JP3173383B2 - Sprouting inhibitor and method for producing the same - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention can prevent the germination of flying weed seeds without adversely affecting the growth of useful plants, and is effective for preserving the beauty of public or private living environments. The present invention relates to a germination inhibitor which can be widely used in public works, landscaping, DIY products (daily carpentry products), and the like.

[0002]

2. Description of the Related Art In public places such as parks and golf courses or in gardens of ordinary households, for example, harm caused by the occurrence of weeds is as follows.
Not only is it aesthetically pleasing and uncomfortable, but it also consumes a significant amount of effort to eliminate it, and the drugs used to eliminate it can potentially cause environmental pollution. is there.

Further, in recent years, various pesticide preparations have been developed for the purpose of removing weeds, but they cannot be expected to have a long-lasting effect.
There is a problem that excessive use may cause destruction of biological systems and contamination of groundwater.

Therefore, Japanese Patent Application Laid-Open No. 7-106965 discloses a method in which an aqueous emulsion of an alkoxysilane compound is used as a germination inhibitor. This is a method in which soil is converted into hydrophobic by an aqueous emulsion of an alkoxysilane-based compound to prevent germination of seeds. This method does not pollute the environment and does not significantly affect plant growth.

However, this method is an emulsion in which an alkyl trialkoxysilane is emulsified in water. Therefore, the stability of the aqueous solution is low, and if an alkylalkoxysilane having a very slow hydrolysis reaction is used to enhance the stability, This time, even if the soil is treated, it does not immediately react with the soil, the effect does not appear, and the soil is often neutral or weakly acidic due to recent acid rain. Alkoxysilane emulsions have the disadvantage that the reaction rate is very slow. Therefore, development of a more effective germination inhibitor free of these disadvantages is desired.

SUMMARY OF THE INVENTION The present invention has been made in view of the above circumstances, has a rapid reaction with soil, has excellent aqueous solution stability, and has a stable ground that suppresses the generation of unnecessary plants for a long period of time. An object of the present invention is to provide a germination inhibitor capable of forming an environment.

[0007]

Means for Solving the Problems and Embodiments of the Invention
The inventor has conducted intensive studies to achieve the above object.
As a result, (A) the following general formula (1) R¹ Si (OR^Two)_Three (1) (where R¹Is a monovalent saturated carbon having 1 to 18 carbon atoms.
Hydrogen group, R^TwoIs an alkyl group having 1 to 4 carbon atoms.
You. )) Or a trialkoxysilane or a partial addition thereof
1 to 30 parts by weight of a hydrolyzate and (B) the following general formula (2) R^Three _a(OR^Two)_bSiO_{(4-ab) / 2} (2) (where R^TwoIs the same as above, and R^ThreeIs the number of carbon atoms
1 to 6 alkyl groups, a is 0.75 to 1.5, b
Satisfies 0.2 to 2 and satisfies 0.95 <a + b <3.4
Is a positive number. ) -Containing siloxy group represented by
70 to 90 parts by weight of sun and (C) the following general formula (3) R^FourR^FiveNR⁶-SiR⁷ _n(OR^Two)_3-n (3) (where R^TwoIs the same as above, and R^Four, R^FiveIs it
A hydrogen atom or the same or different carbon atom number of 1 to 1
5, an alkyl group or an aminoalkyl group, R⁶Is a carbon atom
A divalent hydrocarbon group of the formulas 1 to 18, R⁷Is 1 to 4 carbon atoms
Is an alkyl group. n is 0 or 1. )
Amino group-containing alkoxysilane or its partial hydrolysis
1 to 20 parts by weight of the product in the presence of an organic acid or an inorganic acid
Decomposed water-soluble organosilicon compound, particularly preferably
Component (A) trialkoxysilane of the formula (1) or
Hydrolysis of partially hydrolyzed products in the presence of organic or inorganic acids
After the reaction, the hydrolyzate is added to the component (B) of formula (2).
Organic acids or inorganic acids
Is hydrolyzed in the presence of
Or an amino group-containing alkoxysilane of the formula (3)
Water-soluble obtained by reacting
Silicon compound itself is water-soluble and uniform when dissolved in water
Excellent storage stability after dilution with water.
Excellent permeability and reactivity under neutral and weakly acidic conditions,
And no negative impact on the environment, and therefore such water solubility
Organosilicon compound is sprayed on soil surface as germination inhibitor
Adversely affect the growth of useful plants
To prevent germination of scattered weed seeds
To maintain the aesthetic appearance, the effort for weed removal and
Recognize that it is possible to reduce costs and use herbicides.
The present invention has led to the present invention.

