WO2022270078A1 - Emulsion composition and soil erosion inhibitor - Google Patents

Emulsion composition and soil erosion inhibitor Download PDF

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Publication number
WO2022270078A1
WO2022270078A1 PCT/JP2022/013546 JP2022013546W WO2022270078A1 WO 2022270078 A1 WO2022270078 A1 WO 2022270078A1 JP 2022013546 W JP2022013546 W JP 2022013546W WO 2022270078 A1 WO2022270078 A1 WO 2022270078A1
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water
emulsion composition
temperature
emulsion
mass
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PCT/JP2022/013546
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French (fr)
Japanese (ja)
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純平 高橋
広平 西野
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デンカ株式会社
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J13/00—Colloid chemistry, e.g. the production of colloidal materials or their solutions, not otherwise provided for; Making microcapsules or microballoons
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L101/00—Compositions of unspecified macromolecular compounds
    • C08L101/12—Compositions of unspecified macromolecular compounds characterised by physical features, e.g. anisotropy, viscosity or electrical conductivity
    • C08L101/14—Compositions of unspecified macromolecular compounds characterised by physical features, e.g. anisotropy, viscosity or electrical conductivity the macromolecular compounds being water soluble or water swellable, e.g. aqueous gels
    • 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
    • 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

Definitions

  • the present invention relates to emulsion compositions and soil erosion inhibitors.
  • Patent Document 1 soil erosion is prevented by spraying a spraying material containing an emulsion composition at a rate of 0.5 to 1.5 kg per 1 m 3 of spraying material against the slope.
  • Materials used for slope construction are sometimes stored in warehouses, but sometimes they are brought to the site and stored covered with sheets. In winter in cold regions, the temperature may drop below the freezing point depending on the storage location, causing problems such as freezing and agglomeration of the emulsion composition used as a soil erosion inhibitor. In particular, aggregation of emulsion compositions is a problem when freeze-thaw cycles are repeated.
  • the present invention has been made in view of such problems, and provides an emulsion composition and a soil erosion inhibitor that do not aggregate even when freezing and thawing are repeated.
  • the temperature cycle in which the temperature change in each row is performed from top to bottom in the table below is regarded as one cycle, and after repeating the temperature cycle for 10 cycles, the rough when filtered through a 200 mesh wire mesh
  • An emulsion composition is provided having a particle fraction of 500 ppm or less, wherein the temperature change in each row is performed by changing or maintaining from a start temperature to an end temperature during the holding time.
  • An emulsion composition containing a water-soluble resin emulsion, a water-soluble polymer and a surfactant is preferred.
  • the emulsion composition contains the water-soluble polymer and the surfactant in a mass ratio of 7:1 to 1:7.
  • a water-soluble resin emulsion comprising a water-soluble polymer and a surfactant
  • An emulsion composition is provided, wherein the weight ratio of the content of the water-soluble polymer and the content of the surfactant is 7:1 to 1:7.
  • the emulsion composition contains 1 to 6% by mass of the water-soluble polymer and the surfactant in total.
  • the water-soluble resin emulsion is an emulsion composition that is a resin emulsion containing structural units derived from vinyl acetate.
  • the emulsion composition is such that the water-soluble resin emulsion is an ethylene-vinyl acetate copolymer emulsion.
  • a soil erosion inhibitor containing the above emulsion composition is provided.
  • 1 is a graph showing temperature cycles for verifying freeze-thaw stability of an emulsion composition.
  • Emulsion composition The emulsion composition according to one aspect of the present invention is composed of a temperature cycle in which the temperature in each row is changed from top to bottom in Table 1 below as one cycle, and after repeating the temperature cycle for 10 cycles,
  • the emulsion composition has a coarse particle rate of 500 ppm or less when filtered through a 200-mesh wire mesh.
  • the temperature change in each row is done by changing or maintaining from the start temperature to the end temperature during the hold time.
  • the temperature cycle in Table 1 can be represented as the graph in Figure 1.
  • Such a temperature change can be performed by a test device or the like that can change the temperature, such as an environmental tester.
  • the coarse particle ratio is the ratio (ppm) of the mass of the filtration residue obtained when the emulsion composition is filtered using a wire mesh with an opening of 200 mesh to the mass of the emulsion composition.
  • the emulsion composition according to one aspect of the present invention contains a water-soluble resin emulsion, a water-soluble polymer and a surfactant.
  • the weight ratio of the water-soluble polymer content to the surfactant content in the emulsion composition is preferably 7:1 to 1:7, more preferably 5:1 to 1:7, It is more preferably 1:1 to 1:7.
  • the content of the surfactant is too high, the strength of the film may be low, and the effect of preventing soil erosion may not be obtained. If the surfactant content is too low, the freeze-thaw stability may decrease. On the other hand, if the content of the water-soluble polymer is too high, the viscosity may increase and the handleability may deteriorate. Moreover, when the content of the water-soluble polymer is too small, the freeze-thaw stability may be lowered.
  • the emulsion composition preferably contains 1 to 6% by mass, more preferably 2 to 4% by mass, of the water-soluble polymer and surfactant in total. By setting it as such a range, it can be set as the viscosity suitable for handling property, and a soil erosion prevention effect is acquired. It also has excellent freeze-thaw stability. If the total content of these is too high, not only will the cost increase, but the viscosity will also become too high, and the soil erosion prevention effect will also decrease. Also, if the total content of these is too small, the freeze-thaw stability may decrease. Specifically, the total content of the water-soluble polymer and the surfactant is, for example, 1.0, 1.5, 2.0, 2.5, 3.0, 3.5, 4.0, 4.0. 5, 5.0, 5.5, 6.0% by mass, and may be within a range between any two of the numerical values exemplified here.
  • the water-soluble resin emulsion has water as a dispersion medium and a resin as a dispersoid.
  • a water-soluble resin emulsion prepared by polymerizing one or more of various olefinic compounds such as vinyl acetate, acrylic acid ester, styrene, ethylene and butadiene as main monomers can be used.
  • vinyl acetate resin emulsion vinyl acetate copolymer emulsion, acrylic acid ester resin emulsion, styrene acrylic acid ester copolymer emulsion, ethylene-vinyl acetate copolymer emulsion, styrene-butadiene copolymer emulsion, vinylidene.
  • Examples include resin emulsions, polybutene resin emulsions, acrylonitrile-butadiene resin emulsions, methacrylate-butadiene resin emulsions, asphalt emulsions, epoxy resin emulsions, urethane resin emulsions, silicone resin emulsions, among which structural units derived from vinyl acetate.
  • Emulsions containing resins (vinyl acetate resin emulsions, vinyl acetate copolymer emulsions, ethylene-vinyl acetate copolymer emulsions, etc.) are preferable, and ethylene-vinyl acetate copolymer emulsions are more preferable.
  • the method for producing the water-soluble resin emulsion is not particularly limited, but for example, it can be produced by adding an emulsifier and a monomer to a dispersion medium containing water as a main component, and emulsifying the monomer while stirring.
  • emulsifiers include polymeric additives such as hydroxyethyl cellulose, methyl cellulose and polyvinyl alcohol.
  • the polymer additive is particularly preferably made of polyvinyl alcohol, and its average degree of polymerization is, for example, 200 to 2,500, preferably 400 to 2,200, more preferably 500 to 2,000.
  • polyvinyl alcohol having an appropriate average degree of polymerization may be used so as to obtain an emulsion with a desired degree of dispersion.
  • Polyvinyl alcohols having different average degrees of polymerization may be used in combination.
  • the degree of saponification of polyvinyl alcohol is not particularly limited, it is, for example, 70% or more, preferably 80 to 95%. This is because if the degree of saponification is too low, the solubility in water is extremely reduced, and it cannot be dissolved unless a special dissolution method is used, making it difficult to use industrially.
