WO2016204290A1 - 凍結融解安定性に優れる土壌侵食防止剤 - Google Patents
凍結融解安定性に優れる土壌侵食防止剤 Download PDFInfo
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- WO2016204290A1 WO2016204290A1 PCT/JP2016/068174 JP2016068174W WO2016204290A1 WO 2016204290 A1 WO2016204290 A1 WO 2016204290A1 JP 2016068174 W JP2016068174 W JP 2016068174W WO 2016204290 A1 WO2016204290 A1 WO 2016204290A1
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- soil erosion
- erosion inhibitor
- resin emulsion
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K17/00—Soil-conditioning materials or soil-stabilising materials
- C09K17/14—Soil-conditioning materials or soil-stabilising materials containing organic compounds only
- C09K17/18—Prepolymers; Macromolecular compounds
- C09K17/20—Vinyl polymers
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L31/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an acyloxy radical of a saturated carboxylic acid, of carbonic acid or of a haloformic acid; Compositions of derivatives of such polymers
- C08L31/02—Homopolymers or copolymers of esters of monocarboxylic acids
- C08L31/04—Homopolymers or copolymers of vinyl acetate
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/52—Aqueous emulsion or latex, e.g. containing polymers of a glass transition temperature (Tg) below 20°C
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K2105/00—Erosion prevention
-
- E—FIXED CONSTRUCTIONS
- E02—HYDRAULIC ENGINEERING; FOUNDATIONS; SOIL SHIFTING
- E02D—FOUNDATIONS; EXCAVATIONS; EMBANKMENTS; UNDERGROUND OR UNDERWATER STRUCTURES
- E02D17/00—Excavations; Bordering of excavations; Making embankments
- E02D17/20—Securing of slopes or inclines
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- E—FIXED CONSTRUCTIONS
- E02—HYDRAULIC ENGINEERING; FOUNDATIONS; SOIL SHIFTING
- E02D—FOUNDATIONS; EXCAVATIONS; EMBANKMENTS; UNDERGROUND OR UNDERWATER STRUCTURES
- E02D3/00—Improving or preserving soil or rock, e.g. preserving permafrost soil
- E02D3/12—Consolidating by placing solidifying or pore-filling substances in the soil
Definitions
- the present invention relates to a soil erosion inhibitor that is suitably used to prevent soil erosion from slopes formed by embankments and cuts in the construction of construction sites, roads, dams, and the like.
- Patent Document 1 a spraying material in which a soil drying inhibitor composed of a water-swellable water-absorbing resin, a surfactant, and a synthetic resin emulsion is blended at a ratio of 0.5 to 1.5 kg per 1 m3 of the spraying material is a slope. By spraying on the soil, erosion of the soil is prevented.
- materials used for slope construction may be stored in warehouses, etc., but may be carried to the site and covered with sheets, etc.
- the problem is that the soil erosion inhibitor freezes and aggregates.
- Patent Document 2 relates to a polyacrylamide resin
- Patent Document 3 uses an alkoxylated compound as a constituent component. There is no description regarding improvement of freeze-thaw stability of vinyl acetate resin emulsion.
- the present invention has been made in view of such circumstances, and provides a soil erosion inhibitor that improves freeze-thaw stability without impairing the soil erosion prevention effect.
- the present invention is as follows.
- a soil erosion inhibitor containing an aqueous resin emulsion and a water-soluble polymer wherein the aqueous resin emulsion has a toluene insoluble content of 60% by mass or more, and the content of the water-soluble polymer in the soil erosion inhibitor Is a soil erosion inhibitor characterized by having 1 to 7% by mass.
- the emulsion is an emulsion of a resin containing structural units derived from vinyl acetate.
- the emulsion is an ethylene-vinyl acetate copolymer emulsion.
- the soil erosion inhibitor of the present invention is a soil erosion inhibitor containing an aqueous resin emulsion and a water-soluble polymer, wherein the aqueous resin emulsion has a toluene insoluble content of 60% by mass or more, and the aqueous resin emulsion is water-soluble.
