CN108291144A - 具有良好冻结溶解稳定性的土壤侵蚀防止剂 - Google Patents
具有良好冻结溶解稳定性的土壤侵蚀防止剂 Download PDFInfo
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- CN108291144A CN108291144A CN201680070125.9A CN201680070125A CN108291144A CN 108291144 A CN108291144 A CN 108291144A CN 201680070125 A CN201680070125 A CN 201680070125A CN 108291144 A CN108291144 A CN 108291144A
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Classifications
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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
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
- C08L2205/025—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group containing two or more polymers of the same hierarchy C08L, and differing only in parameters such as density, comonomer content, molecular weight, structure
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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
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
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- E—FIXED CONSTRUCTIONS
- E02—HYDRAULIC ENGINEERING; FOUNDATIONS; SOIL SHIFTING
- E02B—HYDRAULIC ENGINEERING
- E02B3/00—Engineering works in connection with control or use of streams, rivers, coasts, or other marine sites; Sealings or joints for engineering works in general
- E02B3/04—Structures or apparatus for, or methods of, protecting banks, coasts, or harbours
- E02B3/12—Revetment of banks, dams, watercourses, or the like, e.g. the sea-floor
Landscapes
- Engineering & Computer Science (AREA)
- Chemical & Material Sciences (AREA)
- General Life Sciences & Earth Sciences (AREA)
- Mining & Mineral Resources (AREA)
- Life Sciences & Earth Sciences (AREA)
- Organic Chemistry (AREA)
- General Engineering & Computer Science (AREA)
- Structural Engineering (AREA)
- Civil Engineering (AREA)
- Paleontology (AREA)
- Soil Sciences (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Health & Medical Sciences (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Environmental & Geological Engineering (AREA)