  • polyvinyl alcohol having an appropriate degree of saponification may be used so as to obtain an emulsion with a desired degree of dispersion.
  • Different emulsifiers may be used in combination.
  • Polymer additives such as polyethylene glycol and polyvinyl alcohol used as emulsifiers in the production of water-soluble resin emulsions can be regarded as water-soluble polymers contained in the emulsion composition.
  • the water-soluble polymer preferably has a surface tension of 40 mN/m to 75 mN/m as measured by the Wilhelmy method under conditions of an aqueous solution concentration of 0.1 wt % and an aqueous solution temperature of 25° C.
  • the emulsion composition preferably comprises a cellulose derivative and a polymeric alcohol.
  • the content of the water-soluble polymer in the emulsion composition is preferably 0.01-3.0% by mass, more preferably 0.1-2.5% by mass. By setting it to such a range, it is excellent in handleability by moderate viscosity, and also excellent in freeze-thaw stability.
  • the content of polymer alcohol such as polyethylene glycol and polyvinyl alcohol in the emulsion composition is preferably 0.01 to 1.0% by mass, more preferably 0.1 to 0.5% by mass. .
  • the method of adding the water-soluble polymer is not particularly limited, but it may be added as an emulsifier during the production of the water-soluble resin emulsion, or it may be added separately after the production of the water-soluble resin emulsion.
  • the surfactant preferably has a surface tension of 25 mN/m to 45 mN/m as measured by the Wilhelmy method under conditions of an aqueous solution concentration of 0.1 wt% and an aqueous solution temperature of 25°C.
  • - Zwitterionic) surfactants and nonionic (nonionic) surfactants can be mentioned.
  • Examples of cationic surfactants include quaternary ammonium salts and amine salts.
  • anionic surfactants include lauryl sulfate, alkylbenzenesulfonate, alkylphenyl ether sulfate, methyl taurate, sulfosuccinate, ethersulfonate, phosphate, and alkyl ether sulfate. etc.
  • Alkyl carboxy betaine etc. are mentioned as a zwitterionic surfactant.
  • nonionic surfactants include polyoxyethylene alkylaryl ethers such as polyoxyethylene nonylphenyl ether, polyoxyethylene styrenated phenyl ether, polyoxyethylene oleyl ether, and polyoxyethylene lauryl ether, or polyoxyethylene Alkyl ethers, polyoxyalkylene alkyl ethers, polyoxyethylene fatty acid esters such as polyethylene glycol monolaurate, polyethylene glycol monostearate, polyethylene glycol monooleate, polyoxyethylene/polyoxypropylene block copolymers, and the like. .
  • the surfactant preferably has a structure containing a benzene ring.
  • polyoxyethylene styrenated phenyl ether or polyoxyalkylene alkyl ether is preferred. These can be used alone or in any combination.
  • the content of the surfactant in the emulsion composition is preferably 0.1-5.0% by mass, more preferably 0.5-3.5% by mass. By setting it to such a range, the strength when formed into a film is excellent, the effect as a soil erosion inhibitor is high, and the freeze-thaw stability is also excellent.
  • the method of adding the surfactant is not particularly limited, but it may be added during the production of the water-soluble resin emulsion, or may be added separately after the production of the water-soluble resin emulsion. Preferably, it is added separately after the production of the water-soluble resin emulsion.
  • a soil erosion inhibitor according to one embodiment of the present invention is a soil erosion inhibitor comprising an emulsion composition. If necessary, plasticizers, tackifying resins, thickeners, antifoaming agents, pH adjusters, humic acid, amino acids, herbicides, agricultural chemicals, etc. can be blended.
  • the method of spraying the soil erosion inhibitor on the soil There are no particular restrictions on the method of spraying the soil erosion inhibitor on the soil.
  • a boom sprayer or the like can be used.
  • the sprayed soil erosion inhibitor plays a role in forming a consolidated layer consisting of the granular material of the granular sediment and the soil erosion inhibitor in the granular sediment, and rainwater flowing into the consolidated layer and reduce the amount of water flowing into the powdery and granular sediment existing under the consolidated layer, it is effective in preventing the powdery and granular sediment from collapsing and flowing out.
  • Forming a solidified layer can also be effective in preventing the generation of dust.
  • the soil erosion inhibitor may be sprayed alone on the surface to be protected, and should be protected together with the spraying material, which is mainly composed of soil and mixed with seeds, bark compost, or fertilizer. You can also spray it on the surface.
  • the spraying material which is mainly composed of soil and mixed with seeds, bark compost, or fertilizer. You can also spray it on the surface.
  • the method of spraying the spraying material onto the target surface and examples include seed spraying, soil spraying, and substrate spraying. It can also be seeded and sprayed from an aircraft.
  • EVA1 water-soluble resin emulsion 1
  • Table 2 ⁇ Adjustment of water-soluble resin emulsion 1 (EVA1)> EVA1 was adjusted based on the conditions in Table 2.
  • Denka Poval B-05 saponification degree 88 mol%, average polymerization degree 600, manufactured by Denka Co., Ltd.
  • Denka Poval B-17 aponification degree 88 mol%, average polymerization degree 600, manufactured by Denka Co., Ltd.
  • a 10% by mass ammonium persulfate aqueous solution was added to initiate polymerization. Then, 57 parts by mass of vinyl acetate monomer and 17 parts by mass of ethylene monomer were added as partial addition monomers, and 2.7 parts by mass of 10% by mass aqueous ammonium persulfate solution (total with initial addition amount) and 10 parts by mass as partial addition additives. % t-butyl hydroperoxide aqueous solution was continuously added to carry out polymerization. Polymerization was continued until the amount of unreacted vinyl acetate monomer was less than 2%.
  • EVA1 Ethylene remaining after the polymerization was purged, and unreacted vinyl acetate monomer in the resulting emulsion was removed under reduced pressure to obtain EVA1.
  • the water-soluble polymer (polyvinyl alcohol: PVA) in EVA1 was 1.7% by mass, and the surfactant was 0.08% by mass.
  • EVA2 water-soluble resin emulsion 2
  • Table 2 ⁇ Adjustment of water-soluble resin emulsion 2 (EVA2)> EVA2 was adjusted based on the conditions in Table 2.
  • 4.1 parts by mass of Denka Poval B-05 (saponification degree 88 mol%, average polymerization degree 600, manufactured by Denka Co., Ltd.) as an emulsifier and Denka Poval B-17 are added to 100 parts by mass of pure water in advance.
  • a 10% by mass ammonium persulfate aqueous solution was added to initiate polymerization. 26 parts by mass of a vinyl acetate monomer as a partially added monomer, 2.0 parts by mass of a 5% by mass ammonium persulfate aqueous solution as a partially added additive (total with the initial amount added), and a 10% by mass aqueous t-butyl hydroperoxide solution. Polymerization was carried out by continuously adding 0.6 parts by mass. Polymerization was continued until the amount of unreacted vinyl acetate monomer was less than 2%. Ethylene remaining after the polymerization was purged, and unreacted vinyl acetate monomer in the resulting emulsion was removed under reduced pressure to obtain EVA2.
  • the water-soluble polymer (polyvinyl alcohol: PVA) in EVA2 was 2.4% by mass, and the surfactant was 0% by mass.
  • Example 1 A water-soluble resin emulsion (EVA1 or EVA2), water, a surfactant, and a necessary water-soluble polymer were mixed based on the respective mixing ratios in Table 3 to prepare an emulsion composition.
  • Table 3 also shows the total content of each of the water-soluble polymer and surfactant contained in the emulsion composition.
  • each compound in Table 3 is as follows.
  • HEC200 Hydroxyethyl cellulose (2% aqueous solution viscosity (20 ° C.): 200 to 300 mPa s, manufactured by Tokyo Chemical Industry Co., Ltd.)
