JPH0790274A - Soil conditioner - Google Patents
Soil conditionerInfo
- Publication number
- JPH0790274A JPH0790274A JP25942093A JP25942093A JPH0790274A JP H0790274 A JPH0790274 A JP H0790274A JP 25942093 A JP25942093 A JP 25942093A JP 25942093 A JP25942093 A JP 25942093A JP H0790274 A JPH0790274 A JP H0790274A
- Authority
- JP
- Japan
- Prior art keywords
- chitosan
- soil conditioner
- deacetylation degree
- deacetylation
- liquid soil
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
Landscapes
- Soil Conditioners And Soil-Stabilizing Materials (AREA)
Abstract
Description
【０００１】[0001]
【産業上の利用分野】本発明は、土壌の団粒化を促進
し、土壌の物理性即ち、通気性・透水性・保水性・耐侵
食性・易耕性等を改善する液状の土壌改良剤に関する。FIELD OF THE INVENTION The present invention relates to a liquid soil improvement for promoting the aggregation of soil and improving the physical properties of soil, that is, air permeability, water permeability, water retention, erosion resistance, and easy cultivability. Regarding agents.
【０００２】[0002]
【従来の技術】即に我々は、特開昭６３−１４６９８２
号公報により、キトサンを主成分とする土壌改良剤を開
示している。2. Description of the Related Art Immediately, we have disclosed in Japanese Patent Laid-Open No. 63-146982.
Japanese Patent Publication discloses a soil conditioner containing chitosan as a main component.
【０００３】キトサンは、キチンの脱アセチル化物であ
って甲殻類の甲殻や昆虫の皮膚に含まれるキチンを濃ア
ルカリと加熱することによって得られる。一般的にキト
サンとは脱アセチル化度５０％以上ので酸に可溶なもの
を示し、脱アセチル化度８０％位のものが市販されてい
る。Chitosan is a deacetylated product of chitin and is obtained by heating chitin contained in the shells of crustaceans and the skin of insects with concentrated alkali. Generally, chitosan has a deacetylation degree of 50% or more and is soluble in acid, and a deacetylation degree of about 80% is commercially available.
【０００４】キトサンを液剤として使用する時は希酸に
溶解して使用しなければならない。キトサンは天然の高
分子であるため液状での安定性が非常に悪く、長期間保
存すると分解していく。（粘度低下し水のような状態に
達する）When chitosan is used as a liquid agent, it must be dissolved in dilute acid before use. Since chitosan is a natural polymer, its stability in liquid form is very poor and it decomposes when stored for a long time. (Viscosity decreases and reaches a state like water)
【０００５】特開平１−９６２８４号のキトサン及び可
溶性蛋白質を主成分とする液状土壌改良剤もキトサン、
タンパク質が天然の高分子であるために液状での安定性
が悪く低温で増粘し、高温では粘度低下する。製品の経
時的な安定性、特に粘度安定性が悪く、製品の保証期間
が短いという欠点があった。そこで、経時的な団粒形成
効果の低下を少なくし、特に粘度安定性の良好な製品が
望まれていた。Chitosan and a liquid soil conditioner containing a soluble protein as a main component as disclosed in JP-A-1-96284 are also chitosan.
Since the protein is a natural polymer, the stability in liquid form is poor and the viscosity increases at low temperature and decreases at high temperature. There was a defect that the stability of the product over time, particularly the viscosity stability was poor, and the warranty period of the product was short. Therefore, there has been a demand for a product which has less deterioration in the effect of forming aggregates over time and has particularly good viscosity stability.
【０００６】[0006]
【発明が解決しようとする課題】本発明の目的は、キト
サンを主成分とし、粘度安定性に優れた液状の土壌改良
剤を提供することである。SUMMARY OF THE INVENTION An object of the present invention is to provide a liquid soil conditioner containing chitosan as a main component and having excellent viscosity stability.
【０００７】[0007]
【課題を解決するための手段】脱アセチル化度９５％以
上のキトサンを希酸に溶解し、均一系、一定温度にて無
水酢酸を添加し、脱アセチル化度３０％以上のキトサン
を調整し、アルカリで中和することにより、粘度安定性
に優れ、しかも団粒形成能の高い液状土壌改良剤を開発
することができた。脱アセチル化度３０％以下になると
不溶化するため製造できない。[Means for Solving the Problems] Chitosan having a deacetylation degree of 95% or more is dissolved in dilute acid, and acetic anhydride is added at a constant temperature at a constant temperature to prepare a chitosan having a deacetylation degree of 30% or more. By neutralizing with alkali, it was possible to develop a liquid soil conditioner with excellent viscosity stability and high aggregate-forming ability. When the degree of deacetylation is 30% or less, it cannot be manufactured because it becomes insoluble.