Accordingly, the present invention provides (A) 1 to 30 parts by weight of a trialkoxysilane represented by the above general formula (1) or a partial hydrolyzate thereof, and (B) an alkoxysilane represented by the above general formula (2) 70 to 90 parts by weight of a group-containing siloxane and (C) 1 to 20 parts by weight of an amino group-containing alkoxysilane represented by the general formula (3) or a partial hydrolyzate thereof are hydrolyzed in the presence of an organic acid or an inorganic acid. A germination inhibitor, which comprises a water-soluble organosilicon compound obtained by decomposition, and a trialkoxysilane of the formula (1) of the component (A) or a partial hydrolyzate thereof is treated with an organic acid or an inorganic acid. After hydrolysis in the presence, the hydrolyzate is mixed with the alkoxy group-containing siloxane of the formula (2) of the component (B) and hydrolyzed in the presence of an organic acid or an inorganic acid,
Finally, the present invention provides a method for producing the above-mentioned germination inhibitor, which is reacted with the amino group-containing alkoxysilane of the formula (3) or a partial hydrolyzate thereof as the component (C).

Hereinafter, the present invention will be described in more detail.
And the component (A) for obtaining the germination inhibitor of the present invention are as follows:
The general formula (1) R¹ Si (OR^Two)_Three (1) (where R¹Is a monovalent saturated carbon having 1 to 18 carbon atoms.
Hydrogen group, R^TwoIs an alkyl group having 1 to 4 carbon atoms.
You. )) Or a trialkoxysilane or a partial addition thereof
It is a hydrolyzate.

In the trialkoxysilane of the above formula (1), R ¹ is a monovalent saturated hydrocarbon group having 1 to 18 carbon atoms, preferably 7 to 10 carbon atoms, more preferably 7 to 1 carbon atoms.
It is an alkyl group of 0. When the number of carbon atoms is less than 7, the germination prevention property is weakened, and the polymerization may proceed too much.
On the other hand, if it exceeds 18, the production may be difficult. R
¹ may be linear, branched or cyclic, for example, C ₃ H ₇ , C ₆ H ₁₃ , C ₇ H ₁₅ , C ₈ H ₁₇ , C ₉
H ₁₉ , C ₁₀ H _{21 and the} like, and particularly, C ₈ H ₁₇ , C ₁₀
H ₂₁ is preferred.

R ² is an alkyl group having 1 to 4 carbon atoms, such as a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group and an isobutyl group. Is preferred.

The trialkoxy sila of the formula (1)
Specific examples of the compound include the following compounds.
You. C_ThreeH₇Si (OCH_Three)_Three, C_ThreeH₇Si (OC_TwoH_Five)_Three,
C_ThreeH₇Si (OC H (CH_Three)_Two)_Three, C₆H₁₃Si (OC
H_Three)_Three, C₆H₁₃Si (OC_TwoH_Five)_Three, C₆H₁₃Si (O
C H (CH_Three)_Two)_Three, C₈H₁₇Si (OCH_Three)_Three, C₈H
₁₇Si (OC_TwoH_Five)_Three, C₈H₁₇Si (OC H (C
H_Three)_Two)_Three, C_TenH_{twenty one}Si (OCH_Three)_Three, C_TenH_{twenty one}Si
(OC_TwoH_Five)_Three, C_TenH_{twenty one}Si (OC H (CH_Three)_Two)_Three,
C₁₂H_{twenty five}Si (OCH_Three)_Three, C₁₂H_{twenty five}Si (OC_TwoH_Five)
_Three, C₁₂H_{twenty five}Si (OC H (CH_Three)_Two)_Three, C₁₄H₂₉Si
(OCH_Three)_Three, C₁₄H₂₉Si (OC_TwoH_Five)_Three, C₁₄H₂₉
Si (OC H (CH_Three)_Two)_Three, C₁₆H₃₃Si (OCH_Three)
_Three, C₁₆H₃₃Si (OC_TwoH_Five)_Three, C₁₆H₃₃Si (OC H
(CH_Three)_Two)_Three, C₁₈H₃₇Si (OCH_Three)_Three, C₁₈H₃₇
Si (OC_TwoH_Five)_Three, C₁₈H₃₇Si (OC H (C
H_Three)_Two)_Three Among these, the following compounds are particularly preferable. C₈H₁₇Si (OCH_Three)_Three, C_TenH_{twenty one}Si (OCH_Three)_Three

In the present invention, an oligomer obtained by partially hydrolyzing and condensing the silane of the above formula (1) can be used as the component (A). The number of silicon atoms in the partial hydrolyzate is preferably 2 to 10, particularly preferably 2 to 4.