- a soil erosion inhibitor having excellent freeze-thaw stability which contains a polymer and has a water-soluble polymer content in the soil erosion inhibitor of 1 to 7% by mass, preferably 3 to 5% by mass.
- the toluene-insoluble content of the aqueous resin emulsion means a solid content that becomes an insoluble material when the water-based resin emulsion is dried by drying and dissolved in toluene.
- the type of the aqueous resin emulsion is not particularly limited, and is vinyl acetate resin emulsion, vinyl acetate copolymer emulsion, acrylate resin emulsion, styrene acrylate copolymer emulsion, ethylene-vinyl acetate copolymer emulsion, styrene- Examples include butadiene copolymer emulsion, vinylidene resin emulsion, polybutene resin emulsion, acrylonitrile-butadiene resin emulsion, methacrylate-butadiene resin emulsion, asphalt emulsion, epoxy resin emulsion, urethane resin emulsion, silicone resin emulsion, etc.
- Resin emulsion containing structural units derived from vinyl acetate are preferable, ethylene - vinyl acetate copolymer emulsion is more preferred.
- the method for producing the aqueous resin emulsion is not particularly limited, and for example, it can be produced by adding an emulsifier and a monomer to a dispersion medium containing water as a main component and emulsion polymerizing the monomer while stirring. Depending on the type of monomer used during the production and the addition rate, the toluene-insoluble content of the resulting emulsion can be changed.
- the emulsifier include ionic (cationic, anionic, and zwitterionic) surfactants and nonionic (nonionic) surfactants.
- nonionic surfactants include low molecular surfactants such as alkylglycosides, and high molecular surfactants such as polyethylene glycol and polyvinyl alcohol, and high molecular surfactants are preferred.
- the polymer surfactant is particularly preferably made of polyvinyl alcohol, and the average degree of polymerization thereof is, for example, 200 to 2500, preferably 400 to 2200, and more preferably 500 to 2000. Since polyvinyl alcohol has a higher emulsification dispersion power as the average degree of polymerization is larger, polyvinyl alcohol having an appropriate average degree of polymerization may be used so that an emulsion having a desired degree of dispersion can be obtained.
- Polyvinyl alcohol may be used in combination of a plurality of types having different average degrees of polymerization.
- the degree of saponification of polyvinyl alcohol is not particularly limited, but is, for example, 70% or more, and preferably 80 to 95%. This is because if the degree of saponification is too low, the solubility in water is extremely lowered, and it cannot be dissolved unless a special dissolution method is used, and it is difficult to use industrially.
- the lower the degree of saponification the higher the emulsifying and dispersing power of polyvinyl alcohol. Therefore, polyvinyl alcohol having an appropriate degree of saponification may be used so that an emulsion having a desired degree of dispersion can be obtained.
- a plurality of different emulsifiers may be used in combination.
- the amount of the emulsifier added is not particularly limited, but is, for example, 0.5 to 20 parts by mass with respect to 100 parts by mass of the dispersion medium, and preferably 1 to 10 parts by mass. Since the emulsifier dispersibility increases as the added amount of the emulsifier increases, the added amount of the emulsifier is appropriately adjusted so that an emulsion having a desired degree of dispersion can be obtained.
- the solid content of the soil erosion inhibitor is 25 to 60% by mass, preferably 30 to 40% by mass. If the solid content is too low, the amount of the polymer of the soil erosion inhibitor is too small and the soil erosion prevention effect is weak, and if the solid content is too high, the viscosity becomes too high and it is not easy to blend in the spray material. This is also because freeze-thaw stability tends to decrease.
- the water-soluble polymer contained in the soil erosion inhibitor of the present invention is not particularly limited as long as it has a property of being soluble in water.
- the water-soluble polymer contained in the soil erosion inhibitor is preferably 1 to 7% by mass, more preferably 3 to 5% by mass.
