JPH1017409A - Organic acid-containing composition and repellent - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a composition capable of sustaining repelling effects on harmful animals for a long period of time, by combining a (co)polymer having a specific structure and/or a cross-linked material of the (co)polymer with a solution of an organic acid. SOLUTION: This composition comprises a (co)polymer obtained from a monomer of formula I (R<1> and R<2> are each H or methyl or R<1> and R<2> are bonded to form a 3-5C alkylene) and/or a cross-linked material of the (co)polymer (A) and a solution of an organic acid (B). Especially, vinylacetamide is preferable as the compound of formula I. The compound of formula I may be copolymerized with a compound of formula II (R is H or methyl; M is H or an alkali metal) to give a copolymer. Pyroligneous acid is preferable as the organic acid. In the composition, preferably, the component A is a cross- linked material of the (co)polymer, the content of the component A is 99-1 pt.wt. and the content of the solution of the organic acid is 1-99 pts.wt. The repellent is effective for animals such as dog, cat, wild boar, Asian raccoon, crow, etc.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a composition containing an organic acid solution and a repellent using the composition, and in particular, wood vinegar useful as a repellent for animals such as dogs, cats, boars, raccoons, crows and the like. The present invention relates to a composition containing an organic acid solution such as a liquid.

[0002]

2. Description of the Related Art In the cultivation of agricultural crops in mountainous areas, it is necessary to prevent vegetarian animals and the like from overrunning a farm and eating food. In addition to preventing the invasion of such pests by surrounding the farm with nets and fences, various methods of preventing the invasion and approach of pests by emitting specific sounds or light have been attempted. . However, no effective method for sustaining the damage prevention effect for a long time has been found. Also, using the animal's sharp smell in reverse,
Use of odor repellents such as sulfur-containing compounds and nitrogen-containing compounds has also been devised. However, many of such odor repellents are harmful to the human body or cause extremely discomfort, so that their use has been limited.

On the other hand, it has been known that wood vinegar obtained as a by-product when producing charcoal has a repellent effect on harmful animals of agricultural products. Wood vinegar is also used as a deodorant for manure of dogs and cats, an insect repellent such as flies, a soil conditioner, a pharmaceutical raw material, a food additive, and the like, and is a useful substance having low harm to the human body. When a wood vinegar is used as a repellent, a method of directly applying it to a fence, a grove, or the like, or a method of absorbing it with cotton, wood chips, or the like, leaving it on the ground or laying it on a tree is used. However, with such a method, wood vinegar evaporates quickly, and it has been difficult to maintain the repellent effect on harmful animals for a long period of time. Also, studies have been made to contain a repellent such as wood vinegar in a sodium polyacrylate-based resin or a polyacrylamide-based resin to suppress the volatilization rate and maintain the repellent effect for a long time. However, these resins have low weather resistance, cannot maintain the effect of retaining the repellent for a long period of time in a use environment, and have a problem that the resin is deteriorated by the components of wood vinegar.

[0004]

DISCLOSURE OF THE INVENTION The present invention relates to an organic acid solution capable of effectively absorbing and holding an organic acid-containing solution such as wood vinegar and maintaining the repellent effect of crops against harmful animals for a long period of time. The purpose is to develop a contained composition and a method of using the composition.

[0005]

Means for Solving the Problems As a result of various studies for solving the above problems, the present inventors have found that a (co) polymer having a specific structure and / or a crosslinked product of the (co) polymer and an organic acid It has been found that the above object can be achieved by using a composition comprising a solution, and the present invention has been completed. That is, the following general formula (1) CH ₂ ＣＨCH—NR ¹ —COR ² (1) (wherein R ¹ and R ² independently represent a hydrogen atom or a methyl group, or have 3 to 5 carbon atoms bonded thereto. Containing an organic acid solution comprising a (co) polymer and / or a crosslinked product of the (co) polymer (A) and an organic acid solution (B) obtained from the monomer represented by A composition and a repellent containing the composition as a main component.