  • Cellogen WS-C Carboxymethylcellulose (1% aqueous solution viscosity (25°C): 150 to 250 mPa s, manufactured by Daiichi Kogyo Seiyaku Co., Ltd.)
  • Neugen EA-137 Polyoxyethylene styrenated phenyl ether (HLB value: 13.0, manufactured by Daiichi Kogyo Seiyaku Co., Ltd.)
  • Neugen EA-87 Polyoxyethylene styrenated phenyl ether (HLB value: 10.6, manufactured by Daiichi Kogyo Seiyaku Co., Ltd.)
  • Emulgen 1150S-60 Polyoxyethylene alkyl ether (HLB value: 18.5, manufactured by Kao Corporation) Neugen
  • Table 4 shows the surface tensions of the water-soluble polymers and surfactants used.
  • the surface tension was measured under the following conditions (measuring device: automatic surface tension meter DY-300 manufactured by Kyowa Interface Science Co., Ltd.). Measurement temperature: 25°C Aqueous solution concentration: 0.1 wt% Measurement method: Wilhelmy method (platinum plate)
  • Viscosity was measured for the emulsion composition before undergoing the temperature change of the temperature cycle of Table 1. The viscosity was measured at a temperature of 30° C. and a rotation speed of 30 rpm (measurement device: TV-33 viscometer manufactured by Toki Sangyo Co., Ltd.).
  • ⁇ Coarse grain ratio> The emulsion composition before undergoing the temperature change of the temperature cycle in Table 1, and the temperature cycle in which the temperature changes in each row in Table 1 are performed in order from top to bottom as one cycle, and after repeating the temperature cycle for 10 cycles of the emulsion composition was measured.
  • the temperature change in the temperature cycle in Table 1 was controlled by an environmental tester (PR-3K manufactured by Espec Co., Ltd.).

Abstract

Provided is an emulsion composition and a soil erosion inhibitor in which aggregation does not occur even after repeated freezing and thawing.　The present invention provides an emulsion composition configured such that, when a change in temperature of each row in table 1, the change being initiated from high to low, is taken as a temperature cycle, after 10 repetition of this temperature cycle, the fineness modulus obtained when the emulsion composition filtered using a 200 mesh wire screen is 500 ppm or less. The temperature change in each row results from changing the temperature from the start temperature to the end temperature or maintaining a temperature during the retention time.

Description

エマルジョン組成物及び土壌侵食防止剤Emulsion composition and soil erosion inhibitor
　本発明は、エマルジョン組成物及び土壌侵食防止剤に関する。 The present invention relates to emulsion compositions and soil erosion inhibitors.
　造成地、道路、ダムなどの建設では盛土や切土が行われ、それによって形成される法面は、そのまま放置すると降雨や風化などによって侵食され、地滑りや落石などの事故が発生する。そのために、特許文献１では、エマルジョン組成物を吹付資材１ｍ３当り０．５～１．５ｋｇの割合で配合した吹付資材を法面に対して吹き付けることによって、土壌の侵食を防止している。 In the construction of reclaimed land, roads, dams, etc., embankment and cutting are performed, and if the slopes formed by this are left as they are, they will be eroded by rainfall and weathering, and accidents such as landslides and rockfalls will occur. Therefore, in Patent Document 1, soil erosion is prevented by spraying a spraying material containing an emulsion composition at a rate of 0.5 to 1.5 kg per 1 m 3 of spraying material against the slope.
特許第４０４８８００号公報Japanese Patent No. 4048800
　法面工事に使用される資材は倉庫等に保管されることもあるが、現場に運び込みシート等をかぶせて保管されることもある。寒冷地の冬場には、保管場所によっては氷点を下回ることがあり、土壌侵食防止剤として用いるエマルジョン組成物が凍結し凝集するなどの問題がある。特に、凍結融解が繰り返されたときに、エマルジョン組成物が凝集することが問題となっている。 Materials used for slope construction are sometimes stored in warehouses, but sometimes they are brought to the site and stored covered with sheets. In winter in cold regions, the temperature may drop below the freezing point depending on the storage location, causing problems such as freezing and agglomeration of the emulsion composition used as a soil erosion inhibitor. In particular, aggregation of emulsion compositions is a problem when freeze-thaw cycles are repeated.
　本発明はこのような問題に鑑みてなされたものであり、凍結融解を繰り返したときでも、凝集が発生しないエマルジョン組成物及び土壌侵食防止剤を提供するものである。 The present invention has been made in view of such problems, and provides an emulsion composition and a soil erosion inhibitor that do not aggregate even when freezing and thawing are repeated.
　本発明によれば、下表において各行の温度変更を上から下への順に行っていく温度サイクルを１サイクルとして、前記温度サイクルを１０サイクル繰り返した後に、２００メッシュの金網でろ過したときの粗粒率が５００ｐｐｍ以下であり、前記各行の温度変更は、保持時間中に開始温度から終了温度まで変更又は維持することにより行われるエマルジョン組成物が提供される。
Figure JPOXMLDOC01-appb-I000002
According to the present invention, the temperature cycle in which the temperature change in each row is performed from top to bottom in the table below is regarded as one cycle, and after repeating the temperature cycle for 10 cycles, the rough when filtered through a 200 mesh wire mesh An emulsion composition is provided having a particle fraction of 500 ppm or less, wherein the temperature change in each row is performed by changing or maintaining from a start temperature to an end temperature during the holding time.
Figure JPOXMLDOC01-appb-I000002
　以下、本発明の種々の実施形態を例示する。以下に示す実施形態は互いに組み合わせ可能である。
　好ましくは、水溶性樹脂エマルジョン、水溶性高分子および界面活性剤を含む、エマルジョン組成物である。
　好ましくは、前記水溶性高分子と前記界面活性剤との含有量の質量比が７：１～１：７である、エマルジョン組成物である。 Various embodiments of the present invention are illustrated below. The embodiments shown below can be combined with each other.
An emulsion composition containing a water-soluble resin emulsion, a water-soluble polymer and a surfactant is preferred.
Preferably, the emulsion composition contains the water-soluble polymer and the surfactant in a mass ratio of 7:1 to 1:7.
　本発明の別の観点によれば、水溶性樹脂エマルジョン、水溶性高分子および界面活性剤を含み、
前記水溶性高分子の含有量と前記界面活性剤との含有量の質量比が７：１～１：７である、エマルジョン組成物が提供される。 According to another aspect of the present invention, comprising a water-soluble resin emulsion, a water-soluble polymer and a surfactant,
An emulsion composition is provided, wherein the weight ratio of the content of the water-soluble polymer and the content of the surfactant is 7:1 to 1:7.
　好ましくは、前記水溶性高分子と前記界面活性剤とを合計で１～６質量％含む、エマルジョン組成物である。
　好ましくは、前記水溶性樹脂エマルジョンが、酢酸ビニルに由来する構造単位を含む樹脂のエマルジョンである、エマルジョン組成物である。
　好ましくは、前記水溶性樹脂エマルジョンが、エチレン－酢酸ビニル共重合体エマルジョンである、エマルジョン組成物である。 Preferably, the emulsion composition contains 1 to 6% by mass of the water-soluble polymer and the surfactant in total.
Preferably, the water-soluble resin emulsion is an emulsion composition that is a resin emulsion containing structural units derived from vinyl acetate.
Preferably, the emulsion composition is such that the water-soluble resin emulsion is an ethylene-vinyl acetate copolymer emulsion.
　本発明の別の観点によれば、上記エマルジョン組成物を含む土壌侵食防止剤が提供される。 According to another aspect of the present invention, a soil erosion inhibitor containing the above emulsion composition is provided.