- Ocean & Marine Engineering (AREA)
- Mechanical Engineering (AREA)
- Pit Excavations, Shoring, Fill Or Stabilisation Of Slopes (AREA)
- Soil Conditioners And Soil-Stabilizing Materials (AREA)
Abstract
本发明提供一种不损伤土壤侵蚀防止效果而具有良好冻结融解稳定性的土壤侵蚀防止剂。其包含水性树脂乳液和水溶性高分子,该水性树脂乳液相对于源自主单体的结构单元100质量份含有源自多官能单体的结构单元0.01~0.10质量份,该水溶性高分子的含量相对于水性树脂乳液为1~7质量%。优选源自多官能单体的结构单元为0.05~0.10质量份,水溶性高分子的含量为1~5质量%。
Description
【技术领域】
本发明是关于一种土壤侵蚀防止剂,其较好地用以防止由建设用地、道路、水坝等的建设时的填土或切土所形成的坡面等所导致的土壤侵蚀。
背景技术
由建设用地、道路、水坝等的建设时进行的填土或切土所形成的坡面,若放置不顾,则会因降雨或风化等而被侵蚀,从而导致滑坡或落石等事故的发生。因此,对坡面喷洒专利文献1提到的喷涂材料而防止土壤的侵蚀。该喷涂材料是将由水膨润性吸水性树脂、表面活性剂以及合成树脂乳液组成的土壤干燥防止剂以喷涂材料每1m3为0.5~1.5kg的比例调配而成。
使用于坡面工程的材料有时保管在仓库等,有时会被搬到现场且用片材等覆盖保管。在寒冷地带的冬季,有时保管场所会低于冰点,从而存在土壤侵蚀防止剂冻结而凝聚等问题。
【现有技术文献】
【专利文献】
【专利文献1】日本专利第4048800号
【专利文献2】日本特开2000-129259号公报
【专利文献3】日本特表2011-510135号公报
【发明内容】
【发明要解决的课题】
关于土壤侵蚀防止剂,专利文献1中有记载,专利文献2涉及聚丙烯酰胺系的树脂,专利文献3中以烷氧基化合物作为构成成分,尚不知乙酸乙烯酯树脂乳液的冻结融解稳定性改良相关的技术。
本发明是鉴于此种情况而完成的,且提供一种不损伤土壤侵蚀防止效果而提高冻结融解稳定性的土壤侵蚀防止剂。
【为了解决课题的技术手段】
即,本发明为如下所示。
(1)一种土壤侵蚀防止剂,其特征在于:包含水性树脂乳液和水溶性高分子,且水性树脂乳液相对于源自主单体的结构单元100质量份,含有源自多官能单体的结构单元0.01~0.10质量份,且水性树脂乳液的含量为99~93质量%,水溶性高分子的含量为1~7质量%。
(2)如(1)所述的土壤侵蚀防止剂,其特征在于:水性树脂乳液相对于源自于主单体的结构单元100质量份,含有源自于多官能单体的结构单元0.05~0.10质量份。
(3)如(1)~(2)所述的土壤侵蚀防止剂,其特征在于使用含有源自乙酸乙烯酯的结构单元的水性树脂乳液。
(4)如(1)~(3)中任一项的土壤侵蚀防止剂,其特征在于使用乙烯-乙酸乙烯酯共聚物乳液。
(5)一种绿化施工方法,其使用(1)~(4)中任一项的土壤侵蚀防止剂。
(6)一种绿化施工方法,其将(1)~(4)中任一项的土壤侵蚀防止剂以喷涂材料每1m3为1~10kg的方式使用。
(7)一种喷涂材料,其将(1)~(4)中任一项的土壤侵蚀防止剂以喷涂材料每1m3为1~10kg的方式使用。
【发明效果】
根据本发明人进行的实验,可得知水性树脂乳液中的多官能单体含量越多,可用越少的水溶性高分子添加量获得良好的冻结融解稳定性。并且,可得知含有等量水溶性高分子的土壤侵蚀防止剂的情况下,水性树脂乳液中的多官能单体含量不同导致冻结融解稳定性存在差异。具体而言,发现水性树脂乳液相对于源自主单体的结构单元100质量份含有源自多官能单体的结构单元0.01~0.10质量份,且水溶性高分子的含量相对于水性树脂乳液为1~7质量%的土壤侵蚀防止剂可发挥出良好的效果,从而完成了本发明。
【具体实施方式】
以下,对本发明的实施方式进行详细说明。
本发明的土壤侵蚀防止剂水性树脂乳液与水溶性高分子,其特征在于,水性树脂乳液相对于源自主单体的结构单元100质量份,含有源自多官能单体的结构单元0.01~0.10质量份,水溶性高分子的含量相对于水性树脂乳液为1~7质量%。优选相对于源自主单体的结构单元100质量份,源自于多官能单体的结构单元为0.05~0.10质量份,且水溶性高分子的含量相对于水性树脂乳液为1~5质量%。
