was added and allowed to react for 3 hours to obtain 1000 g of an aqueous solution of chitosan-copper complex.

Example 1
Preparation of repellent sheet:
Superflex E-2000 as an aqueous solution and aqueous resin of chitosan-copper complex obtained in Production Example 1 (urethane resin, nonionic properties, viscosity 612 mPa · s, ester skeleton structure, forced emulsification grade, manufactured by Daiichi Kogyo Seiyaku Co., Ltd.) Were mixed so that the mass ratio was 1:23 (in terms of solid content) to prepare a repellent composition. This repellent composition was applied to a 3.5 cm wide Japanese paper sheet using a 40 mesh gravure coater, then dried at 180 ° C. for 2 minutes, and again applied using a 40 mesh gravure coater. It was dried for a minute to form a repellent layer (coating amount 43.1 g / m ² ).

Example 2
A repellent sheet was obtained in the same manner as in Example 1 except that the repellent composition mixed so as to have a content mass ratio of 1:12 (in terms of solid content) was applied (coating amount: 43.5 g / m ² ).

Example 3
Using N-Nicazole RX672A (acrylic resin, cationic, viscosity 33 mPa · s, acrylic copolymer, forced emulsification grade, manufactured by Nippon Carbide Co., Ltd.) as the water-based resin, the content mass ratio is 1:19 (in terms of solid content). A repellent sheet was obtained in the same manner as in Example 1 except that the repellent composition thus mixed was applied (coating amount: 31.3 g / m ² ).

Example 4
A repellent sheet was obtained in the same manner as in Example 3, except that the repellent composition mixed so as to have a content mass ratio of 1: 9 (in terms of solid content) was applied (amount of application: 35.2 g / m ² ).

Example 5
Using Polysol AE-821 (acrylic resin, cationic, viscosity 29 mPa · s, styrene / acrylic acid ester copolymer, forced emulsification grade, Showa Denko KK) as a water-based resin, a mass ratio of 1:21 (solid A repellent sheet was obtained in the same manner as in Example 1 except that the repellent composition mixed so as to be (in terms of minute) was applied (coating amount: 40.1 g / m ² ).

Example 6
A repellent sheet was obtained in the same manner as in Example 5 except that the repellent composition mixed so as to have a content mass ratio of 1:11 (in terms of solid content) was applied (coating amount: 37.0 g / m ² ).

Comparative Example 1
A repellent sheet was obtained without applying anything to a 3.5 cm wide Japanese paper sheet.

Comparative Example 2
Only the aqueous solution of chitosan-copper complex obtained in Production Example 1 was applied to a 3.5 cm wide Japanese paper sheet using a 40 mesh gravure coater (application amount 24.3 g / m ² ), and then at 180 ° C. for 2 minutes. Dried and formed a repellent layer.

Comparative Example 3
An aqueous solution of chitosan-copper complex obtained in Production Example 1 and a water-soluble resin, Denka size W-100 (polyvinyl alcohol resin, nonionic, viscosity 1000 mPa · s, complete saponification, manufactured by Denki Kagaku Kogyo) 10% aqueous solution A repellent composition was prepared by mixing so that the content mass ratio was 1:45 (in terms of solid content). This repellent composition was applied to a 3.5 cm wide Japanese paper sheet using a gravure coater (coating amount 16.2 g / m ² ), and then dried at 180 ° C. for 2 minutes to form a repellent layer.

Comparative Example 4
A repellent sheet was obtained in the same manner as in Comparative Example 3 except that the repellent composition mixed so as to have a content mass ratio of 1:22 (in terms of solid content) was applied (coating amount 14.7 g / m ² ).

Comparative Example 5
A repellent sheet was obtained in the same manner as in Comparative Example 3 except that the repellent composition mixed so as to have a content mass ratio of 1:11 (in terms of solid content) was applied (coating amount 10.6 g / m ² ).

Comparative Example 6
Using Adekabon titer HUX-380 (urethane resin, anionic, viscosity 19 mPa · s, ester skeletal structure, forced emulsification grade, manufactured by ADEKA) as water-based resin, a mass ratio of 1: 4 (solid content conversion) and A repellent sheet was obtained in the same manner as in Comparative Example 3 except that the mixed repellent composition was applied.