エマルジョン組成物の凍結融解に対する安定性を検証するための温度サイクルを表すグラフである。1 is a graph showing temperature cycles for verifying freeze-thaw stability of an emulsion composition.
　以下、本発明の実施形態について説明する。以下に示す実施形態中で示した各種特徴事項は、互いに組み合わせ可能である。また、各特徴事項について独立して発明が成立する。 Embodiments of the present invention will be described below. Various features shown in the embodiments shown below can be combined with each other. In addition, the invention is established independently for each characteristic item.
１．エマルジョン組成物
　本発明の一態様に係るエマルジョン組成物は、下表１において各行の温度変更を上から下への順に行っていく温度サイクルを１サイクルとして、当該温度サイクルを１０サイクル繰り返した後に、２００メッシュの金網でろ過したときの粗粒率が５００ｐｐｍ以下であるエマルジョン組成物である。各行の温度変更は、保持時間中に開始温度から終了温度まで変更又は維持することにより行われる。 1. Emulsion composition The emulsion composition according to one aspect of the present invention is composed of a temperature cycle in which the temperature in each row is changed from top to bottom in Table 1 below as one cycle, and after repeating the temperature cycle for 10 cycles, The emulsion composition has a coarse particle rate of 500 ppm or less when filtered through a 200-mesh wire mesh. The temperature change in each row is done by changing or maintaining from the start temperature to the end temperature during the hold time.
Figure JPOXMLDOC01-appb-T000003
Figure JPOXMLDOC01-appb-T000003
　表１の温度サイクルは、図１のグラフのように表すことができる。このような温度変化は、環境試験機などの温度を変化させることのできる試験装置等によって行われうる。 The temperature cycle in Table 1 can be represented as the graph in Figure 1. Such a temperature change can be performed by a test device or the like that can change the temperature, such as an environmental tester.
　また、粗粒率は、エマルジョン組成物を目開きが２００メッシュの金網を用いてろ過した際に得られるろ過残渣の質量のエマルジョン組成物の質量に対する割合（ｐｐｍ）である。 In addition, the coarse particle ratio is the ratio (ppm) of the mass of the filtration residue obtained when the emulsion composition is filtered using a wire mesh with an opening of 200 mesh to the mass of the emulsion composition.
　本発明の一態様に係るエマルジョン組成物は、水溶性樹脂エマルジョン、水溶性高分子および界面活性剤を含む。エマルジョン組成物中の水溶性高分子の含有量と界面活性剤との含有量の質量比は、好ましくは７：１～１：７であり、より好ましくは５：１～１：７であり、さらに好ましくは１：１～１：７である。このような範囲とすることにより、フィルムとしたときの強度に優れ土壌侵食防止剤としての効果が高く、また適度な粘度によるハンドリング性に優れ、さらに凍結融解安定性にも優れる。また、界面活性剤の含有量が多すぎるとフィルムとしたときの強度が低く、土壌侵食防止効果を得られない場合がある。界面活性剤の含有量が少なすぎると、凍結融解安定性が低下する場合がある。また、水溶性高分子の含有量が多すぎると、粘度が高くなり、ハンドリング性が低下する場合がある。また、水溶性高分子の含有量が少なすぎると、凍結融解安定性が低下する場合がある。 The emulsion composition according to one aspect of the present invention contains a water-soluble resin emulsion, a water-soluble polymer and a surfactant. The weight ratio of the water-soluble polymer content to the surfactant content in the emulsion composition is preferably 7:1 to 1:7, more preferably 5:1 to 1:7, It is more preferably 1:1 to 1:7. By setting it to such a range, it is excellent in strength when formed into a film and highly effective as a soil erosion inhibitor, and is excellent in handleability due to its moderate viscosity, and is also excellent in freeze-thaw stability. On the other hand, if the content of the surfactant is too high, the strength of the film may be low, and the effect of preventing soil erosion may not be obtained. If the surfactant content is too low, the freeze-thaw stability may decrease. On the other hand, if the content of the water-soluble polymer is too high, the viscosity may increase and the handleability may deteriorate. Moreover, when the content of the water-soluble polymer is too small, the freeze-thaw stability may be lowered.
　エマルジョン組成物は、水溶性高分子と界面活性剤とを合計で、好ましくは１～６質量％含み、より好ましくは２～４質量％含む。このような範囲とすることにより、ハンドリング性に適した粘度とすることができ、土壌侵食防止効果が得られる。また、凍結融解安定性にも優れる。これらの合計含有量が多すぎると、コストが高くなるばかりでなく、粘度が高くなりすぎ、また土壌侵食防止効果も低下することがある。また、これらの合計含有量が少なすぎると、凍結融解安定性が低下することがある。水溶性高分子と界面活性剤の合計含有量は、具体的には例えば、１．０，１．５，２．０，２．５，３．０，３．５，４．０，４．５，５．０，５．５，６．０質量％であり、ここで例示した数値の何れか２つの間の範囲内であってもよい。 The emulsion composition preferably contains 1 to 6% by mass, more preferably 2 to 4% by mass, of the water-soluble polymer and surfactant in total. By setting it as such a range, it can be set as the viscosity suitable for handling property, and a soil erosion prevention effect is acquired. It also has excellent freeze-thaw stability. If the total content of these is too high, not only will the cost increase, but the viscosity will also become too high, and the soil erosion prevention effect will also decrease. Also, if the total content of these is too small, the freeze-thaw stability may decrease. Specifically, the total content of the water-soluble polymer and the surfactant is, for example, 1.0, 1.5, 2.0, 2.5, 3.0, 3.5, 4.0, 4.0. 5, 5.0, 5.5, 6.0% by mass, and may be within a range between any two of the numerical values exemplified here.
＜水溶性樹脂エマルジョン＞
　水溶性樹脂エマルジョンは、水を分散媒、樹脂を分散質としたものである。水溶性樹脂エマルジョンは、例えば、主モノマーとして、酢酸ビニル、アクリル酸エステル、スチレン、エチレン、ブタジエン等の、種々のオレフィン系化合物を単独または複数用いて重合し調製した水溶性樹脂エマルジョンが使用できる。具体的には、酢酸ビニル樹脂エマルジョン、酢酸ビニル共重合体エマルジョン、アクリル酸エステル樹脂エマルジョン、スチレンアクリル酸エステル共重合体エマルジョン、エチレン－酢酸ビニル共重合体エマルジョン、スチレン－ブタジエン共重合体エマルジョン、ビニリデン樹脂エマルジョン、ポリブテン樹脂エマルジョン、アクリルニトリル－ブタジエン樹脂エマルジョン、メタアクリレート－ブタジエン樹脂エマルジョン、アスファルトエマルジョン、エポキシ樹脂エマルジョン、ウレタン樹脂エマルジョン、シリコン樹脂エマルジョンなどが例示され、このうち、酢酸ビニルに由来する構造単位を含む樹脂のエマルジョン（酢酸ビニル樹脂エマルジョン、酢酸ビニル共重合体エマルジョン、エチレン－酢酸ビニル共重合体エマルジョン等）が好ましく、エチレン－酢酸ビニル共重合体エマルジョンがさらに好ましい。 <Water-soluble resin emulsion>
The water-soluble resin emulsion has water as a dispersion medium and a resin as a dispersoid. As the water-soluble resin emulsion, for example, a water-soluble resin emulsion prepared by polymerizing one or more of various olefinic compounds such as vinyl acetate, acrylic acid ester, styrene, ethylene and butadiene as main monomers can be used. Specifically, vinyl acetate resin emulsion, vinyl acetate copolymer emulsion, acrylic acid ester resin emulsion, styrene acrylic acid ester copolymer emulsion, ethylene-vinyl acetate copolymer emulsion, styrene-butadiene copolymer emulsion, vinylidene. Examples include resin emulsions, polybutene resin emulsions, acrylonitrile-butadiene resin emulsions, methacrylate-butadiene resin emulsions, asphalt emulsions, epoxy resin emulsions, urethane resin emulsions, silicone resin emulsions, among which structural units derived from vinyl acetate. Emulsions containing resins (vinyl acetate resin emulsions, vinyl acetate copolymer emulsions, ethylene-vinyl acetate copolymer emulsions, etc.) are preferable, and ethylene-vinyl acetate copolymer emulsions are more preferable.