水性树脂乳液的种类,只要是将水作为分散介质、将树脂作为分散物质则无特别限定,可使用将乙酸乙烯酯、丙烯酸酯、苯乙烯、乙烯、丁二烯等各种烯烃系化合物中的一种或多种用作主单体进行聚合而制得的水性树脂乳液。具体而言、可例举:乙酸乙烯酯树脂乳液、乙酸乙烯酯共聚物乳液、丙烯酸酯树脂乳液、苯乙烯丙烯酸酯共聚物乳液、乙烯-乙酸乙烯酯共聚物乳液、苯乙烯-丁二烯共聚物乳液、亚乙烯树脂乳液、聚丁烯树脂乳液、丙烯腈-丁二烯树脂乳液、甲基丙烯酸甲酯-丁二烯树脂乳液、沥青乳液、环氧树脂乳液、聚氨酯树脂乳液、硅树脂乳液,其中,优选含有源自乙酸乙烯酯的结构单元的树脂的乳液(乙酸乙烯酯树脂乳液、乙酸乙烯酯共聚物乳液、乙烯-乙酸乙烯酯共聚物乳液等),更优选乙烯-乙酸乙烯酯共聚物乳液。
【关于水性树脂乳液的补记预定】
本发明中的所谓多官能单体,是指在成为共聚物的构成成分的情况下,可提供两个以上的乙烯性双键的单体。具体而言,可例举氰尿酸三烯丙酯、异氰脲酸三烯丙酯、邻苯二甲酸二烯丙酯。
水性树脂乳液的制造方法并无特别限定,例如,在以水作为主成分的分散介质中添加乳化剂与单体,边进行搅拌边使单体进行乳化聚合而制造。根据该制造时所使用的单体的种类或添加速度,可使所获得的乳液的甲苯不溶物成分产生变化。作为乳化剂,可列举离子性(阳离子性、阴离子性、两性)表面活性剂或非离子性(Nonionic)表面活性剂。作为非离子性表面活性剂,可列举烷基糖苷之类的低分子系表面活性剂或者聚乙二醇或聚乙烯醇之类的高分子系表面活性剂,优选高分子系表面活性剂。高分子系表面活性剂特别优选由聚乙烯醇构成的表面活性剂,例如,其平均聚合度为200~2500,优选400~2200,更优选500~2000。聚乙烯醇的平均聚合度越大,其乳化分散力越高,因此为了获得所需分散度的乳液,只要使用具有适当平均聚合度的聚乙烯醇即可。并且,可组合使用多个平均聚合度互不相同的聚乙烯醇。聚乙烯醇的皂化度并无特别限定,例如,70%以上,优选80~95%。其原因在于:若皂化度过低,则水溶性会极度降低,若不使用特殊的溶解方法则无法溶解,而难以使用于工业。聚乙烯醇的皂化度越低,乳化分散力越高,因此为了获得所需分散度的乳液,只要使用具有适当皂化度的聚乙烯醇即可。可组合使用多个不同的乳化剂。乳化剂的添加量并无特别限定,例如,相对于分散介质100质量份为0.5~20质量份,优选1至10质量份。乳化剂的添加量越多,乳化分散力越高,因此为了获得所需分散度的乳液,可适当调整乳化剂的添加量。
土壤侵蚀防止剂的固形物成分比例为25~60质量%,优选30~40质量%。其原因在于:若该固形物成分比例过低,则土壤侵蚀防止剂的聚合物量过少而土壤侵蚀防止效果较弱,若固形物成分比例过高,则粘度变得过高而难以调配于喷涂材料中,并且,有降低冻结融解稳定性的倾向。
并且,本发明的水性树脂乳液中所包含的水溶性高分子并无特别限定,可例示:甲基纤维素、乙基纤维素、羟甲基纤维素、羟丙基甲基纤维素、羟丁基甲基纤维素、羟乙基纤维素、羧甲基纤维素、胺基甲基羟基丙基纤维素、胺基乙基羟丙基纤维素等纤维素衍生物类;淀粉、角叉菜胶、甘露聚醣、琼脂糖、葡聚糖、黄耆胶、果胶、牛皮胶、海藻酸或其盐;明胶;聚乙烯吡咯啶酮;聚丙烯酸或其盐、聚甲基丙烯酸或其盐;聚丙烯酰胺、聚甲基丙烯酰胺等丙烯酰胺类;透明质酸及其盐、硫酸软骨素及其盐、聚乙烯醇、聚乙亚胺、聚环氧乙烷、聚乙二醇、聚丙二醇、甘油,亦可将多种组合使用。并且,亦可使用与水混合的非离子性表面活性剂,可例示:聚氧乙烯壬基苯醚、聚氧乙烯苯乙烯化苯醚、聚氧乙烯油醚、聚氧乙烯月桂醚等聚氧烯烷基芳基醚类或聚氧乙烯烷基醚类;聚乙二醇单月桂酸酯、聚乙二醇单硬脂酸酯、聚乙二醇单油酸酯等聚氧乙烯脂肪酸酯类;及氧化乙烯/氧化丙烯嵌段共聚物等。
水溶性高分子在土壤侵蚀防止剂中的含量越多,水性树脂乳液的冻结融解稳定性越得到提高,但另一方面,有降低土壤侵蚀防止效果的倾向。因此所含有的水溶性高分子优选1~7质量%,更优选11~5质量%。
接下来,对本发明的土壤侵蚀防止剂的使用方法进行说明。该土壤侵蚀防止剂既可单独喷涂至应保护的面,也可调配于将土壤作为主体并混有种子、肥料等的喷涂材料中,与喷涂材料一并喷涂至应保护的面。将喷涂材料喷涂至对应面的方法并无特别限制,可列举:种子散布法、客土喷涂法、基材喷涂法等,或者在对象面广阔的情况下,也可由直升机等航空器进行喷涂。
所使用的喷涂材料并无特别限制,例如,可使用树皮堆肥、泥炭沼等有机质材料或砂质土中混有种子、肥料等的喷涂材料。
土壤侵蚀防止剂的添加量并无特别限定,以相对于喷涂材料1m3为1~10kg、优选4~6kg的方式进行添加。