【０００８】キトサンは一般的に不均一系で濃アルカリ
処理により脱アセチル化させるため、アセチル基の分布
も不均一になっている。本発明の土壌改良剤は、９５％
以上脱アセチル化度のキトサンを均一系でアセチル化処
理するため、ランダムにアセチル化され、結晶性が低
く、溶解性や粘度安定性が良好になると考えられる。Chitosan is generally a heterogeneous system and is deacetylated by a concentrated alkali treatment, so that the distribution of acetyl groups is also nonuniform. The soil improver of the present invention is 95%
It is considered that since chitosan having a deacetylation degree as described above is subjected to acetylation treatment in a uniform system, it is randomly acetylated, has low crystallinity, and has good solubility and viscosity stability.
【０００９】本発明の製造方法について述べる。まず、
脱アセチル化度９５％以上のキトサンを酸溶液に溶解す
る。酸としては、酢酸・乳酸・クエン酸・リンゴ酸・塩
酸等が用いられる。このキトサン液を攪拌し、均一系に
おいて無水酢酸を徐添し、アセチル化を行う。反応温度
は、５０℃以下が好ましい。５０℃を越えると中和時に
不溶物を生じることがあるので好ましくない。次にアル
カリ溶液を添加し中和する。使用するアルカリは苛性カ
リ・苛性ソーダ・炭酸ソーダ・炭酸カリ・アンモニア水
等がある。特に苛性カリが好ましい。The manufacturing method of the present invention will be described. First,
Chitosan having a deacetylation degree of 95% or more is dissolved in an acid solution. As the acid, acetic acid, lactic acid, citric acid, malic acid, hydrochloric acid or the like is used. This chitosan solution is stirred, and acetic anhydride is gradually added in a homogeneous system for acetylation. The reaction temperature is preferably 50 ° C or lower. If the temperature exceeds 50 ° C, insoluble matter may be generated during neutralization, which is not preferable. Next, an alkaline solution is added to neutralize. The alkali used includes caustic potash, caustic soda, sodium carbonate, potash carbonate, ammonia water, and the like. Particularly, caustic potash is preferable.
【００１０】得られた液状土壌改良剤を６０〜９０℃の
温度で加熱処理することにより、低粘度の製品とするこ
とができる。液状の土壌改良剤は希釈し、灌水チューブ
等を用い散布することが多く、粘度が低いと製品を希釈
する時も混溶しやすいし、液も出しやすく作業性が改善
される。又、加熱処理した液状の土壌改良剤は、さらに
製品の粘度安定性が増大する。加熱温度６０℃以下では
粘度低下しにくく、９０℃を越えると不溶物等が生じ安
定性が低下する。By heating the obtained liquid soil conditioner at a temperature of 60 to 90 ° C., a product having a low viscosity can be obtained. Liquid soil conditioners are often diluted and then sprayed using a watering tube or the like. When the viscosity is low, the product is easily mixed even when diluting the product, and the liquid is easily discharged to improve workability. In addition, the heat-treated liquid soil conditioner further increases the viscosity stability of the product. If the heating temperature is 60 ° C. or less, the viscosity is unlikely to decrease, and if it exceeds 90 ° C., insoluble matter and the like are generated and the stability decreases.
【００１１】本発明の土壌改良剤には、肥料成分を含有
することもできる。肥料成分としては、窒素質肥料（硝
安・硫安・尿素・硝酸カリ・硝酸ソーダ・塩安等）、リ
ン酸質肥料・カリ質肥料（リン酸１カリウム・リン酸２
カリウム・塩化カリウム等）の他に多量要素のカルシウ
ム、マグネシウム、微量要素のマンガン、鉄、ほう素、
亜鉛、銅等の塩類が用いられる。The soil improving agent of the present invention may contain a fertilizer component. As fertilizer components, nitrogenous fertilizers (ammonium nitrate, ammonium sulfate, urea, potassium nitrate, sodium nitrate, ammonium chloride, etc.), phosphate fertilizers, potash fertilizers (1 potassium phosphate, 2 phosphates)
In addition to potassium, potassium chloride, etc.), the major elements calcium, magnesium, the trace elements manganese, iron, boron,
Salts such as zinc and copper are used.