　水溶性樹脂エマルジョンの製造方法は、特に限定されないが、例えば、水を主成分とする分散媒中に乳化剤とモノマーを添加し、撹拌させながらモノマーを乳化重合させることによって製造することができる。乳化剤としては、例えば、ヒドロキシエチルセルロース、メチルセルロース、ポリビニルアルコール等の高分子添加剤が挙げられる。高分子添加剤は、ポリビニルアルコールからなるものが特に好ましく、その平均重合度は例えば２００～２５００であり、４００～２２００が好ましく、５００～２０００がさらに好ましい。ポリビニルアルコールは、平均重合度が大きいほど乳化分散力が高まるので、所望の分散度のエマルジョンが得られるように、適切な平均重合度を有するポリビニルアルコールを使用すればよい。また、ポリビニルアルコールは、平均重合度が互いに異なる複数種類のものを組み合わせて使用してもよい。ポリビニルアルコールのケン化度は、特に限定されないが、例えば、７０％以上であり、８０～９５％が好ましい。ケン化度が低すぎると極端に水への溶解性が低下し、特殊な溶解方法を用いなければ溶解できず、工業的には使用し難いからである。ポリビニルアルコールは、ケン化度が低いほど乳化分散力が高まるので、所望の分散度のエマルジョンが得られるように、適切なケン化度を有するポリビニルアルコールを使用すればよい。乳化剤は異なる複数種類のものを組み合わせて使用してもよい。 The method for producing the water-soluble resin emulsion is not particularly limited, but for example, it can be produced by adding an emulsifier and a monomer to a dispersion medium containing water as a main component, and emulsifying the monomer while stirring. Examples of emulsifiers include polymeric additives such as hydroxyethyl cellulose, methyl cellulose and polyvinyl alcohol. The polymer additive is particularly preferably made of polyvinyl alcohol, and its average degree of polymerization is, for example, 200 to 2,500, preferably 400 to 2,200, more preferably 500 to 2,000. Since the higher the average degree of polymerization of polyvinyl alcohol, the higher the emulsifying and dispersing power, polyvinyl alcohol having an appropriate average degree of polymerization may be used so as to obtain an emulsion with a desired degree of dispersion. Polyvinyl alcohols having different average degrees of polymerization may be used in combination. Although the degree of saponification of polyvinyl alcohol is not particularly limited, it is, for example, 70% or more, preferably 80 to 95%. This is because if the degree of saponification is too low, the solubility in water is extremely reduced, and it cannot be dissolved unless a special dissolution method is used, making it difficult to use industrially. Since the lower the degree of saponification of polyvinyl alcohol, the higher the emulsifying and dispersing power, polyvinyl alcohol having an appropriate degree of saponification may be used so as to obtain an emulsion with a desired degree of dispersion. Different emulsifiers may be used in combination.
　なお、水溶性樹脂エマルジョンの製造において乳化剤として用いられた、ポリエチレングリコールやポリビニルアルコール等の高分子添加剤は、エマルジョン組成物に含まれる水溶性高分子とみなされうる。 Polymer additives such as polyethylene glycol and polyvinyl alcohol used as emulsifiers in the production of water-soluble resin emulsions can be regarded as water-soluble polymers contained in the emulsion composition.
＜水溶性高分子＞
　水溶性高分子は、水溶液濃度０．１ｗｔ％、水溶液温度２５℃の条件下、Ｗｉｌｈｅｌｍｙ法で測定した表面張力が４０ｍＮ／ｍ～７５ｍＮ／ｍのものが好ましく、例えば、メチルセルロース、エチルセルロース、ヒドロキシメチルセルロース、ヒドロキシプロピルメチルセルロース、ヒドロキシブチルメチルセルロース、ヒドロキシエチルセルロース、カルボキシメチルセルロース、アミノメチルヒドロキシプロピルセルロース、アミノエチルヒドロキシプロピルセルロース等のセルロース誘導体類；デンプン、カラギーナン、マンナン、アガロース、デキストラン、トラガント、ペクチン、グルー、アルギン酸又はその塩；ゼラチン；ポリビニルピロリドン；ポリアクリル酸又はその塩ポリメタクリル酸又はその塩；ポリアクリルアミド、ポリメタクリルアミド等のアクリルアミド類；ヒアルロン酸及びその塩、コンドロイチン硫酸及びその塩、ポリビニルアルコール、ポリエチレンイミン、ポリエチレンオキシド、ポリエチレングリコール、ポリプロピレングリコール等が挙げられる。これらは単独又は任意の組み合わせにより用いることができる。一態様においては、エマルジョン組成物は、セルロース誘導体及び高分子アルコールを含むことが好ましい。 <Water-soluble polymer>
The water-soluble polymer preferably has a surface tension of 40 mN/m to 75 mN/m as measured by the Wilhelmy method under conditions of an aqueous solution concentration of 0.1 wt % and an aqueous solution temperature of 25° C. Examples include methyl cellulose, ethyl cellulose, hydroxymethyl cellulose, Cellulose derivatives such as hydroxypropylmethylcellulose, hydroxybutylmethylcellulose, hydroxyethylcellulose, carboxymethylcellulose, aminomethylhydroxypropylcellulose, aminoethylhydroxypropylcellulose; starch, carrageenan, mannan, agarose, dextran, tragacanth, pectin, glue, alginic acid or its Salt; gelatin; polyvinylpyrrolidone; polyacrylic acid or its salt polymethacrylic acid or its salt; polyacrylamide, polymethacrylamide and other acrylamides; Ethylene oxide, polyethylene glycol, polypropylene glycol and the like can be mentioned. These can be used alone or in any combination. In one aspect, the emulsion composition preferably comprises a cellulose derivative and a polymeric alcohol.
　エマルジョン組成物中の水溶性高分子の含有量は、好ましくは０．０１～３．０質量％であり、より好ましくは０．１～２．５質量％である。このような範囲とすることにより、適度な粘度によるハンドリング性に優れ、また凍結融解安定性にも優れる。また、エマルジョン組成物中のポリエチレングリコール、ポリビニルアルコール等の高分子アルコールの含有量は、好ましくは０．０１～１．０質量％であり、より好ましくは０．１～０．５質量％である。 The content of the water-soluble polymer in the emulsion composition is preferably 0.01-3.0% by mass, more preferably 0.1-2.5% by mass. By setting it to such a range, it is excellent in handleability by moderate viscosity, and also excellent in freeze-thaw stability. The content of polymer alcohol such as polyethylene glycol and polyvinyl alcohol in the emulsion composition is preferably 0.01 to 1.0% by mass, more preferably 0.1 to 0.5% by mass. .
　水溶性高分子の添加方法は、特に限定されないが、水溶性樹脂エマルジョンの製造において乳化剤として添加されてもよく、水溶性樹脂エマルジョンの製造後に別途添加されてもよい。 The method of adding the water-soluble polymer is not particularly limited, but it may be added as an emulsifier during the production of the water-soluble resin emulsion, or it may be added separately after the production of the water-soluble resin emulsion.