[0006]

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the present invention will be described in more detail. The organic acid solution-containing composition of the present invention contains a (co) polymer obtained from the monomer represented by the general formula (1) and / or a crosslinked product of the (co) polymer and an organic acid solution. Things are essential. In this composition, a (co) polymer (crosslinked product) is added to an organic acid solution to thicken or gel the solution (liquid absorption).
It is prepared by The (co) polymer used in this case and / or a crosslinked product thereof (hereinafter, simply referred to as (crosslinked product)) can be obtained by polymerizing a monomer represented by the general formula (1). Examples of the monomer of the general formula (1) include N
-Vinylformamide, N-methyl-N-vinylformamide, N-vinylacetamide, N-methyl-N-vinylacetamide, N-vinylpyrrolidone, and the like, with N-vinylacetamide being particularly preferred. The (co) polymer (crosslinked product) may be a homopolymer (crosslinked product) of the monomer of the general formula (1), or may be a copolymer with another copolymerizable monomer ( Crosslinked product).
There are various other copolymerizable monomers,
Examples include acrylamide, methacrylamide,
N, N-dimethyl (meth) acrylamide, N, N-dimethylaminoethyl (meth) acrylamide, N, N-
(Meth) acrylamide monomers such as dimethylaminopropyl (meth) acrylamide, acryloylmorpholine, N, N-diethyl (meth) acrylamide and N-isopropyl (meth) acrylamide; and (meth) acrylic acid, maleic acid, fumaric acid, etc. Unsaturated carboxylic acids,
Methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, hexyl (meth) acrylate, octyl (meth) acrylate, lauryl (meth) acrylate, ( Meta)
Benzyl acrylate, methyl fumarate, ethyl fumarate, propyl fumarate, butyl fumarate, dimethyl fumarate, diethyl fumarate, dimethyl fumarate, diethyl fumarate, dipropyl fumarate, dibutyl fumarate, methyl methyl maleate, maleic acid Unsaturated carboxylic acid alkyl esters such as ethyl, propyl maleate, butyl maleate, dimethyl maleate, diethyl maleate, dipropyl maleate and dibutyl maleate; vinyl esters such as vinyl acetate and vinyl propionate; , (Meth) acrylonitrile, sodium 2- (meth) acrylamido-2-methylpropanesulfonate, sodium 2-[(meth) acryloyloxy] ethylsulfonate, and the like. It may be used in combination of at least. When a monomer represented by the general formula (2) is used among these monomers, a particularly suitable composition can be obtained. Examples of the compound represented by the general formula (2) include acrylic acid, sodium acrylate, potassium acrylate, methacrylic acid, sodium methacrylate, and the like.
The content of these other monomers is preferably 50% by weight or less based on all the monomers, and if it exceeds this, it is not preferable because the viscosity of the organic acid solution and the liquid absorbing ability decrease.

In the case where a crosslinked (co) polymer is used in the present invention, a polymerizable crosslinking agent having two or more polymerizable unsaturated groups is further added to the monomer (mixture) to carry out polymerization.
A method of crosslinking, further comprising a reactive cross-linking agent having two or more functional groups (eg, epoxy groups) that react with functional groups (eg, carboxylic acid groups or hydroxyl groups) in the monomers (mixture). In addition, a method of polymerizing and cross-linking, a method of synthesizing a (co) polymer in advance, and adding a reactive cross-linking agent having at least two functional groups that react with the functional group in the (co) polymer to perform cross-linking It can be crosslinked and these methods are optionally employed in combination. Examples of the polymerizable crosslinking agent include N, N-1,4-butylenebis (N
-Vinylacetamide), N, N-1,6-hexylenebis (N-vinylacetamide), N, N-decylenebis (N-vinylacetamide), N, N-3-oxa-
1,5-pentylenebis (N-vinylacetamide),
N, N-3,6-dioxaoctylenebis (N-vinylacetamide), N, Np-xylenebis (N-vinylacetamide), N, N'-diacetyl-N, N'-
Divinyl-1,4-bisaminomethylcyclohexane,
Tetraallyloxyethane, triallyl phosphate, trimethylolpropane diallyl ether, trimethylolpropane triallyl ether, sucrose allyl ether, N, N'-methylenebisacrylamide, ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate , Triethylene glycol di (meth) acrylate, polyethylene glycol di (meth) acrylate, trimethylolpropane tri (meth) acrylate, pentaerythritol triallyl ether, pentaerythritol tetra (meth) acrylate, divinyl adipate, divinyl maleate,
Examples thereof include compounds having two or more unsaturated groups in one molecule, such as divinylbenzene and divinyl ether. Examples of the reactive cross-linking agent that reacts with a functional group in a monomer or a polymer include polyglycidyl ether, polyisocyanate, polyalcohol, and polyvalent metal salts (for example, aluminum salts and calcium salts). . The amount of the crosslinking agent used is 0.005 to 1 based on the total amount of the monomers.
0% by weight, preferably in the range of 0.1 to 5% by weight.
If the amount of the crosslinking agent used is less than this range, the effect of crosslinking is not obtained and is meaningless. If the ratio exceeds this range, the crosslinking density becomes too high, and the absorption amount of the organic acid solution becomes extremely small, which is not preferable.