- the total amount of the emulsifier and the water-soluble polymer contained in the soil erosion inhibitor is preferably 1.5 to 8.5% by mass, and more preferably 3.5 to 6.5% by mass.
- This soil erosion inhibitor may be sprayed alone on the surface to be protected. It is mixed with the spray material made mainly of soil and mixed with seeds, fertilizer, etc. and sprayed on the surface to be protected together with the spray material. Also good.
- the method of spraying the spray material onto the target surface includes seed sprayers, customer soil sprayers, base material sprayers, etc., or if the target surface is vast, such as a helicopter It can also be seeded and sprayed from an aircraft.
- the amount of the soil erosion inhibitor added is not particularly limited, but it is preferably 1 to 10 kg, preferably 4 to 6 kg, with respect to 1 m 3 of the spray material.
- part and % mean “part by mass” and “% by mass”, respectively.
- aqueous resin emulsion 3 to 5 Polymerization was carried out by the procedure according to Production Example 1 with the composition shown in Table 1 below. As shown in Table 1, aqueous resin emulsion 3 having a toluene insoluble content of 55% by mass, and aqueous resin emulsion 4 having a toluene insoluble content of 44% by mass, respectively. An aqueous resin emulsion 5 having a toluene insoluble content of 31% by mass was obtained.
- PEG400 manufactured by Junsei Chemical
- PEG 20000 manufactured by Junsei Chemical
- hydroxyethyl cellulose 2% aqueous solution viscosity (20 ° C.): 200-300 mPa ⁇ s, manufactured by Tokyo Chemical Industry
- carboxymethylcellulose cellogen 7A (Daiichi Kogyo) Pharmaceutical
- A mass%
- the soil erosion inhibitor containing the aqueous resin emulsion of the present invention improves the freezing and thawing stability without impairing the soil erosion prevention effect, so it is excellent in storage stability even in cold regions in winter and used for construction such as slopes. it can.
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Life Sciences & Earth Sciences (AREA)
- General Life Sciences & Earth Sciences (AREA)
- Polymers & Plastics (AREA)