＜界面活性剤＞
　界面活性剤は、水溶液濃度０．１ｗｔ％、水溶液温度２５℃の条件下、Ｗｉｌｈｅｌｍｙ法で測定した表面張力が２５ｍＮ／ｍ～４５ｍＮ／ｍのものが好ましく、例えば、イオン性（カチオン性・アニオン性・双性）界面活性剤や非イオン性（ノニオン性）界面活性剤が挙げられる。カチオン性界面活性剤としては、例えば、第４級アンモニウム塩やアミン塩類等が挙げられる。アニオン性界面活性剤としては、例えば、ラウリル硫酸エステル、アルキルベンゼンスルホン酸塩、アルキルフェニルエーテル硫酸エステル塩やメチルタウリン酸塩、スルホコハク酸塩、エーテルスルホン酸塩、リン酸エステル塩、アルキルエーテル硫酸エステル塩等が挙げられる。双性界面活性剤としては、アルキルカルボキシベタイン等が挙げられる。非イオン性界面活性剤としては、例えば、ポリオキシエチレンノニルフェニルエーテル、ポリオキシエチレンスチレン化フェニルエーテル、ポリオキシエチレンオレイルエーテル、ポリオキシエチレンラウリルエーテル等のポリオキシエチレンアルキルアリールエーテル類又はポリオキシエチレンアルキルエーテル類、ポリオキシアルキレンアルキルエーテル類、ポリエチレングリコールモノラウレート、ポリエチレングリコールモノステアレート、ポリエチレングリコールモノオレエート等のポリオキシエチレン脂肪酸エステル類、ポリオキシエチレン／ポリオキシプロピレンブロックコポリマー等が挙げられる。中でも、界面活性剤は、ベンゼン環を含む構造を有していることが好ましい。また、非イオン性界面活性剤としては、ポリオキシエチレンスチレン化フェニルエーテル又はポリオキシアルキレンアルキルエーテルが好ましい。これらは単独又は任意の組み合わせにより用いることができる。 <Surfactant>
The surfactant preferably has a surface tension of 25 mN/m to 45 mN/m as measured by the Wilhelmy method under conditions of an aqueous solution concentration of 0.1 wt% and an aqueous solution temperature of 25°C. - Zwitterionic) surfactants and nonionic (nonionic) surfactants can be mentioned. Examples of cationic surfactants include quaternary ammonium salts and amine salts. Examples of anionic surfactants include lauryl sulfate, alkylbenzenesulfonate, alkylphenyl ether sulfate, methyl taurate, sulfosuccinate, ethersulfonate, phosphate, and alkyl ether sulfate. etc. Alkyl carboxy betaine etc. are mentioned as a zwitterionic surfactant. Examples of nonionic surfactants include polyoxyethylene alkylaryl ethers such as polyoxyethylene nonylphenyl ether, polyoxyethylene styrenated phenyl ether, polyoxyethylene oleyl ether, and polyoxyethylene lauryl ether, or polyoxyethylene Alkyl ethers, polyoxyalkylene alkyl ethers, polyoxyethylene fatty acid esters such as polyethylene glycol monolaurate, polyethylene glycol monostearate, polyethylene glycol monooleate, polyoxyethylene/polyoxypropylene block copolymers, and the like. . Among them, the surfactant preferably has a structure containing a benzene ring. As the nonionic surfactant, polyoxyethylene styrenated phenyl ether or polyoxyalkylene alkyl ether is preferred. These can be used alone or in any combination.
　エマルジョン組成物中の界面活性剤の含有量は、好ましくは０．１～５．０質量％であり、より好ましくは０．５～３．５質量％である。このような範囲とすることにより、フィルムとしたときの強度に優れ土壌侵食防止剤としての効果が高く、また凍結融解安定性にも優れる。 The content of the surfactant in the emulsion composition is preferably 0.1-5.0% by mass, more preferably 0.5-3.5% by mass. By setting it to such a range, the strength when formed into a film is excellent, the effect as a soil erosion inhibitor is high, and the freeze-thaw stability is also excellent.
　界面活性剤の添加方法は、特に限定されないが、水溶性樹脂エマルジョンの製造において添加されてもよく、水溶性樹脂エマルジョンの製造後に別途添加されてもよい。好ましくは、水溶性樹脂エマルジョンの製造後に別途添加される。 The method of adding the surfactant is not particularly limited, but it may be added during the production of the water-soluble resin emulsion, or may be added separately after the production of the water-soluble resin emulsion. Preferably, it is added separately after the production of the water-soluble resin emulsion.
２．土壌侵食防止剤
　本発明の一実施形態に係る土壌侵食防止剤は、エマルジョン組成物を含む土壌侵食防止剤である。必要に応じて、可塑剤、粘着付与樹脂、増粘剤、消泡剤、ｐＨ調節剤、腐植酸、アミノ酸、除草剤、農薬等を配合することができる。 2. Soil Erosion Inhibitor A soil erosion inhibitor according to one embodiment of the present invention is a soil erosion inhibitor comprising an emulsion composition. If necessary, plasticizers, tackifying resins, thickeners, antifoaming agents, pH adjusters, humic acid, amino acids, herbicides, agricultural chemicals, etc. can be blended.
　土壌侵食防止剤を土壌に散布する方法に特に制限はないが、例えば、小面積に散布する場合では、じょうろや動力散布機等を使用することができ、大面積を散布する場合ではハイドロシーダーやブームスプレーヤ等を使用することができる。また、散布された土壌侵食防止剤は粉粒状堆積物に、粉粒状堆積物の粉粒体と土壌侵食防止剤とからなる固結層を形成する役割を果たすとともに、固結層に流入した雨水を保持し、固結層下に存在する粉粒状堆積物へ流入する水量を少なくすることにより、粉粒状堆積物の崩れ、流出防止に効果を示しうる。また、固結層を形成することにより、粉塵発生の防止にも効果を示しうる。 There are no particular restrictions on the method of spraying the soil erosion inhibitor on the soil. A boom sprayer or the like can be used. In addition, the sprayed soil erosion inhibitor plays a role in forming a consolidated layer consisting of the granular material of the granular sediment and the soil erosion inhibitor in the granular sediment, and rainwater flowing into the consolidated layer and reduce the amount of water flowing into the powdery and granular sediment existing under the consolidated layer, it is effective in preventing the powdery and granular sediment from collapsing and flowing out. Forming a solidified layer can also be effective in preventing the generation of dust.
　また、土壌侵食防止剤は、保護すべき面に対して単独で吹き付けてもよく、土壌を主体とし、種子、バーク堆肥、又は肥料などを混合した吹付資材に配合して吹付資材と共に保護すべき面に対して吹き付けてもよい。吹付資材を対象面に吹き付ける工法に特に制限はなく、例えば、種子散布工、客土吹付工、基材吹付工などを挙げることができ、あるいは、対象面が広大な場合には、ヘリコプターなどの航空機から実播して吹き付けることもできる。 In addition, the soil erosion inhibitor may be sprayed alone on the surface to be protected, and should be protected together with the spraying material, which is mainly composed of soil and mixed with seeds, bark compost, or fertilizer. You can also spray it on the surface. There are no particular restrictions on the method of spraying the spraying material onto the target surface, and examples include seed spraying, soil spraying, and substrate spraying. It can also be seeded and sprayed from an aircraft.
　以下に実施例をあげて本発明を更に詳細に説明する。また、これらはいずれも例示的なものであって、本発明の内容を限定するものではない。 The present invention will be described in more detail with the following examples. Moreover, these are all examples, and do not limit the content of the present invention.