【００１２】[0012]
（実施例１）キトサン（脱アセチル化度１００％）１０
ｇを水８６７ｇに分散させ、９０％酢酸１０mlを投入
し、攪拌溶解した。攪拌下３０℃にて無水酢酸２．５ml
を滴下した。３０分後に１０W／V％ＫＯＨ８８mlを滴下
し、中和した。中和後、１時間攪拌し、脱アセチル化度
８０％のキトサンを含有する液状土壌改良剤１Kgが得ら
れた。（脱アセチル化度は、土壌改良剤の５００ｇにエ
タノール５００ｇを加え、沈澱物をろ過後、５０％Ｅｔ
ＯＨで洗浄し、乾燥したものをコロイド滴定法により算
出した。方法は最終項に記載。）(Example 1) Chitosan (deacetylation degree 100%) 10
g was dispersed in 867 g of water, 10 ml of 90% acetic acid was added, and the mixture was stirred and dissolved. 2.5 ml of acetic anhydride at 30 ° C with stirring
Was dripped. After 30 minutes, 88 ml of 10 W / V% KOH was added dropwise to neutralize. After neutralization, the mixture was stirred for 1 hour, and 1 kg of a liquid soil conditioner containing chitosan having a deacetylation degree of 80% was obtained. (Deacetylation degree is 50% Et after adding 500g of ethanol to 500g of soil conditioner and filtering the precipitate.
The product washed with OH and dried was calculated by the colloid titration method. The method is described in the final section. )
【００１３】（実施例２）水８６７ｇ、無水酢酸２．５
ml、１０W／V％ＫＯＨ８８mlをそれぞれ８６３ｇ、３．
３ml、１０３mlに変え、他は実施例１と同様にして、脱
アセチル化度７１％のキトサンを含有する液状土壌改良
剤１Kgが得られた。Example 2 Water 867 g, acetic anhydride 2.5
ml, 10 W / V% KOH 88 ml, respectively 863 g, 3.
In the same manner as in Example 1 except that the amounts were changed to 3 ml and 103 ml, 1 kg of a liquid soil conditioner containing chitosan having a deacetylation degree of 71% was obtained.
【００１４】（実施例３）キトサン（脱アセチル化度１
００％）１０ｇを水８４６ｇに分散させ、９０％酢酸１
０mlを投入し、攪拌溶解した。攪拌下２５℃にて無水酢
酸３．３mlを滴下した。３０分後に１０W／V％ＫＯＨ１
０３mlを滴下し中和した。中和３０分後に無水酢酸１ml
を滴下し１０W／V％ＫＯＨ１５mlを滴下し中和した。中
和後、１時間攪拌し、脱アセチル化度５８％のキトサン
を含有する液状土壌改良剤１Kgが得られた。Example 3 Chitosan (Deacetylation Degree 1
(00%) 10 g was dispersed in 846 g of water, and 90% acetic acid 1
0 ml was added and dissolved by stirring. 3.3 ml of acetic anhydride was added dropwise at 25 ° C. with stirring. After 30 minutes, 10 W / V% KOH1
03 ml was added dropwise to neutralize. After 30 minutes of neutralization, 1 ml of acetic anhydride
Was added dropwise, and 15 ml of 10 W / V% KOH was added dropwise to neutralize. After the neutralization, the mixture was stirred for 1 hour to obtain 1 kg of a liquid soil conditioner containing chitosan having a deacetylation degree of 58%.
【００１５】（実施例４）水８４６ｇ、無水酢酸１ml、
１０W／V％ＫＯＨ１５mlを水８３４ｇ、無水酢酸１．６
５ml、１０W／V％ＫＯＨ２５mlに変え、他は実施例３と
同様にして、脱アセチル化度４９％のキトサンを含有す
る液状土壌改良剤１Kgが得られた。(Example 4) 846 g of water, 1 ml of acetic anhydride,
10 W / V% KOH 15 ml, water 834 g, acetic anhydride 1.6
In the same manner as in Example 3 except that 5 ml and 10 W / V% KOH were changed to 25 ml, 1 kg of a liquid soil conditioner containing chitosan having a deacetylation degree of 49% was obtained.