In the present invention, various silanes represented by the above formula (1) may be used alone, a mixture of two or more types may be used, or a partial hydrolyzate of the mixed silane may be used. .

The component (B) is represented by the following general formula (2): R ³ _a (OR ² ) _b SiO _{(4-ab) / 2} (2) (where R ² is the same as above, and R ³ Is an alkyl group having 1 to 6 carbon atoms, a is 0.75 to 1.5, b
Is a positive number that satisfies 0.2 to 2 and satisfies 0.95 <a + b <3.4. ) Is an alkoxy group-containing siloxane represented by

As R ² in the above formula (2), the same groups as in the above formula (1) can be mentioned. R ³ is an alkyl group having 1 to 6 carbon atoms, and specific examples include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, and an n-
Examples thereof include a butyl group, isobutyl group, t-butyl group, n-pentyl group, isopentyl group, neopentyl group, t-pentyl group, and hexyl group. R ³ is particularly preferably a methyl group or an ethyl group among these.

A is 0.75 to 1.5, b is 0.2 to 2
And a positive number satisfying 0.95 <a + b <3.4, preferably a is 0.85 to 1.2, and b is 0.5 to 2
And 1.1 <a + b <3.4.

The alkoxy group-containing siloxane of the above formula (2) preferably has 2 to 6, especially 2 to 4, silicon atoms, and has a viscosity of not more than 300 mm ² / s at 25 ° C. Are preferable, and especially 1 to 100 mm ² /
Those having a viscosity of s are preferred.

The alkoxy group-containing siloxane of the above formula (2) can be synthesized by a usual method, but it is particularly advantageous to use an alkyltrichlorosilane having 1 to 6 carbon atoms alone or a mixture thereof in water with methanol. Alternatively, it is obtained by reaction with ethanol.

The component (C) of the present invention is represented by the following general formula (3): R ⁴ R ⁵ NR ⁶ —SiR ⁷ _n (OR ² ) _3-n (3) (where R ² is the same as above) R ⁴ and R ⁵ each represent a hydrogen atom or the same or different carbon atoms having 1 to 1
5 alkyl groups or aminoalkyl groups, R ⁶ is a divalent hydrocarbon group having 1 to 18 carbon atoms, R ⁷ is 1 to 4 carbon atoms.
Is an alkyl group. n is 0 or 1. ) Or a partial hydrolyzate thereof.

In the above formula (3), R ⁴ and R ⁵ each represent a hydrogen atom or the same or different carbon atoms having 1 to 15 carbon atoms.
And alkyl groups such as methyl group, ethyl group, propyl group, butyl group and the like, and aminoalkyl groups such as aminomethyl group, aminoethyl group, aminopropyl group and aminobutyl group. Can be R ⁷ is an alkyl group having 1 to 4 carbon atoms, such as a methyl group, an ethyl group, a propyl group, and a butyl group.