＜水溶性樹脂エマルジョン１（ＥＶＡ１）の調整＞
　ＥＶＡ１を表２の条件に基づき調整した。攪拌機付きの高圧重合缶に、予め１００質量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、デンカ株式会社製）３．４質量部及びデンカポバールＢ－１７（鹸化度８８ｍｏｌ％、平均重合度１７００、デンカ株式会社製）０．７質量部、プルロニックＬ－６４（株式会社アデカ製）０．２質量部、助剤としてホルムアミジンスルフィン酸０．２質量部、酢酸ソーダ０．２質量部、硫酸第一鉄七水和物０．００５質量部、エチレンジアミン四酢酸四ナトリウム０．０１質量部を溶解したものを投入後、攪拌下酢酸ビニルモノマー３３質量部、及びエチレンモノマー２２質量部を充填し内液温度を５５℃とした。１０質量％過硫酸アンモニウム水溶液を添加して重合を開始した。
そこへ、分添モノマーとして酢酸ビニルモノマーを５７質量部及びエチレンモノマー１７質量部、さらに、分添添加剤として１０質量％過硫酸アンモニウム水溶液２．７質量部（初期添加量との合計）及び１０質量％ｔ－ブチルハイドロパーオキサイド水溶液０．９質量部を連続添加し、重合を行った。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ＥＶＡ１を得た。ＥＶＡ１中の水溶性高分子（ポリビニルアルコール：ＰＶＡ）は１．７質量％であり、界面活性剤は０．０８質量％であった。 <Adjustment of water-soluble resin emulsion 1 (EVA1)>
EVA1 was adjusted based on the conditions in Table 2. In a high-pressure polymerization vessel equipped with a stirrer, 3.4 parts by mass of Denka Poval B-05 (saponification degree 88 mol%, average polymerization degree 600, manufactured by Denka Co., Ltd.) as an emulsifier and Denka Poval B-17 are added to 100 parts by mass of pure water in advance. (degree of saponification 88 mol%, average degree of polymerization 1700, manufactured by Denka Co., Ltd.) 0.7 parts by mass, Pluronic L-64 (manufactured by Adeka Co., Ltd.) 0.2 parts by mass, formamidine sulfinic acid 0.2 parts by mass as an auxiliary agent , 0.2 parts by mass of sodium acetate, 0.005 parts by mass of ferrous sulfate heptahydrate, and 0.01 parts by mass of tetrasodium ethylenediaminetetraacetate dissolved therein are added, and then 33 parts by mass of vinyl acetate monomer are added while stirring. and 22 parts by mass of ethylene monomer, and the internal liquid temperature was adjusted to 55°C. A 10% by mass ammonium persulfate aqueous solution was added to initiate polymerization.
Then, 57 parts by mass of vinyl acetate monomer and 17 parts by mass of ethylene monomer were added as partial addition monomers, and 2.7 parts by mass of 10% by mass aqueous ammonium persulfate solution (total with initial addition amount) and 10 parts by mass as partial addition additives. % t-butyl hydroperoxide aqueous solution was continuously added to carry out polymerization. Polymerization was continued until the amount of unreacted vinyl acetate monomer was less than 2%.
Ethylene remaining after the polymerization was purged, and unreacted vinyl acetate monomer in the resulting emulsion was removed under reduced pressure to obtain EVA1. The water-soluble polymer (polyvinyl alcohol: PVA) in EVA1 was 1.7% by mass, and the surfactant was 0.08% by mass.
＜水溶性樹脂エマルジョン２（ＥＶＡ２）の調整＞
　ＥＶＡ２を表２の条件に基づき調整した。攪拌機付きの高圧重合缶に、予め１００質量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、デンカ株式会社製）４．１質量部及びデンカポバールＢ－１７（鹸化度８８ｍｏｌ％、平均重合度１７００、デンカ株式会社製）１．５質量部、助剤としてホルムアミジンスルフィン酸０．１質量部、酢酸ソーダ０．２質量部、硫酸第一鉄七水和物０．００５質量部、エチレンジアミン四酢酸四ナトリウム０．０１質量部を溶解したものを投入後、攪拌下酢酸ビニルモノマー８３質量部、及びエチレンモノマー２０質量部を充填し内液温度を５５℃とした。１０質量％過硫酸アンモニウム水溶液を添加して重合を開始した。そこへ、分添モノマーとして酢酸ビニルモノマーを２６質量部、分添添加剤として５質量％過硫酸アンモニウム水溶液２．０質量部（初期添加量との合計）及び１０質量％ｔ－ブチルハイドロパーオキサイド水溶液０．６質量部を連続添加し、重合を行った。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ＥＶＡ２を得た。ＥＶＡ２中の水溶性高分子（ポリビニルアルコール：ＰＶＡ）は２．４質量％であり、界面活性剤は０質量％であった。 <Adjustment of water-soluble resin emulsion 2 (EVA2)>
EVA2 was adjusted based on the conditions in Table 2. In a high-pressure polymerization vessel equipped with a stirrer, 4.1 parts by mass of Denka Poval B-05 (saponification degree 88 mol%, average polymerization degree 600, manufactured by Denka Co., Ltd.) as an emulsifier and Denka Poval B-17 are added to 100 parts by mass of pure water in advance. (degree of saponification 88 mol%, average degree of polymerization 1700, manufactured by Denka Co., Ltd.) 1.5 parts by mass, 0.1 parts by mass of formamidinesulfinic acid, 0.2 parts by mass of sodium acetate, ferrous sulfate heptahydrate as auxiliary agents After adding 0.005 parts by mass of tetrasodium ethylenediaminetetraacetate and 0.01 parts by mass of tetrasodium ethylenediaminetetraacetate dissolved therein, 83 parts by mass of vinyl acetate monomer and 20 parts by mass of ethylene monomer were charged under stirring, and the temperature of the liquid was adjusted to 55°C. did. A 10% by mass ammonium persulfate aqueous solution was added to initiate polymerization. 26 parts by mass of a vinyl acetate monomer as a partially added monomer, 2.0 parts by mass of a 5% by mass ammonium persulfate aqueous solution as a partially added additive (total with the initial amount added), and a 10% by mass aqueous t-butyl hydroperoxide solution. Polymerization was carried out by continuously adding 0.6 parts by mass. Polymerization was continued until the amount of unreacted vinyl acetate monomer was less than 2%.
Ethylene remaining after the polymerization was purged, and unreacted vinyl acetate monomer in the resulting emulsion was removed under reduced pressure to obtain EVA2. The water-soluble polymer (polyvinyl alcohol: PVA) in EVA2 was 2.4% by mass, and the surfactant was 0% by mass.
Figure JPOXMLDOC01-appb-T000004
Figure JPOXMLDOC01-appb-T000004
［実施例１～１１、比較例１］
　水溶性樹脂エマルジョン（ＥＶＡ１又はＥＶＡ２）と、水と、界面活性剤、必要な水溶性高分子を、表３のそれぞれの配合比率に基づき混合しエマルジョン組成物を調整した。エマルジョン組成物中に含まれる水溶性高分子及び界面活性剤の夫々の合計含有量も表３に示す。 [Examples 1 to 11, Comparative Example 1]
A water-soluble resin emulsion (EVA1 or EVA2), water, a surfactant, and a necessary water-soluble polymer were mixed based on the respective mixing ratios in Table 3 to prepare an emulsion composition. Table 3 also shows the total content of each of the water-soluble polymer and surfactant contained in the emulsion composition.
　なお、表３中の各化合物については次の通りである。
ＨＥＣ２００：ヒドロキシエチルセルロース（２％水溶液粘度（２０℃）：２００～３００ｍＰａ・ｓ、東京化成工業株式会社製）
セロゲンＷＳ－Ｃ：カルボキシメチルセルロース（１％水溶液粘度（２５℃）：１５０～２５０ｍＰａ・ｓ、第一工業製薬株式会社製）
ノイゲンＥＡ－１３７：ポリオキシエチレンスチレン化フェニルエーテル（ＨＬＢ値：１３．０、第一工業製薬株式会社製）
ノイゲンＥＡ－８７：ポリオキシエチレンスチレン化フェニルエーテル（ＨＬＢ値：１０．６、第一工業製薬株式会社製）
エマルゲン１１５０Ｓ－６０：ポリオキシエチレンアルキルエーテル（ＨＬＢ値：１８．５、花王株式会社製）
ノイゲンＬＦ－６０Ｘ：ポリオキシアルキレンアルキルエーテル（ＨＬＢ値：１３．３、第一工業製薬株式会社製） In addition, each compound in Table 3 is as follows.