【实施例】
以下,对本发明的实施例进行说明。在以下的说明中,只要没有特别事先说明,则「份」、「%」分别意指「质量份」、「质量%」。
(制造例1:水性树脂乳液1)
预先在100份的纯水中溶解作为乳化剂的DENKA POVAL B-05(皂化度88mol%,平均聚合度600,电气化学工业公司制造)1.6份及DENKA POVAL B-17(皂化度88mol%,平均聚合度1700,电气化学工业公司制造)2.7份,作为助剂的甲脒亚磺酸0.1份、乙酸钠0.2份、硫酸亚铁七水合物0.005份、乙二胺四乙酸四钠0.01份,溶解后投入附带搅拌机的高压聚合罐中,其后,搅拌下填充乙酸乙烯酯单体57份、乙烯19份、及氰尿酸三烯丙酯单体0.06份并使内液温度为55℃后,连续添加5%叔丁基过氧化氢水溶液2.7份而进行聚合。聚合途中分别添加乙酸乙烯酯单体25份、氰尿酸三烯丙酯单体0.02份。继续进行聚合直至未反应的乙酸乙烯酯单体量小于2%为止。
去除聚合后剩余的乙烯,并于减压下去除所生成的乳液中的未反应的乙酸乙烯酯单体后,得到表1中记载的、多官能单体相对于主单体的含有份数为0.10份的水性树脂乳液1。
(制造例2~6:水性树脂乳液2~6)
以下述表1记载的组成并依据制造例1的步骤进行聚合,如表1所记载,分别获得多官能单体相对于主单体的含有份数为0.05份的水性树脂胶2、多官能单体相对于主单体的含有份数为0.01份的水性树脂乳液3、不含多官能单体的水性树脂乳液4、多官能单体相对于主单体的含有份数为0.20份的水性树脂乳液5、多官能单体相对于主单体的含有份数为0.10份的水性树脂乳液6。
(土壤侵蚀防止剂的制备:实施例1)
将作为水溶性高分子的PEG400(纯正化学制造)以相对于最终获得的水性树脂乳液整体成为表2记载的特定含量(质量%)的方式向制造例1中所获得的水性树脂乳液1进行添加,并适当地添加水进行调整以使水性树脂乳液整体的固形物成分比例成为30%,制成实施例1的土壤侵蚀防止剂。再者,表2中,所使用的水溶性高分子种类用“*”表示。
(土壤侵蚀防止剂的制备:实施例2~14及比较例1~3)
依据表2记载的组成、比例而制成实施例2~14及比较例1~3的土壤侵蚀防止剂。并且,水溶性高分子分别使用PEG400(纯正化学制造)、PEG20000(纯正化学制造)、DENKA POVALB-05(皂化度88mol%,平均聚合度600,电气化学工业公司制造)、DENKA POVAL B-17(皂化度88mol%,平均聚合度1700,电气化学工业公司制造)、DENKA POVALB-33(皂化度88mol%,平均聚合度3300,电气化学工业公司制造)、羟乙基纤维素(2%水溶液粘度(20℃):200-300mPa·s东京化成工业制造)、羧甲基纤维素Cellogen 7A(第一工业制药制造)。
针对所获得的各个土壤侵蚀防止剂,进行冻结融解稳定性、土壤侵蚀防止性能的评价,将其结果示于表2。
(甲苯不溶物成分比例测定)
(1)将乳液10g塗布于氟树脂板(设为100cm2左右的面积)上,在23℃下干燥5天。
(2)将干燥皮膜切割成5mm见方,将其1g放入至螺旋管中,用甲苯50g填满并塞严。
(3)在50℃的热水浴中振荡5小时。
(4)利用200目金属筛网进行过滤,将回收的不溶物成分在通风室内以23℃干燥1夜后,利用干燥机(105℃)干燥3小时,测定不溶物成分的干燥重量。
(5)根据下述式求出甲苯不溶物成分比例。甲苯不溶物成分比例(%)=回收的不溶物成分干燥重量÷投入的膜重量×100
(冻结融解稳定性评价)
(1)称取50g乳液至100ml容器中。
(2)在环境试验机中(-20℃)静置16小时使其冻结。
(3)从环境试验机中取出,在30℃的热水浴中静置1小时使其融解。
(4)目视观察融解后的状态,并以下述标准判定凝聚的程度。
○:与冻结前的乳液同等
△:虽流动而成为液状,但可发现凝聚物
×:成为海绵状,且无流动
(土壤侵蚀防止评价)
此后,通过以下的方法,制作厚层基材喷涂的植物生长基盘,其中配合有所制作的样品,测定因降水试验而流出的土壤的量。
(1)混合:容器中添加树皮堆肥(富士见环境绿化公司制造的Fujimi soil 5号)7L、高度化成肥料(日东FC公司制造,15-15-15)21g、种子(KANEKO SEEDS公司制造的Italianryegrass)3.5g、各种侵蚀防止剂21g并进行混练,制成植物生长基盘材料。
(2)施工:将植物生长基盘材料填充至木框(30cm×30cm的矩形,高度10cm)中并摊平后,自上方进行压缩直至体积成为一半。
(3)养护:取下木框,在23℃的室内固化1夜。