The (co) polymer or crosslinked (co) polymer containing the monomer represented by the formula (1) as a main component can be produced by a known method. For example, aqueous solution polymerization in which a monomer component is dissolved in water and polymerized as it is, reverse-phase suspension polymerization in which an aqueous solution of a monomer component is dispersed in an organic solvent, and a polymer in which the monomer component dissolves but is obtained Is a method in which monomer components are uniformly dissolved in an insoluble organic solvent to carry out polymerization to carry out polymerization, for example, by dispersion precipitation polymerization (slurry polymerization). In some cases, a method of producing by mass polymerization using water (methanol), ethanol, or other (mixed) organic solvent capable of dissolving other monomer components as a solvent, followed by drying and removing the used solvent is also used. is there. Examples of the polymerization initiator used in the polymerization include azo compounds such as azobisisobutyronitrile, 2,2′-azobis-2-amidinopropane hydrochloride, t-butyl peroxide, hydrogen peroxide, and the like. peroxides such as t-amyl peroxide, cumyl peroxide, acetyl peroxide, propionyl peroxide, benzoyl peroxide, benzoyl isopropyl peroxide, lauroyl peroxide, t-butyl hydroperoxide, cyclohexyl hydroperoxide, and tetralin hydroperoxide; Oxides,
For example, a so-called redox-based initiator obtained by combining a persulfate and an organic amine can be used. The polymerization temperature varies depending on the type of polymerization initiator used, but is usually -2.
The range is from 0 to 150 ° C, preferably from 0 to 100 ° C. The polymerization is preferably carried out by deoxygenating the polymerization solution with an inert gas such as a nitrogen gas or an argon gas. Further, it is preferable to produce the polymerization reaction vessel in an inert gas atmosphere. The polymerization product is washed with a hydrophilic solvent such as acetone or MEK, and then dried and solidified before use.

The organic acid solution used in the present invention includes:
For example, lower fatty acids having 1 to 10 carbon atoms such as formic acid, acetic acid, propionic acid, butyric acid, valeric acid, and caproic acid, and phenols such as guaiacol and cresol can be prepared by using water or methanol, ethanol, ethylene glycol monobutyl ether, and propanol. Use a solution diluted with a lower monohydric alcohol such as propylene glycol, 1,3-butanediol, triethylene glycol, glycerin, or other polyhydric alcohol, or a wood vinegar solution obtained when producing charcoal from natural wood. Can also. The wood vinegar may be used as it is without dilution, but may be diluted with water, methanol, ethanol, isopropanol, or the like. Among these organic acid solutions, wood vinegar is most preferably used.

The concentration of these organic acid solutions varies greatly depending on the method of use of the composition, the purpose of use (the kind of the target pest) and the place of use, so it is difficult to unconditionally define the concentration. If the concentration is 001% by weight or more, a repellent effect on harmful animals can be expected. In order to produce the organic acid solution-containing composition of the present invention, the (co) polymer (crosslinked product) described above and the organic acid solution can be easily mixed at room temperature or while heating as needed. Can be obtained. The amount of the organic acid solution used for the organic acid solution-containing composition of the present invention is in the range of 1 to 99% by weight, preferably 50 to 99% by weight, based on the total amount of the organic acid-containing composition. . If the amount used is below this range, the duration of the repellent effect on the harmful animals is undesirably too short. Conversely, when the organic acid solution is used outside this range, the (co) polymer (crosslinked product) loses its thickening effect or solution holding effect, which is not preferable.