- Soil Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Materials Engineering (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Soil Conditioners And Soil-Stabilizing Materials (AREA)
- Mining & Mineral Resources (AREA)
- Structural Engineering (AREA)
- Pit Excavations, Shoring, Fill Or Stabilisation Of Slopes (AREA)
- Paleontology (AREA)
- Civil Engineering (AREA)
- General Engineering & Computer Science (AREA)
- Agronomy & Crop Science (AREA)
- Environmental & Geological Engineering (AREA)
Abstract
Description
(1)水性樹脂エマルジョンと水溶性高分子とを含む土壌侵食防止剤であって、水性樹脂エマルジョンのトルエン不溶分が60質量%以上であり、かつ水溶性高分子の土壌侵食防止剤中の含量が1~7質量%である事を特徴とする土壌侵食防止剤。
(2)水溶性高分子の土壌侵食防止剤中の含量が3~5質量%である事を特徴とする、(1)に記載の土壌侵食防止剤。
(3)酢酸ビニルに由来する構造単位を含む水性樹脂エマルジョンを用いる事を特徴とする、(1)又は(2)に記載の土壌侵食防止剤。
(4)水性樹脂エマルジョンは、エチレン-酢酸ビニル共重合体エマルジョンである事を特徴とする、(1)~(3)のいずれかに記載の土壌侵食防止剤。
(5) (1)~(4)のいずれかに記載の土壌侵食防止剤を使用した緑化工法。
(6) (1)~(4)のいずれかに記載の土壌侵食防止剤を吹付資材1m3当たり1~10kg使用した吹付資材。
攪拌機付きの高圧重合缶に、予め100部の純水に乳化剤としてデンカポバールB-05(鹸化度88mol%、平均重合度600、電気化学工業社製)3.6部及びデンカポバールB-17(鹸化度88mol%、平均重合度1700、電気化学工業社製)0.7部、プルロニックL-64(ADEKA製)0.2部、助剤としてホルムアミジンスルフィン酸0.2部、酢酸ソーダ0.2部、硫酸第一鉄七水和物0.005部、エチレンジアミン四酢酸四ナトリウム0.01部を溶解したものを投入後、攪拌下酢酸ビニルモノマー35部及びエチレン23部を充填し内液温度を55℃とした後、10%過硫酸アンモニウム水溶液4.1部を連続添加し重合を行った。重合途中に酢酸ビニルモノマーを60部、エチレンは18部を分添した。重合末期に10%t-ブチルハイドロパーオキサイド水溶液1.0部を添加し、未反応の酢酸ビニルモノマー量が2%未満になるまで重合を継続した。
重合後に残存するエチレンをパージし、生成したエマルジョン中の未反応の酢酸ビニルモノマーを減圧除去した結果、表1に記した通り、未反応の酢酸ビニルモノマーが0.5%以下でトルエン不溶分66%の水性樹脂エマルジョン1を得た。
攪拌機付きの高圧重合缶に、予め100部の純水に乳化剤としてデンカポバールB-05を2.6部及びデンカポバールB-17を2.1部、助剤としてホルムアミジンスルフィン酸0.1部、酢酸ソーダ0.2部、硫酸第一鉄七水和物0.005部、エチレンジアミン四酢酸四ナトリウム0.01部を溶解したものを投入後、攪拌下酢酸ビニルモノマー及びエチレンを充填し内液温度を55℃とした後、5%過硫酸アンモニウム水溶液1.6部を連続添加し重合を行った。酢酸ビニルモノマーは107部、エチレンは20部を使用した。重合末期に10%t-ブチルハイドロパーオキサイド水溶液0.7部を添加し、未反応の酢酸ビニルモノマー量が2%未満になるまで重合を継続した。
重合後に残存するエチレンをパージし、攪拌下新たに酢酸ビニル7部、トリアリルシアヌレート0.05部を投入し内液温度を55℃とした後、10%過硫酸アンモニウム水溶液1.6部を連続添加し、未反応の酢酸ビニルモノマー量が1%未満になるまで重合を継続した。生成したエマルジョン中の未反応の酢酸ビニルモノマーを減圧除去した結果、表1に記した通り、未反応の酢酸ビニルモノマーが0.5%以下でトルエン不溶分62質量%の水性樹脂エマルジョン2を得た。
以下表1記載の組成で製造例1に準じた手順で重合を行い、表1に記した通り、それぞれトルエン不溶分55質量%の水性樹脂エマルジョン3、トルエン不溶分44質量%の水性樹脂エマルジョン4、トルエン不溶分31質量%の水性樹脂エマルジョン5を得た。
製造例1で得た水性樹脂エマルジョン1に対し水溶性高分子としてデンカポバールB-05(鹸化度88mol%、平均重合度600、電気化学工業社製)を最終的に得られる土壌侵食防止剤に対して表2記載の所定の含有量(質量%)となるよう加え、土壌侵食防止剤の固形分率が30%となるよう適宜水を加えて調整し実施例1の土壌侵食防止剤とした。なお表2の各実施例において、水溶性高分子は「*」で表示した行に記載の物を使用した。また、乳化剤と水溶性高分子の合計量の土壌侵食防止剤に対する割合はA(質量%)として示す。