Specific examples of the amino group-containing alkoxysilane of the formula (3) include the following compounds. H ₂ N (CH ₂ ) ₂ Si (OCH ₃ ) ₃ , H ₂ N (CH ₂ ) ₂ S
i (OC ₂ H ₅ ) ₃ , H ₂ N (CH ₂ ) ₃ Si (OCH ₃ ) ₃ ,
H ₂ N (CH ₂ ) ₃ Si (OC ₂ H ₅ ) ₃ , CH ₃ NH (C
H ₂ ) ₃ Si (OCH ₃ ) ₃ , CH ₃ NH (CH ₂ ) ₃ Si
(OC ₂ H ₅ ) ₃ , CH ₃ NH (CH ₂ ) ₅ Si (OC
H ₃ ) ₃ , CH ₃ NH (CH ₂ ) ₅ Si (OC ₂ H ₅ ) ₃ , H ₂
N (CH ₂ ) ₂ NH (CH ₂ ) ₃ Si (OCH ₃ ) ₃ , H ₂ N
(CH ₂ ) ₂ NH (CH ₂ ) ₃ Si (OC ₂ H ₅ ) ₃ , CH ₃ N
H (CH ₂ ) ₂ NH (CH ₂ ) ₃ Si (OCH ₃ ) ₃ , CH ₃
NH (CH ₂ ) ₂ NH (CH ₂ ) ₃ Si (OC ₂ H ₅ ) ₃ , C ₄
H ₉ NH (CH ₂ ) ₂ NH (CH ₂ ) ₃ Si (OCH ₃ ) ₃ ,
_{C 4 H 9 NH (CH 2} ) 2 NH (CH 2) 3 Si (OC 2 H 5)
₃ , H ₂ N (CH ₂ ) ₂ SiCH ₃ (OCH ₃ ) ₂ , H ₂ N (C
H ₂ ) ₂ SiCH ₃ (OC ₂ H ₅ ) ₂ , H ₂ N (CH ₂ ) ₃ Si
CH ₃ (OCH ₃ ) ₂ , H ₂ N (CH ₂ ) ₃ SiCH ₃ (OC _{2
H 5) 2, CH 3 NH} (CH 2) 3 SiCH 3 (OCH 3) 2,
CH ₃ NH (CH ₂ ) ₃ SiCH ₃ (OC ₂ H ₅ ) ₂ , CH ₃ N
H (CH ₂ ) ₅ SiCH ₃ (OCH ₃ ) ₂ , CH ₃ NH (CH
₂ ) ₅ SiCH ₃ (OC ₂ H ₅ ) ₂ , H ₂ N (CH ₂ ) ₂ NH
(CH ₂ ) ₃ SiCH ₃ (OCH ₃ ) ₂ , H ₂ N (CH ₂ ) ₂ N
H (CH ₂ ) ₃ SiCH ₃ (OC ₂ H ₅ ) ₂ , CH ₃ NH (C
H ₂ ) ₂ NH (CH ₂ ) ₃ SiCH ₃ (OCH ₃ ) ₂ , CH ₃ N
H (CH ₂ ) ₂ NH (CH ₂ ) ₃ SiCH ₃ (OC ₂ H ₅ ) ₂ ,
C ₄ H ₉ NH (CH ₂ ) ₂ NH (CH ₂ ) ₃ SiCH ₃ (OC
_{H 3) 2, C 4 H} 9 NH (CH 2) 2 NH (CH 2) 3 SiCH
₃ (OC ₂ H ₅ ) ₂ Of these compounds, the following compounds are particularly preferred. H ₂ N (CH ₂ ) ₂ Si (OCH ₃ ) ₃ , H ₂ N (CH ₂ ) ₂ N
H (CH ₂ ) ₃ Si (OCH ₃ ) ₃ , H ₂ N (CH ₂ ) ₂ NH
(CH ₂ ) ₃ SiCH ₃ (OCH ₃ ) ₂

The proportion of the components (A), (B) and (C) used is 1 to 30 parts (parts by weight, hereinafter the same) of the component (A),
Preferably 5 to 20 parts, 70 to 90 parts, preferably 70 to 80 parts of component (B) and 1 to 20 parts, preferably 10 to 20 parts of component (C). When the amount of the component (A) is less than 1 part, the germination inhibitory property is weakened. When the amount is more than 30 parts, the stability of the germination inhibitor in an aqueous solution is deteriorated. When the amount of the component (B) is less than 70 parts, it is difficult to maintain a stable germination prevention property, and when it is more than 90 parts, the germination prevention property is weak.
When the amount of the component (C) is less than 1 part, the water solubility becomes poor,
When the amount is more than the part, the germination prevention property is weakened.

In the present invention, when producing a germination inhibitor using these components (A), (B) and (C), co-hydrolysis is carried out in the presence of an organic acid or an inorganic acid. In this case, the component (A) is first hydrolyzed in the presence of an organic acid or an inorganic acid from the viewpoint of the stability of the organosilicon compound, and the hydrolyzate of the component (A) and the component (B) are mixed. In the presence of an organic or inorganic acid, water is added to further hydrolyze, and finally (C)
It is preferred to react with the components.

Here, the organic acid and the inorganic acid used for hydrolyzing the component (A) are, for example, hydrochloric acid,
Sulfuric acid, methanesulfonic acid, formic acid, acetic acid, propionic acid,
At least one acid selected from citric acid, oxalic acid, maleic acid and the like is used, and acetic acid and propionic acid are particularly preferred. The amount of the acid used depends on the amount of component (A) 10
2 to 40 parts, particularly 3 to 15 parts, is suitable for 0 parts.