Comparative Example 7
Polysol AP-1900 (acrylic resin, anionic, viscosity 3200 mPa · s, styrene-acrylic acid ester copolymer, forced emulsification grade, Showa Denko Co., Ltd.) was used as the aqueous resin, and the mass ratio 1: 6 (solid A repellent sheet was obtained in the same manner as in Comparative Example 3 except that the mixed repellent composition was applied so that

Comparative Example 8
Using a water sol ACD02001 (acrylic resin, viscosity 3210 mPa · s, organic solvent-containing grade, manufactured by DIC) as a resin, a repellent composition mixed so as to have a mass ratio of 1: 5 (in terms of solid content) A repellent sheet was obtained in the same manner as in Comparative Example 3 except that coating was performed.

Test example 1
Water resistance test:
The repellent sheets 1 obtained in Examples 1 to 6 were cut to a length of 15 cm, stuck to the wall 5 as shown in FIG. 1, and from a shower (φ0.5 mm × 69 holes) 4 at a flow rate of 3 liters / minute. Watering for 30 minutes, or submerging in an approximately 1.5 liter water tank (11 cm × 8 cm × 16.5 cm height) 2 filled with 1 liter of water 3 as shown in FIG. The leaching rate (%) was determined as a ratio of the mass of the coating film after watering treatment or water immersion treatment to the mass of the coating film before watering treatment or water immersion treatment. The results are shown in Table 1.

  In Comparative Example 2 using only the chitosan-copper complex, the coating property on the sheet material was excellent, but the water resistance was low, and 90% or more leached after watering treatment. In Comparative Examples 3 to 5 using a polyvinyl alcohol resin, the compatibility with the chitosan-copper complex was good, but the water resistance was low, and a coating film of about 25 to 70% was leached. In Comparative Examples 6 to 8 using an anionic resin or a resin containing an organic solvent, the compatibility is low, and it is difficult to form a film because the coated surface becomes rough even when separated or coated. The repellent sheet could not be prepared sufficiently. In contrast, all the repellent compositions used in Examples 1 to 6 have good compatibility between the chitosan-copper complex and the water-based resin, excellent coating properties on the sheet material, and high water resistance and strongness. A stable coating film was formed, and leaching after watering / immersing was slight.

Test example 2
Snail water repellent test:
Using the repellent sheet after each water immersion and water sprinkling test obtained in Test Example 1, a snail water repellent test was performed as shown in FIG. That is, the repellent sheet 1 having a width of 3.5 cm and a length of 15 cm was attached to the inside of the cylindrical container 6 having an inner diameter of 4.8 cm with an adhesive seal. One snail 7 was left in the container. It was observed whether the snail climbed the repellent sheet and went out within 10 minutes. The test was repeated 5 times or more, and the snail was changed for each test. The value obtained by dividing the number of times the snail did not go out by the number of all tests was defined as the repelling rate (%). In addition, it tested similarly using only the sheet | seat which has not applied the repellent composition as control. The results are shown in Table 2.

  The repellent sheets of Examples 1 to 6 show that the coating film remains in the state before immersion without being smeared even after being immersed in water, maintains the repellent effect to a certain extent, and is excellent in water resistance. It was.

  The terrestrial gastropod repellent composition and the repellant sheet using the terrestrial gastropod repellent composition of the present invention are excellent in the repellency effect on the terrestrial gastropod and its sustainability, and are therefore useful as a terrestrial gastropod control material that damages crops.

1 Repellent sheet 2 Water tank 3 Water 4 Shower 5 Wall 6 Cylindrical container 7 Snail

Claims (6)

  One or more selected from the group consisting of a chitosan-copper complex and an aqueous resin, wherein the aqueous resin is composed of a cationic acrylic resin, a nonionic acrylic resin, a cationic urethane resin, and a nonionic urethane resin. A terrestrial gastropod repellent composition characterized by being a resin of   The terrestrial gastropod repellent composition according to claim 1, wherein the aqueous resin is a cationic acrylic resin or a nonionic urethane resin.   The terrestrial gastropod repellent composition according to claim 2, wherein the cationic acrylic resin is a styrene-acrylic copolymer.   The terrestrial gastropod repellent composition according to any one of claims 1 to 3, wherein the aqueous resin is a forced emulsification type resin emulsion.   The terrestrial gastropod repellent composition according to any one of claims 1 to 4, wherein the mass ratio of the water-based resin and the chitosan-copper complex is 80: 1 to 1:20 (in terms of solid content). A land and gastropod repellent sheet having a repellent layer formed from the land and gastropod repellent composition according to any one of claims 1 to 5 on at least one surface of a substrate.