(4)降水:利用喷壶经养护的植物生长基盘进行降水。使植物生长基盘倾斜9°,并自50cm的高度以1小时200mm的强度实施30分钟降水,目视观察流出的土壤量,以下述方式进行判定。
○:几乎未发现流出。
△:发现一部分流出。
×:发现整体流出。
参照表2,则可得知有如下倾向:水溶性高分子的含量越多,水性树脂乳液的冻结融解稳定性越提高,土壤侵蚀防止效果越降低。并且,可知在水溶性高分子含量相同的情况下,水性树脂乳液中的多官能单体含量越多,越会在添加少量的水溶性高分子的情况下提高冻结融解稳定性。
根据上述,使用如下的土壤侵蚀防止剂,可无损土壤侵蚀防止效果而获得较高的冻结融解稳定性。该土壤侵蚀防止剂的特征在于,含有水性树脂乳液和水溶性高分子,该水性树脂乳液相对于源自主单体的结构单元100质量份含有源自多官能单体的结构单元0.01~0.10质量份,该水溶性高分子的含量相对于水性树脂乳液为1~7质量%。
【表1】
【表2】
【产业上的可利用性】
本发明中由水性树脂乳液组成的土壤侵蚀防止剂,其不损伤土壤侵蚀防止效果且拥有良好的冻结融解稳定性,即便是在寒冷地带的冬季,因其良好的保管稳定性,也可利用于绿化工程等。
Claims (7)
1.一种土壤侵蚀防止剂,其特征在于:其包含水性树脂乳液与水溶性高分子,所述水性树脂乳液相对于源自主单体的结构单元100质量份,含有源自多官能单体的结构单元0.01~0.10质量份,且水性树脂乳液的含量为99~93质量%,水溶性高分子的含量为1~7质量%。
2.根据权利要求1所述的土壤侵蚀防止剂,其特征在于,所述水性树脂乳液相对于源自主单体的结构单元100质量份,含有源自多官能单体的结构单元0.05~0.10质量份。
3.根据权利要求1或2所述的土壤侵蚀防止剂,其特征在于,使用包含源自乙酸乙烯酯的结构单元的水性树脂乳液。
4.根据权利要求1~3中任一项所述的土壤侵蚀防止剂,其特征在于,使用乙烯-乙酸乙烯酯共聚物乳液。
5.一种绿化施工方法,其特征在于,使用权利要求1~4中任一项所述的土壤侵蚀防止剂。
6.一种绿化施工方法,其特征在于,将权利要求1~4中任一项所述的土壤侵蚀防止剂以喷涂材料每1m3为1~10kg的方式使用。
7.一种喷涂材料,其特征在于,将权利要求1~4中任一项所述的土壤侵蚀防止剂以喷涂材料每1m3为1~10kg的方式使用。
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PCT/JP2016/085477 WO2017094747A1 (ja) | 2015-11-30 | 2016-11-30 | 凍結融解安定性に優れる土壌侵食防止剤 |
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CN114375230A (zh) * | 2019-11-05 | 2022-04-19 | 电化株式会社 | 土壤改性方法 |
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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 |
TW202309248A (zh) * | 2021-04-30 | 2023-03-01 | 日商電化股份有限公司 | 土壤侵蝕防止劑之散佈方法 |
TW202311499A (zh) * | 2021-05-20 | 2023-03-16 | 日商電化股份有限公司 | 乙烯-乙酸乙烯酯系共聚物乳液、其製造方法、以及土壤侵蝕防止劑 |
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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US20180320070A1 (en) | 2018-11-08 |
TW201728746A (zh) | 2017-08-16 |
JPWO2017094747A1 (ja) | 2018-09-13 |
TWI714675B (zh) | 2021-01-01 |
US10150916B2 (en) | 2018-12-11 |
JP6767384B2 (ja) | 2020-10-14 |
WO2017094747A1 (ja) | 2017-06-08 |
CN108291144B (zh) | 2021-03-09 |
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