The above-mentioned hydrolysis reaction is preferably carried out in a state diluted appropriately with a solvent. As the solvent, an alcohol solvent is preferable, and particularly, methanol, ethanol, isopropanol, and tert-butyl alcohol are preferable.
The amount of the solvent used is 50 parts per 100 parts of the component (A).
It is preferably from 300 to 300 parts, particularly preferably from 70 to 200 parts. If the amount of the solvent is less than 50 parts, the condensation may proceed, and if it exceeds 300 parts, the hydrolysis may take a long time to be unfavorable.

The amount of water added to hydrolyze the component (A) is 1 to 4 moles per 1 mole of the component (A).
Particularly, the amount is preferably 2 to 3.5 mol. If the amount of water added is less than 1 mol, a large amount of alkoxy groups may remain. If the amount exceeds 4 mol, condensation may proceed too much, which is not preferable.

The reaction conditions for hydrolyzing the component (A) are preferably a reaction temperature of 10 to 40 ° C., particularly preferably 20 to 30 ° C.
The reaction time is preferably 1 to 3 hours.

Next, the hydrolyzate of the component (A) hydrolyzed by such a method and the component (B) are mixed. At this time, the component (B) may be diluted with a solvent. As the solvent, the same alcohol-based solvent as described above is preferably used. The amount of the solvent to be used is preferably 0 to 300 parts, particularly preferably 50 to 200 parts, per 100 parts of the component (B). The temperature at the time of mixing the hydrolyzate of the component (A) and the component (B) is preferably 10 to 40 ° C, particularly preferably 20 to 30 ° C.
It is good to mix in 3 hours.

Further, when a mixture of the hydrolyzate of the component (A) and the component (B) is hydrolyzed, it is desirable to add an organic acid or an inorganic acid together with water. As the organic acid or the inorganic acid, the same ones that can be used for the hydrolysis of the component (A) can be used.

In this case, the amount of the organic acid or inorganic acid used is
(B) 2 to 40 parts, especially 3 to 15 parts per 100 parts of the component
Parts are preferred. The amount of water to be added is preferably from 0.5 to 1.5 mol, more preferably from 0.6 to 1 mol, per 1 mol of the component (B). If the amount of water is less than 0.5 molar amount, hydrolysis is not so much, and the water solubility of the final product
The storage stability of the aqueous solution may deteriorate, and the amount of water may be reduced to 1.
If the amount exceeds 5 mol, the condensation proceeds too much, and the permeability to soil may be deteriorated.

The reaction conditions for this hydrolysis are as follows:
-40 ° C, especially 20-30 ° C, and the reaction time is 1-3
Time is desirable.

Next, the hydrolyzate of the component (A) and the hydrolyzate of the component (B) obtained above are reacted with the component (C). The reaction conditions are as follows:
C. and a reaction time of 1 to 3 hours are preferred. After completion of the reaction, it is desirable to elevate the temperature to the boiling point of the solvent or higher and distill off the solvent. The reaction product which can be produced by the above method preferably has a weight average molecular weight of 500 to 5,000, particularly preferably 1,000 to 2,000.

The germination inhibitor of the present invention comprises a co-hydrolysis / condensation reaction product of the components (A), (B) and (C) obtained by the method described above, and comprises the component (B) as a main component. By using it, the molecular weight is appropriately controlled, the permeability to soil is improved, and stable germination prevention can be exhibited over a long period of time. Furthermore, when diluted with water, the polymerization reaction in water is suppressed, and the storage stability is improved. On the other hand, without using the component (B), for example, (A)
If it is produced using only the component (C) and the component (C), the polymerization proceeds excessively, so that it is difficult to dissolve in water and the appearance may be deteriorated. In this case, when the component (A) is manufactured with less than 7 carbon atoms, water solubility and appearance are good, but the germination prevention property may be deteriorated.

Further, the component (C) is a component for imparting water solubility, and without it, it does not dissolve in water. Further, by using the component (B) as the main agent, the amount of the component (C) used can be reduced.

When the germination inhibitor using the water-soluble organosilicon compound of the present invention is applied to soil or the like, it is preferably 0.1 to 50% by weight, more preferably 1 to 30% by weight with water.
Used after dilution. If the dilution is less than 0.1% by weight, not only the original performance is not exhibited, but also a large amount must be sprayed, which may be inefficient. Also, 50
If the concentration is higher than% by weight, the dilution will not be sufficient,
In some cases, the viscosity is increased, and the permeability to soil is deteriorated, and the stability of the aqueous solution is also deteriorated.