【００１６】（実施例５）水８４６ｇ、無水酢酸１ml、
１０W／V％ＫＯＨ１５mlを水８２８．５ｇ、無水酢酸
２．２ml、１０W／V％ＫＯＨ３１mlに変え、他は実施例
３と同様にして脱アセチル化度３３％のキトサンを含有
する液状土壌改良剤１Kgが得られた。(Example 5) 846 g of water, 1 ml of acetic anhydride,
Liquid soil conditioner 1 kg containing 158.5 ml of 10 W / V% KOH, 828.5 g of water, 2.2 ml of acetic anhydride and 31 ml of 10 W / V% KOH, and chitosan having a deacetylation degree of 33% in the same manner as in Example 3 was gotten.
【００１７】（実施例６）実施例２と同様にして製造し
た後、最後に８０℃にて１時間加熱し、室温まで冷却し
て液状土壌改良剤１Kgが得られた。(Example 6) After manufacturing in the same manner as in Example 2, finally, heating at 80 ° C for 1 hour and cooling to room temperature, 1 kg of a liquid soil conditioner was obtained.
【００１８】[0018]
【比較例】キトサン（脱アセチル化度８０％，キチンを
濃アルカリ処理し製造されたキトサン。）１０ｇを水８
４６ｇに分散させ、９０％酢酸１０mlを投入し攪拌溶解
した。１０W／V％ＫＯＨ８０mlを滴下し中和した。中和
後、１時間攪拌し、キトサンを含有する液状土壌改良剤
１Kgが得られた。Comparative Example 10 g of chitosan (deacetylation degree 80%, chitosan produced by treating chitin with concentrated alkali) in water 8
Dispersed in 46 g, 10 ml of 90% acetic acid was added, and the mixture was dissolved with stirring. 80 W of 10 W / V% KOH was added dropwise for neutralization. After neutralization, the mixture was stirred for 1 hour to obtain 1 kg of a liquid soil conditioner containing chitosan.
【００１９】[0019]
【試験例】実施例１〜６及び比較例で製造した土壌改良
剤を室温４０℃、５℃にて３ヶ月間保存しpH、粘度、団
粒効果を測定し、液状土壌改良剤の安定性を調査した。[Test Example] Soil improvers prepared in Examples 1 to 6 and Comparative Example were stored at room temperature of 40 ° C. and 5 ° C. for 3 months, pH, viscosity and aggregate effect were measured, and stability of the liquid soil improver was measured. investigated.
【００２０】[0020]
【表１】 [Table 1]
【００２１】（団粒効果の測定法）１００ml容の共栓付
きメスシリンダーに土壌（荒尾のなし園より採取し、
０．２５mmのふるいを通した粘度質土壌）２０ｇを入れ
実施例１〜６、比較例１の各２００倍希釈液を加えて１
００mlとした。メスシリンダーを数回転倒して均質な懸
濁液とした後静置し、６０分後の懸濁液相の容積を読み
とった。対照としては水を用いた。６０分後の容積増大
率（％）は、対照を１００とした場合の試験液の相対比
率である。団粒形成能が大きい場合は、土が凝集して大
きな粒子が形成され、そのため粒子間が増えて懸濁液相
の容積が増大する。(Measurement Method of Aggregate Effect) Soil (collected from Arao-no-Nashien,
20 g of viscous soil) that has passed through a 0.25 mm sieve is added, and 200 times diluted solutions of Examples 1 to 6 and Comparative Example 1 are added to add 1
It was set to 00 ml. The graduated cylinder was inverted several times to make a homogeneous suspension, which was then left standing and the volume of the suspension phase after 60 minutes was read. Water was used as a control. The volume increase rate (%) after 60 minutes is the relative ratio of the test solution when the control is 100. When the aggregate-forming ability is large, the soil is aggregated to form large particles, which increases the number of particles to increase the volume of the suspension phase.