HEC200: Hydroxyethyl cellulose (2% aqueous solution viscosity (20 ° C.): 200 to 300 mPa s, manufactured by Tokyo Chemical Industry Co., Ltd.)
Cellogen WS-C: Carboxymethylcellulose (1% aqueous solution viscosity (25°C): 150 to 250 mPa s, manufactured by Daiichi Kogyo Seiyaku Co., Ltd.)
Neugen EA-137: Polyoxyethylene styrenated phenyl ether (HLB value: 13.0, manufactured by Daiichi Kogyo Seiyaku Co., Ltd.)
Neugen EA-87: Polyoxyethylene styrenated phenyl ether (HLB value: 10.6, manufactured by Daiichi Kogyo Seiyaku Co., Ltd.)
Emulgen 1150S-60: Polyoxyethylene alkyl ether (HLB value: 18.5, manufactured by Kao Corporation)
Neugen LF-60X: Polyoxyalkylene alkyl ether (HLB value: 13.3, manufactured by Daiichi Kogyo Seiyaku Co., Ltd.)
　また、使用した水溶性高分子及び界面活性剤の表面張力は表４に示す。なお、表面張力は下記の条件に基づいて測定した（測定装置：協和界面科学株式会社製　自動表面張力計ＤＹ－３００）。
　測定温度：２５℃
　水溶液濃度：０．１ｗｔ％
　測定方法：Ｗｉｌｈｅｌｍｙ法（白金プレート） Table 4 shows the surface tensions of the water-soluble polymers and surfactants used. The surface tension was measured under the following conditions (measuring device: automatic surface tension meter DY-300 manufactured by Kyowa Interface Science Co., Ltd.).
Measurement temperature: 25°C
Aqueous solution concentration: 0.1 wt%
Measurement method: Wilhelmy method (platinum plate)
＜粘度＞
　表１の温度サイクルの温度変化を経る前のエマルジョン組成物について粘度を測定した。粘度は、温度３０℃、回転数３０ｒｐｍ（測定装置：東機産業株式会社製　ＴＶ－３３形粘度計）で測定した。 <Viscosity>
Viscosity was measured for the emulsion composition before undergoing the temperature change of the temperature cycle of Table 1. The viscosity was measured at a temperature of 30° C. and a rotation speed of 30 rpm (measurement device: TV-33 viscometer manufactured by Toki Sangyo Co., Ltd.).
＜粗粒率＞
　表１の温度サイクルの温度変化を経る前のエマルジョン組成物、及び表１において各行の温度変更を上から下への順に行っていく温度サイクルを１サイクルとして、当該温度サイクルを１０サイクル繰り返した後のエマルジョン組成物について粗粒率を測定した。粗粒率は、温度サイクルの温度変化を経る前のエマルジョン組成物、及び経た後のエマルジョン組成物を試料とし、目開きが２００メッシュの金網を用いて、ＪＩＳ　Ｋ　６８２８に準じてろ過残渣の質量Ｍ１を測定し、試料（エマルジョン組成物Ｍ０）の質量に対する割合（＝［Ｍ１／Ｍ０］）をｐｐｍで算出した。
　なお、表１の温度サイクルの温度変化は、環境試験機（エスペック株式会社製　ＰＲ－３Ｋ）により制御することにより行った。 <Coarse grain ratio>
The emulsion composition before undergoing the temperature change of the temperature cycle in Table 1, and the temperature cycle in which the temperature changes in each row in Table 1 are performed in order from top to bottom as one cycle, and after repeating the temperature cycle for 10 cycles of the emulsion composition was measured. The coarse particle ratio is obtained by using the emulsion composition before and after the temperature change of the temperature cycle as a sample, using a wire mesh with an opening of 200 mesh, and measuring the mass of the filtration residue according to JIS K 6828. M 1 was measured and the ratio (=[M 1 /M 0 ]) to the mass of the sample (emulsion composition M 0 ) was calculated in ppm.
The temperature change in the temperature cycle in Table 1 was controlled by an environmental tester (PR-3K manufactured by Espec Co., Ltd.).
Figure JPOXMLDOC01-appb-T000005
Figure JPOXMLDOC01-appb-T000005
Figure JPOXMLDOC01-appb-T000006
Figure JPOXMLDOC01-appb-T000006

Claims (8)

  1. 下表において各行の温度変更を上から下への順に行っていく温度サイクルを１サイクルとして、前記温度サイクルを１０サイクル繰り返した後に、２００メッシュの金網でろ過したときの粗粒率が５００ｐｐｍ以下であり、
    前記各行の温度変更は、保持時間中に開始温度から終了温度まで変更又は維持することにより行われるエマルジョン組成物。
    Figure JPOXMLDOC01-appb-I000001
    In the table below, the temperature cycle in which the temperature changes in each row are performed in order from top to bottom is regarded as one cycle, and after repeating the temperature cycle for 10 cycles, when filtering with a 200 mesh wire mesh, the coarse particle rate is 500 ppm or less. can be,
    The emulsion composition wherein the temperature change in each row is by changing or maintaining from a starting temperature to an ending temperature during the holding time.
    Figure JPOXMLDOC01-appb-I000001
  2. 水溶性樹脂エマルジョン、水溶性高分子および界面活性剤を含む、請求項１記載のエマルジョン組成物。 2. The emulsion composition of claim 1, comprising a water-soluble resin emulsion, a water-soluble polymer and a surfactant.
  3. 前記水溶性高分子と前記界面活性剤との含有量の質量比が７：１～１：７である、請求項２に記載のエマルジョン組成物。 3. The emulsion composition according to claim 2, wherein the weight ratio of the content of the water-soluble polymer and the surfactant is 7:1 to 1:7.
  4. 水溶性樹脂エマルジョン、水溶性高分子および界面活性剤を含み、
    前記水溶性高分子の含有量と前記界面活性剤との含有量の質量比が７：１～１：７である、
    エマルジョン組成物。     including a water-soluble resin emulsion, a water-soluble polymer and a surfactant,
    The mass ratio of the content of the water-soluble polymer and the content of the surfactant is 7:1 to 1:7.
    emulsion composition.
  5. 前記水溶性高分子と前記界面活性剤とを合計で１～６質量％含む、請求項２～請求項４の何れか１項に記載のエマルジョン組成物。 5. The emulsion composition according to any one of claims 2 to 4, comprising a total of 1 to 6% by mass of said water-soluble polymer and said surfactant.
  6. 前記水溶性樹脂エマルジョンが、酢酸ビニルに由来する構造単位を含む樹脂のエマルジョンである、請求項２～請求項５の何れか１項に記載のエマルジョン組成物。 6. The emulsion composition according to any one of claims 2 to 5, wherein the water-soluble resin emulsion is a resin emulsion containing structural units derived from vinyl acetate.
  7. 前記水溶性樹脂エマルジョンが、エチレン－酢酸ビニル共重合体エマルジョンである、請求項２～請求項５の何れか１項に記載のエマルジョン組成物。 The emulsion composition according to any one of claims 2 to 5, wherein the water-soluble resin emulsion is an ethylene-vinyl acetate copolymer emulsion.
  8. 請求項１～７のいずれか一項に記載のエマルジョン組成物を含む土壌侵食防止剤。 A soil erosion inhibitor comprising the emulsion composition according to any one of claims 1 to 7.
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