When the water-soluble organosilicon compound of the present invention is used as a germination inhibitor by diluting it with water, an insecticide and other pesticides, preservatives, fungicides, fragrances and the like can be used as long as the effectiveness is not reduced. Various additives such as an agent, a thickener, an antifoaming agent, an antibacterial agent or a fertilizer component can be compounded and used. In addition,
The addition amount of these optional components can be a usual amount as long as the effects of the present invention are not hindered.

The method of using the germination inhibitor of the present invention includes
An ordinary method of spraying a liquid pesticide is adopted, and the applied amount is generally in the range of 0.1 to 20 kg per unit area (m ² ). If the applied amount is less than 0.1 kg, it may not be possible to obtain an effective soil thickness for preventing germination, and if the applied amount exceeds 20 kg, the chemical solution penetrates deeper than necessary and is uneconomical. Not only that, the environment of the soil at the root of the growing plant is changed, which may not be a preferable method.

The germination inhibitor of the present invention easily penetrates into the soil when sprayed on the surface of the soil. Thereafter, the water-soluble organosilicon compound is siloxane-bonded to the soil and is fixed, thereby modifying the soil to be hydrophobic. It is said that the humidity of the environment must be above a certain level in order for plant seeds to germinate.Soil modified to be hydrophobic by a water-soluble organosilicon compound creates an unsuitable environment for seed germination. It is estimated that In addition, this germination inhibitor, which is an aqueous solution of a water-soluble organosilicon compound, does not significantly affect the growth of plants. Also, the modified soil does not prevent air or moisture from migrating into the interior. Furthermore, since the transfer to the surface of soil water is suppressed, a water retention effect can also be expected.

[0040]

EFFECT OF THE INVENTION By spraying the germination inhibitor according to the present invention on the soil surface, the germination of flying weed seeds is prevented without adversely affecting the growth of useful plants. Since the effect is also long-term, it is possible to reduce the enormous labor and cost required for removing weeds, which has been conventionally required, and also to reduce the use of environmentally undesirable herbicides. In addition, the germination inhibitor of the present invention has a higher reactivity with soil than the conventional one,
Has high storage stability.

[0041]

EXAMPLES Hereinafter, the present invention will be described specifically with reference to Synthesis Examples, Examples, Comparative Examples, and Practical Test Examples, but the present invention is not limited to the following Examples.

Synthesis Example 1 In a 5.0 L four-necked flask equipped with a cooling tube, a thermometer, and a dropping funnel, 126.0 g (0.48 mol) of decyltrimethoxysilane, 106.0 g of methanol, and acetic acid 9 0.6 g and water 30.0 g (1.
70 mol) and stirred at 25 ° C. for 2 hours to obtain a clear solution.

1212.0 g of methyltrimethoxysilane oligomer (4.56 mol in terms of dimer) and 1848.0 g of methanol were added dropwise to the solution with stirring, and the mixture was stirred at 25 ° C. for 1 hour. Then, acetic acid 144.
Then, 0 g and 81.6 g (4.50 mol) of water were added, and the mixture was further stirred for 1 hour. There N- (2-aminoethyl) -3
-213.6 g of aminopropyltrimethoxysilane
(0.96 mol) was added dropwise. Then, after heating to the reflux temperature of methanol and reacting for 1 hour, methanol was distilled off with an ester adapter until the internal temperature reached 110 ° C.
A light yellow transparent solution was obtained (weight average molecular weight 1100) (N
o. 1).

[Synthesis Example 2] In a 5.0 L four-necked flask equipped with a cooling tube, a thermometer and a dropping funnel, 126.0 g (0.48 mol) of decyltrimethoxysilane, 106.0 g of methanol, and acetic acid 9 0.6 g and water 30.0 g (1.
70 mol) and stirred at 25 ° C. for 2 hours to obtain a clear solution.