【００２２】（脱アセチル化度の測定方法）キトサン粉
末０．５ｇを正確に秤量し、これを５容量％酢酸に溶か
して正確に１００ｇとする。このキトサン酢酸溶液１ｇ
を２００ml容の三角フラスコに正確にはかりとり、脱イ
オン水３０mlを加え、充分攪拌混合する。指示薬として
０．１％トルイジンブルー溶液２〜３滴を加え、Ｎ／４
００ポリビニル硫酸カリウム溶液〔（C2H3OSK)n n=1500
以上〕で滴定する。脱アセチル化度は数式１を使って算
出した。(Method for measuring the degree of deacetylation) 0.5 g of chitosan powder is accurately weighed and dissolved in 5% by volume acetic acid to make exactly 100 g. 1g of this chitosan acetic acid solution
Accurately weigh the mixture in a 200 ml Erlenmeyer flask, add 30 ml of deionized water, and mix with sufficient stirring. Add 2-3 drops of 0.1% toluidine blue solution as an indicator, N / 4
00 Polyvinyl potassium sulfate solution [(C 2 H 3 OSK) n n = 1500
Above]. The degree of deacetylation was calculated using Equation 1.
【００２３】[0023]
【数１】 [Equation 1]
【００２４】[0024]
【発明の効果】キトサンを用いた液状の土壌改良剤がす
でに開示されているが、天然の高分子であるために、経
時的な安定性、特に粘度安定性が悪く、高温による急激
な粘度低下、及び団粒効果の低下が生じる。又、低温に
よる粘度の上昇、ゲル化といった問題点があった。本発
明の高脱アセチル化度キトサンを均一系でアセチル化し
て、脱アセチル化度３０％以上に調整することにより、
団粒効果の低下も殆んどなく、粘度安定性に優れた液状
の土壌改良剤を製造することが可能となった。EFFECTS OF THE INVENTION A liquid soil conditioner using chitosan has already been disclosed. However, since it is a natural polymer, its stability over time, particularly the viscosity stability, is poor, resulting in a sharp decrease in viscosity at high temperatures. , And a decrease in the aggregate effect. In addition, there are problems such as an increase in viscosity and gelation due to low temperature. The highly deacetylated chitosan of the present invention is acetylated in a homogeneous system to adjust the deacetylation degree to 30% or more,
It was possible to produce a liquid soil conditioner having excellent viscosity stability with almost no deterioration in the aggregate effect.
Claims (2)
を希酸に溶解し、５０℃以下の一定温度で、均一系で無
水酢酸を徐添し、脱アセチル化度３０％以上のキトサン
を調整した後、アルカリ溶液で中和して得られる液状の
土壌改良剤。1. Chitosan (deacetylation degree of 95% or more)
Is dissolved in a dilute acid, acetic anhydride is gradually added in a homogeneous system at a constant temperature of 50 ° C. or lower to adjust chitosan having a deacetylation degree of 30% or more, and then neutralized with an alkaline solution to obtain a liquid form. Soil conditioner.
とする第１項記載の液状土壌改良剤。2. The liquid soil conditioner according to claim 1, which is heat-treated at 60 to 90 ° C.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP25942093A JPH0790274A (en) | 1993-09-24 | 1993-09-24 | Soil conditioner |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP25942093A JPH0790274A (en) | 1993-09-24 | 1993-09-24 | Soil conditioner |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH0790274A true JPH0790274A (en) | 1995-04-04 |
Family
ID=17333857
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP25942093A Pending JPH0790274A (en) | 1993-09-24 | 1993-09-24 | Soil conditioner |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0790274A (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH08283306A (en) * | 1995-04-12 | 1996-10-29 | Yaizu Suisan Kagaku Kogyo Kk | Water-soluble partially deacetylated chitin and its production |
| WO2003037935A1 (en) * | 2001-11-02 | 2003-05-08 | Kunpoong Bio Co.,Ltd | The acetylation method of chitosan |
| CN115558316A (en) * | 2022-08-11 | 2023-01-03 | 秦志强 | Low-alkalinity calcium carbonate and preparation process thereof |
-
1993
- 1993-09-24 JP JP25942093A patent/JPH0790274A/en active Pending
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH08283306A (en) * | 1995-04-12 | 1996-10-29 | Yaizu Suisan Kagaku Kogyo Kk | Water-soluble partially deacetylated chitin and its production |
| WO2003037935A1 (en) * | 2001-11-02 | 2003-05-08 | Kunpoong Bio Co.,Ltd | The acetylation method of chitosan |
| CN115558316A (en) * | 2022-08-11 | 2023-01-03 | 秦志强 | Low-alkalinity calcium carbonate and preparation process thereof |
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