The composition containing an organic acid solution described above includes:
It is also possible to use it as a highly complexed composition in combination with other components. Other components used here are those that do not lose the thickening effect or retention effect of the (co) polymer (crosslinked product) and that do not lose the effect of the organic acid solution as a repellent. There is no particular limitation if it is. Some examples of such other components include silicone rubber, acrylic rubber, guar gum, locust bean gum, natural rubber, urethane rubber, ethylene-propylene rubber (EPR), and ethylene-propylene-diene rubber (EPDM). ), Rubber materials such as styrene-butadiene rubbers (SBR, SEBR, etc.), polyvinyl alkyl ether, polyvinyl alcohol, polyvinyl acetate, methyl vinyl ether / maleic anhydride copolymer, polyvinyl pyrrolidone, carboxyl vinyl polymer, vinyl pyrrolidone / Vinyl acetate alkylaminoacrylic acid copolymer, metacarboxybetaine / metacarboxyester copolymer, styrene / maleic acid copolymer, ethylene / vinyl acetate copolymer, partially saponified ethylene / vinyl acetate copolymer, partial soap Polyvinyl acetate, polyethylene, polypropylene, polyethylene terephthalate, polybutylene terephthalate, polyamide, polyacetal, polyphenylene sulfide, polyimide, polyetherketone, polyetherimide, polyetheretherketone, polyacrylonitrile, alkyl poly (meth) acrylate, poly Synthetic polymers such as alkylene oxides, chitin, chitoic acid, starch, collagen, starch, pullulan, ethylcellulose, methylcellulose,
Examples include natural polymer materials such as cellulose acetate, hydroxyethyl cellulose, hydroxypropyl cellulose, phthalate methyl cellulose, carboxymethyl cellulose, and the like. In addition, inorganic substances such as silica, alumina and zeolite, and soil components such as sand, clay, montmorillonite and bentonite can also be used. Further, the composition can be used by being applied to other base materials such as non-woven fabric, rock wool, urethane foam, paper, cotton, felt and the like or laminated.

[0012]

The composition containing an organic acid solution according to the present invention is easy to handle and can effectively hold an organic acid solution such as wood vinegar. In addition, it has sufficient weather resistance and quality stability in the use environment. In addition, the repellent using the present organic acid solution-containing composition can suppress the volatilization rate of the solution and maintain the repellent effect on harmful animals for a long period of time.

[0013]

EXAMPLES Hereinafter, the present invention will be described in detail with reference to Reference Examples, Examples, and Comparative Examples, but it goes without saying that the technical scope of the present invention is not limited to the following contents. In Reference Example, a production example of a (co) polymer (crosslinked product) is shown. <Reference Example 1> A stirrer, a thermometer, and a nitrogen inlet tube were attached to a 1-liter four-neck separable flask, and N was added thereto.
-70 g of vinylacetamide, 1.05 g of pentaerythritol triallyl ether as a cross-linking agent, and 630 g of ethyl acetate were added to dissolve N-vinylacetamide.
Stir while introducing nitrogen gas to drive out dissolved oxygen,
A solution prepared by dissolving 0.49 g of 2,2′-azobis (2-propionate) as a polymerization initiator in about 5 ml of ethyl acetate was added to the reactor. The temperature of the inner solution was raised to 70 ° C., and polymerization was performed at this temperature for 5 hours. N- with the progress of polymerization
Since the vinylacetamide polymer was precipitated as a precipitate, the internal solution was filtered after completion of the polymerization to obtain an N-vinylacetamide polymer. After washing the polymer several times with ethyl acetate, it was dried at 50 ° C. for 14 hours in a vacuum drier to obtain a white fine powder crosslinked polymer. The particle size was 1 μm or less, and the viscosity was 200 cps in a 1% by weight aqueous solution. This crosslinked polymer is used as a substrate (1).

Reference Example 2 A 1-liter four-neck separable flask was equipped with a stirrer, a thermometer, and a nitrogen inlet tube, and 93.5 g of N-vinylacetamide, 6.5 g of acrylonitrile, and deionized water. 280 g of water was added and dissolved. After introducing nitrogen gas to drive out dissolved oxygen and stirring to raise the internal temperature to 30 ° C., 20 g of a 5% by weight aqueous solution of 2,2′-azobis-2-amidinopropane dihydrochloride as a polymerization initiator was used. Was added. Thereafter, the stirring was stopped and the polymerization was allowed to stand for 10 hours. The obtained gel was cut with a mincer and washed with acetone, and then dried under vacuum at 80 ° C. for 12 hours. The viscosity of the obtained copolymer was 650 cps in a 1% by weight aqueous solution. This copolymer is used as a substrate (2).