表2及び3記載の組成、固形分率に従い実施例2~14及び比較例1~3の土壌侵食防止剤とした。なお、水溶性高分子はそれぞれデンカポバールB-17(鹸化度88mol%、平均重合度1700、電気化学工業社製)、デンカポバールB-33(鹸化度88mol%、平均重合度3300、電気化学工業社製)、PEG400(純正化学製)、PEG20000(純正化学製)、ヒドロキシエチルセルロース(2%水溶液粘度(20℃):200-300mPa・s東京化成工業製)、カルボキシメチルセルロースセロゲン7A(第一工業製薬製)を用いた。また、乳化剤と水溶性高分子の合計量の土壌侵食防止剤に対する割合はA(質量%)として示す。
(1)水性樹脂エマルジョン10gをフッ素樹脂板に塗布し(100cm2程度の面積とする)、23℃で5日間乾燥させ乾燥皮膜を得る。
(2)5mm角に細かく切り分けた乾燥皮膜を、スクリュー管に1g(仕込みフィルム重量)に入れ、トルエン50gで満たし密栓する。
(3)50℃の湯浴中で5時間振とうする。
(4)200メッシュ金網で濾過し、回収した不溶分をドラフト内で23℃、1晩乾燥後、乾燥機(105℃)にて3時間乾燥させ、不溶分の乾燥重量を測定する。
(5)次式からトルエン不溶分を求める。トルエン不溶分(%) = 回収不溶分乾燥重量 ÷ 仕込みフィルム重量 × 100
(1)土壌侵食防止剤を100ml容器に50g計り取る。
(2)環境試験機中(-20℃)で16時間静置し、凍結させる。
(3)環境試験機から取り出し、30℃の湯浴中で1時間静置し、融解させる。
(4)融解後の状態を目視で観察し、凝集の程度を下記基準で判定する。
○: 凍結前の土壌侵食防止剤と同等
△: 流動し液状になるが凝集物が見られる
×: スポンジ状になり流動しない
次に、以下の方法により、作製した土壌侵食防止剤を配合した厚層基材吹付工の植生基盤を作製し、降水試験により流出してくる土壌の量を測定した。
(1)混合: 容器にバーク堆肥(富士見環境緑化社製フジミソイル5号)を7L、高度化成肥料(日東エフシー社製、15-15-15)を21g、種子(カネコ種苗社製イタリアンライグラス)を3.5g、各種土壌侵食防止剤を21g加え混練し、植生基盤材とした。
(2)施工: 植生基盤材を木枠(30cm×30cmの矩形、高さ10cm)に充填し平らに均したのちに上から体積半分まで圧縮した。
(3)養生: 木枠を外し、23℃室内で1晩養生した。
(4)降水: 養生した植生基盤に対し、ジョウロで降水した。植生基盤に9°の傾斜を与え、降水は50cmの高さから1時間に200mmの強さで30分間実施し、流出した土壌量を目視により観察し以下のように判定した。
○: ほとんど流出が認められない。
△: 一部流出が認められる。
×: 全体的に流出が認められる。
Claims (6)
- 水性樹脂エマルジョンと水溶性高分子とを含む土壌侵食防止剤であって、水性樹脂エマルジョンのトルエン不溶分が60質量%以上であり、かつ水溶性高分子の土壌侵食防止剤中の含量が1~7質量%である事を特徴とする土壌侵食防止剤。
- 水溶性高分子の土壌侵食防止剤中の含量が3~5質量%である事を特徴とする、請求項1に記載の土壌侵食防止剤。
- 酢酸ビニルに由来する構造単位を含む水性樹脂エマルジョンを用いる事を特徴とする、請求項1又は2に記載の土壌侵食防止剤。
- 前記水性樹脂エマルジョンは、エチレン-酢酸ビニル共重合体エマルジョンである事を特徴とする、請求項1~3のいずれかに記載の土壌侵食防止剤。
- 請求項1~4のいずれかに記載の土壌侵食防止剤を使用した緑化工法。
- 請求項1~4のいずれかに記載の土壌侵食防止剤を吹付資材1m3当たり1~10kg使用した吹付資材。
Priority Applications (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US15/576,122 US10519372B2 (en) | 2015-06-18 | 2016-06-17 | Soil erosion prevention agent excellent in freeze-thaw stability |
| CN201680035736.XA CN107709671B (zh) | 2015-06-18 | 2016-06-17 | 冻结溶解稳定性优异的土壤侵蚀防止剂 |
| JP2017524874A JP6691116B2 (ja) | 2015-06-18 | 2016-06-17 | 凍結融解安定性に優れる土壌侵食防止剤 |
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2015122706 | 2015-06-18 | ||
| JP2015-122706 | 2015-06-18 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| WO2016204290A1 true WO2016204290A1 (ja) | 2016-12-22 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| PCT/JP2016/068174 Ceased WO2016204290A1 (ja) | 2015-06-18 | 2016-06-17 | 凍結融解安定性に優れる土壌侵食防止剤 |