1212.0 g of methyltrimethoxysilane oligomer (4.56 mol in terms of dimer) and 1848.0 g of methanol were added dropwise to the solution with stirring, and the mixture was stirred at 25 ° C. for 1 hour. Thereafter, acetic acid 86.4
g and 81.6 g (4.50 mol) of water.
Stirred for hours. There, 171.8 g (0.96 mol) of 3-aminopropyltrimethoxysilane was added dropwise. Then, after heating to the reflux temperature of methanol and reacting for 1 hour,
Methanol was distilled off with an ester adapter until the internal temperature reached 110 ° C. to obtain a transparent solution (weight average molecular weight 1).
000) (No. 2).

Synthesis Example 3 98.9 g (0.48 mol) of hexyltrimethoxysilane, 106.0 g of methanol, and acetic acid 9 were placed in a 5.0 L four-necked flask equipped with a cooling tube, a thermometer and a dropping funnel. 0.6 g and water 30.0 g (1.
70 mol) and stirred at 25 ° C. for 2 hours to obtain a clear solution.

1212.0 g of methyltrimethoxysilane oligomer (4.56 mol in terms of dimer) and 1848.0 g of methanol were added dropwise to the solution with stirring, and the mixture was stirred at 25 ° C. for 1 hour. Then, acetic acid 144.
Then, 0 g and 81.6 g (4.50 mol) of water were added, and the mixture was further stirred for 1 hour. There N- (2-aminoethyl) -3
-213.6 g of aminopropyltrimethoxysilane
(0.96 mol) was added dropwise. Then, after heating to the reflux temperature of methanol and reacting for 1 hour, methanol was distilled off with an ester adapter until the internal temperature reached 110 ° C.
A light yellow transparent solution was obtained (weight average molecular weight 1500) (N
o. 3).

Synthesis Example 4 A 5.0 L four-necked flask equipped with a condenser, a thermometer and a dropping funnel was charged with 78.7 g (0.48 mol) of propyltrimethoxysilane, 106.0 g of methanol, and 9% of acetic acid. 0.6 g and water 30.0 g (1.
70 mol) and stirred at 25 ° C. for 2 hours to obtain a clear solution.

1212.0 g of methyltrimethoxysilane oligomer (4.56 mol in terms of dimer) and 1848.0 g of methanol were added dropwise to the solution with stirring, followed by stirring at 25 ° C. for 1 hour. Then, acetic acid 144.
Then, 0 g and 81.6 g (4.50 mol) of water were added, and the mixture was further stirred for 1 hour. There N- (2-aminoethyl) -3
-213.6 g of aminopropyltrimethoxysilane
(0.96 mol) was added dropwise. Then, after heating to the reflux temperature of methanol and reacting for 1 hour, methanol was distilled off with an ester adapter until the internal temperature reached 110 ° C.
A light yellow transparent solution was obtained (weight average molecular weight: 1600) (N
o. 4).

[Synthesis Example 5] 200 g of hexyltriethoxysilane and 8 g of polyoxyethylene octyl phenyl ether having an HLB of 15 as an emulsifier were used, and 292 g of tap water and sodium bicarbonate as a buffer were added to a mixture thereof. 0.1% to prepare an aqueous concentrate milk suspension (No. 5).

[Synthesis Example 6] 68 g (0.5 mol) of methyltrimethoxysilane and N- (2-aminoethyl) -3 were placed in a 5.0 L four-necked flask equipped with a condenser, a thermometer and an aspirator. -222 g (1.0 mol) of aminopropyltrimethoxysilane and 21.6 g (1.2 mol) of water were charged and mixed. Heating was performed while stripping with an aspirator until the temperature reached 60 ° C. to obtain a transparent solution (No. 6).

[Examples 1 to 4] The organosilicon compounds obtained in Synthesis Examples 1 to 4 were diluted with tap water and sprayed on the simulated soil at a rate of 5 kg / m ² as shown below as a germination inhibitor. A germination prevention test was performed. Table 1 shows the test results.

[Comparative Examples 1 and 2] The aqueous stock emulsion obtained in Synthesis Example 5 and the organosilicon compound obtained in Synthesis Example 6 were diluted with tap water to form a germination inhibitor as described below. An initial germination prevention test was conducted by spraying 5 kg / m ^{2 on the} simulated soil. Table 1 shows the test results. Sprouting prevention test A 100-mesh mesh was placed on the lower surface of a transparent acrylic resin pipe having a diameter of 70 mm and 60 mm, and 30
Filling was performed using compacted silica sand while compacting. A predetermined amount of the germination inhibitor prepared above was sprayed thereon, and dried for 7 days (2 days).
(0 ° C., 60% RH). After curing, 20 seeds of Japanese radish were embedded at a depth of about 5 mm from the surface of the simulated soil. Spread absorbent cotton soaked in water on the tray,
An acrylic pipe was placed thereon, and water was sucked up from the lower surface to perform a test for preventing germination. The test environment is 20 ° C,
Replenishment of 60% RH and water was performed as needed. After the test starts, 28
The number of germinations was measured during the measurement of the water rise depth per day, the observation of the water repellency of the surface soil, and an arbitrary test period, and the germination rate was determined by the following equation. Germination rate (%) = [germination number (pieces) / 20] × 100