REFERENCE EXAMPLE 3 A 1-liter four-neck separable flask was equipped with a stirrer, a thermometer, and a nitrogen inlet tube, 80 g of N-vinylacetamide, and 0 pentaerythritol triallyl ether as a crosslinking agent. 0.5 g and 280 g of deionized water were added and dissolved. Introduce nitrogen gas to drive out dissolved oxygen and agitate while keeping the internal temperature at 30 ° C.
After the temperature was raised to 20 ° C., 20 g of a 0.5% by weight aqueous solution of 2,2′-azobis-2-amidinopropane dihydrochloride was added as a polymerization initiator. Thereafter, the stirring was stopped and the polymerization was allowed to stand for 10 hours. The obtained gel was cut with a mincer and washed with acetone, and then dried under vacuum at 80 ° C. for 12 hours. The obtained crosslinked polymer swelled in water, ethanol, dimethylformamide and the like, and could maintain the shape of an insoluble gel. This crosslinked polymer is used as a substrate (3).

<Examples 1 to 8 and Comparative Examples 1 to 3>
Was added to 10 g of each of the various repellent solutions shown in (1) above, placed in a petri dish having a diameter of 10 cm, and air-dried at 25 ° C. When the repellent solution remained even after 10 days or more, ◎ when the repellent solution remained after 5 days. Δ When the repellent solution had almost remained after 5 days. Those that were not found were marked with x. In addition, the test material after 5 days was placed together with a petri dish in which food was placed in one of the boxes provided with a detachable partition plate at the center in the longitudinal direction of 2 m in length, 50 cm in height and 50 cm in width. After placing 10 guinea pigs in the other, the central divider was removed and it was observed whether the guinea pigs approached the food to test their repellent effect. When no guinea pigs approached the food even after 30 minutes had passed, ◎ was given when 1 to 5 guinea pigs approached the food, and x was given when 6 or more guinea pigs approached the food. It can be seen that each of the substrates manufactured in the reference examples can maintain the organic acid solution for a long period of time and can maintain the repellent effect, as compared with the case where no substrate is used or the case where absorbent cotton or a commercially available water-absorbing resin is used.

[0017]

[Table 1]

[0018]

According to the present invention, a new organic acid containing an organic acid solution such as a wood vinegar solution, which has sufficient weather resistance and quality stability in an environment of use and is easy to handle. It is intended to provide a composition and a repellent using the same.
In the present composition, the volatilization rate is suppressed by including the organic acid solution in the resin. Therefore, the repellent using the present composition can maintain the repellent effect on pests for a long period of time.

Claims (6)

[Claims] 1. The following general formula (1): CH ₂ ＣＨCH—NR ¹ —COR ² (1) (wherein, R ¹ and R ² independently represent a hydrogen atom or a methyl group, or the number of carbon atoms bonded thereto) (Representing an alkylene group of 3 to 5)) and / or a (co) polymer obtained from a monomer represented by the formula (C) and / or a crosslinked product of the (co) polymer (A) and an organic acid solution (B). An acid solution containing composition. 2. The organic acid solution-containing composition according to claim 1, wherein the monomer represented by the general formula (1) is N-vinylacetamide. 3. A copolymer and / or a cross-linked product (A) of the copolymer comprises a monomer represented by the general formula (1) and a monomer represented by the following general formula (2): CH ₂ ＣＲCR—COOM (2 (Wherein R represents a hydrogen atom or a methyl group, and M represents a hydrogen atom and / or an alkali metal atom). Item 3. The composition containing an organic acid solution according to Item 1 or 2. 4. The organic acid solution-containing composition according to claim 1, wherein the organic acid solution (B) is a wood vinegar solution. 5. The method according to claim 1, wherein (A) is a crosslinked (co) polymer, the content of (A) is 99 to 1 part by weight, and the content of the organic acid solution is 1 to 99 parts by weight. Item 5. The organic acid solution-containing composition according to items 1 to 4. 6. A repellent comprising the organic acid solution-containing composition according to claim 5 as a main component.