Country Status (5)
| Country | Link |
|---|---|
| US (1) | US10519372B2 (ja) |
| JP (1) | JP6691116B2 (ja) |
| CN (1) | CN107709671B (ja) |
| TW (1) | TWI727956B (ja) |
| WO (1) | WO2016204290A1 (ja) |
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|---|---|---|---|---|
| JP2020114890A (ja) * | 2019-01-17 | 2020-07-30 | デンカ株式会社 | 土壌流出防止材及び土壌流出防止方法 |
| WO2022018919A1 (ja) * | 2020-07-20 | 2022-01-27 | デンカ株式会社 | エマルジョン組成物および土壌流出防止材 |
| CN114340373A (zh) * | 2019-10-18 | 2022-04-12 | 电化株式会社 | 树脂乳液的散布方法 |
| WO2022079960A1 (ja) * | 2020-10-16 | 2022-04-21 | デンカ株式会社 | 樹脂エマルジョン散布液、樹脂エマルジョン散布液の評価方法 |
| WO2022244456A1 (ja) * | 2021-05-20 | 2022-11-24 | デンカ株式会社 | エチレン-酢酸ビニル系共重合体エマルジョン、その製造方法、及び土壌侵食防止剤 |
| WO2022270078A1 (ja) * | 2021-06-24 | 2022-12-29 | デンカ株式会社 | エマルジョン組成物及び土壌侵食防止剤 |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN110230290B (zh) * | 2019-06-18 | 2021-06-04 | 江苏健达交通工程有限公司 | 一种将污水沟淤泥改造形成排水渠的方法 |
| CN116606655A (zh) * | 2023-04-26 | 2023-08-18 | 成都理工大学 | 一种冻融驱动力增强型固土材料及其在冻融荒漠化治理中的应用 |
| CN118273305A (zh) * | 2024-03-21 | 2024-07-02 | 中国科学院西北生态环境资源研究院 | 一种冻土区降低土壤冻融作用的设备及整治方法 |
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| JP2020114890A (ja) * | 2019-01-17 | 2020-07-30 | デンカ株式会社 | 土壌流出防止材及び土壌流出防止方法 |
| JP7236277B2 (ja) | 2019-01-17 | 2023-03-09 | デンカ株式会社 | 土壌流出防止材及び土壌流出防止方法 |
| CN114340373A (zh) * | 2019-10-18 | 2022-04-12 | 电化株式会社 | 树脂乳液的散布方法 |
| WO2022018919A1 (ja) * | 2020-07-20 | 2022-01-27 | デンカ株式会社 | エマルジョン組成物および土壌流出防止材 |
| WO2022079960A1 (ja) * | 2020-10-16 | 2022-04-21 | デンカ株式会社 | 樹脂エマルジョン散布液、樹脂エマルジョン散布液の評価方法 |
| WO2022244456A1 (ja) * | 2021-05-20 | 2022-11-24 | デンカ株式会社 | エチレン-酢酸ビニル系共重合体エマルジョン、その製造方法、及び土壌侵食防止剤 |
| WO2022270078A1 (ja) * | 2021-06-24 | 2022-12-29 | デンカ株式会社 | エマルジョン組成物及び土壌侵食防止剤 |
Also Published As
| Publication number | Publication date |
|---|---|
| US10519372B2 (en) | 2019-12-31 |
| US20180148646A1 (en) | 2018-05-31 |
| TW201710471A (zh) | 2017-03-16 |
| TWI727956B (zh) | 2021-05-21 |
| JPWO2016204290A1 (ja) | 2018-04-12 |
| CN107709671B (zh) | 2020-10-27 |
| CN107709671A (zh) | 2018-02-16 |
| JP6691116B2 (ja) | 2020-04-28 |
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