[0054]

[Table 1]

From the results shown in Table 1, it was confirmed that the germination inhibitor of the present invention (Examples 1 to 4) exhibited an excellent germination prevention effect continuously over a long period of time.

Next, the organosilicon compound obtained in Synthesis Examples 1 to 4 and Synthesis Example 6 and the aqueous emulsion milk suspension obtained in Synthesis Example 5 were diluted with tap water to obtain a sprout inhibitor. After storage for 1 month in an environment at ℃, the state of the aqueous solution was observed, and 5 kg / m ^{2 was} sprayed on the simulated soil to carry out a germination prevention test. Table 2 shows the test results.

[0057]

[Table 2]

From the results shown in Table 2, it was confirmed that the germination inhibitor (Examples 1 to 4) of the present invention was excellent in storage stability.

Further, using the various germination inhibitors prepared in the same manner as above, a field test was carried out by the following method. Table 3 shows the results. Lawn mascarenegrass removal of the field test weeds were divided into 3m × 3m, various germination inhibitor was sprayed on 5 kg / m ² uniformly in summer, the status of lawn surface after 1 month (grass state, presence or absence of weed ) Was observed.

[0060]

[Table 3]

────────────────────────────────────────────────── ─── Continuation of the front page (56) References JP-A-4-257507 (JP, A) JP-A-7-194286 (JP, A) JP-A-9-67571 (JP, A) JP-A-5-257 25010 (JP, A) JP-A-9-157117 (JP, A) JP-A-8-119815 (JP, A) JP-A-51-67731 (JP, A) JP-A-6-179605 (JP, A) JP-A-6-172112 (JP, A) JP-A-8-35218 (JP, A) (58) Fields investigated (Int. Cl. ⁷ , DB name) A01N 55/00

Claims (2)

(57) [Claims] (A) The following general formula (1): R¹ Si (OR^Two)_Three (1) (where R¹Is a monovalent saturated carbon having 1 to 18 carbon atoms.
Hydrogen group, R^TwoIs an alkyl group having 1 to 4 carbon atoms.
You. )) Or a trialkoxysilane or a partial addition thereof
1 to 30 parts by weight of a hydrolyzate and (B) the following general formula (2) R^Three _a(OR^Two)_bSiO_{(4-ab) / 2} (2) (where R^TwoIs the same as above, and R^ThreeIs the number of carbon atoms
1 to 6 alkyl groups, a is 0.75 to 1.5, b
Satisfies 0.2 to 2 and satisfies 0.95 <a + b <3.4
Is a positive number. ) -Containing siloxy group represented by
70 to 90 parts by weight of sun and (C) the following general formula (3) R^FourR^FiveNR⁶-SiR⁷ _n(OR^Two)_3-n (3) (where R^TwoIs the same as above, and R^Four, R^FiveIs it
A hydrogen atom or the same or different carbon atom number of 1 to 1
5, an alkyl group or an aminoalkyl group, R⁶Is a carbon atom
A divalent hydrocarbon group of the formulas 1 to 18, R⁷Is 1 to 4 carbon atoms
Is an alkyl group. n is 0 or 1. )
Amino group-containing alkoxysilane or its partial hydrolysis
1 to 20 parts by weight of the product in the presence of an organic acid or an inorganic acid
Water-soluble organosilicon compound obtained by decomposition
A germination inhibitor comprising: 2. The (A) component trialkoxysilane of the formula (1) or its partial hydrolyzate is hydrolyzed in the presence of an organic acid or an inorganic acid, and the hydrolyzate is added to the component (B). An alkoxy group-containing siloxane of the formula (2) is mixed and hydrolyzed in the presence of an organic or inorganic acid, and finally (C)
The method for producing a germination inhibitor according to claim 1, wherein the component is reacted with an amino group-containing alkoxysilane represented by the formula (3) or a partial hydrolyzate thereof.