WO2012071698A1 - 一种仿生胶及其制备方法与应用 - Google Patents
一种仿生胶及其制备方法与应用 Download PDFInfo
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- WO2012071698A1 WO2012071698A1 PCT/CN2010/079249 CN2010079249W WO2012071698A1 WO 2012071698 A1 WO2012071698 A1 WO 2012071698A1 CN 2010079249 W CN2010079249 W CN 2010079249W WO 2012071698 A1 WO2012071698 A1 WO 2012071698A1
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- WIPO (PCT)
- Prior art keywords
- biomimetic
- deionized water
- added
- mass percentage
- catalyst
- Prior art date
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Classifications
-
- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
- A01N25/00—Biocides, pest repellants or attractants, or plant growth regulators, characterised by their forms, or by their non-active ingredients or by their methods of application, e.g. seed treatment or sequential application; Substances for reducing the noxious effect of the active ingredients to organisms other than pests
- A01N25/24—Biocides, pest repellants or attractants, or plant growth regulators, characterised by their forms, or by their non-active ingredients or by their methods of application, e.g. seed treatment or sequential application; Substances for reducing the noxious effect of the active ingredients to organisms other than pests containing ingredients to enhance the sticking of the active ingredients
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/10—Esters
- C08F220/12—Esters of monohydric alcohols or phenols
- C08F220/16—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms
- C08F220/18—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms with acrylic or methacrylic acids
- C08F220/1804—C4-(meth)acrylate, e.g. butyl (meth)acrylate, isobutyl (meth)acrylate or tert-butyl (meth)acrylate
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J133/00—Adhesives based on 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 only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Adhesives based on derivatives of such polymers
- C09J133/04—Homopolymers or copolymers of esters
- C09J133/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, the oxygen atom being present only as part of the carboxyl radical
- C09J133/10—Homopolymers or copolymers of methacrylic acid esters
Definitions
- the invention belongs to the field of plant pest control, and particularly relates to a biomimetic adhesive having the characteristics of armyworm, and a preparation method and use of the bionic rubber.
- Harmful organisms in agricultural production such as various pests, pathogenic microorganisms, etc., are one of the main obstacles to high yield and stable production of agricultural production, especially for various small pests, due to large amount of occurrence, strong adaptability, and easy to produce drug resistance. The problem becomes a difficult point in prevention and control in production.
- Current pest control master book
- the first type gel or semi-solid state at room temperature (5 ⁇ 40 °C), mainly composed of rosin, paraffin or polybutene, adding castor oil Or oily gums of other organic solvents, usually added with a thickener, etc., such as sticky gums have high viscosity, such as CN200410008453, CN200510014730, CN200510064422, CN200720006978 and the like.
- This type of shellac can only be used by brushing, or it must be applied to the base material, such as cardboard, swatch, plastic paper, etc., in combination with other insect attractants (such as sex pheromones).
- the role of armyworm The main problems of this glue are: It is toxic to plants and cannot be in direct contact with young branches such as plant branches and leaves. Secondly, because of its high adhesive consistency, it can not be sprayed, and the application is inconvenient, and the control efficiency is low.
- the second type liquid at room temperature, the main component of this mucopolysaccharide is an organic solvent, such as the adhesive shellac of polyacrylamide and Taikoo oil (sulfonated castor oil) as disclosed in CN200610025325.
- the problem with this kind of mucilage is: It is harmful to plant tissues and cannot be sprayed directly on plant leaves and young tissues. Secondly, the organic solvent contained will pollute the environment. (3)
- the third type is a liquid state at room temperature, and has a quick-drying adhesive shellac after spraying.
- JP84023352 and JP53124181 disclose resin derivatives, polysaccharide derivatives, such as natural or synthetic rubber, poly(iso).
- the problems with this type of muscoid gum are: (a) must be sprayed directly onto the pest to act as a moldworm; (b) the viscous component loses its viscosity within a few minutes after spraying and does not maintain the performance of the armyworm for a long time; (c) Volatile solvent components contaminate the environment; (d) Do not spray on the surface of plants and leaves, causing damage to plants. Therefore, this type of adhesive shellac can only be used for the prevention and control of indoor sanitary pests.
- Chinese patent CN99120025. X discloses an adhesive shelly consisting of polyvinyl alcohol, water-soluble silicate, surfactant, polyvinylpyrrolidone and water.
- the shellac glue cures rapidly within a few minutes after spraying, fixing the pests.
- the appendages such as the feet and the wings make it incapable of moving, thereby achieving the purpose of reducing pests.
- the sticky shellac also has the following problems: It must be sprayed directly on the pest worm to effectively fix the pest. Secondly, the viscous component fails quickly, and the sticky worm has a short effective period, and must be sprayed frequently to function, wasting manpower and material resources. high cost.
- a first object of the present invention is to provide a biomimetic adhesive having the characteristics of armyworm, which has good effect and long duration, and can be sprayed on the surface of the stem and leaves of the plant without affecting the normal growth of the plant.
- Another object of the present invention is to provide a method for preparing the above-mentioned biomimetic glue.
- the acrylic soft monomer described in the above biomimetic rubber is ethyl acrylate, ethyl methacrylate, butyl acrylate, butyl methacrylate, octyl acrylate, isooctyl acrylate, methyl methacrylate or methacrylic acid.
- the acrylic monomer described in the above biomimetic rubber means acrylic acid or methacrylic acid.
- the nonionic emulsifier described in the above biomimetic rubber is one of a nonylphenol ethoxylate, a fatty alcohol polyoxyethylene ether mixture, a polyether modified trisiloxane, or the like, or a mixture thereof.
- the anionic emulsifier described in the above biomimetic rubber refers to a fatty alcohol polyoxyethylene ether sulfate, a sulfhydryl group.
- the preservatives described in the above biomimetic rubber are isothiazolinone compounds, or bronopol compounds.
- bronopol compounds such as the American Rohm and Haas Kathon® LXE fungicide (5-chloro-2-methyl-4-isothiazolin-3-one + 2-methyl-4-isothiazolin-3-one), bronopol A water-soluble preservative such as an alcohol (2-bromo-2-nitro-1,3-propanediol, C 3 H 6 BrN0 4 ).
- the antifoaming agent described in the above biomimetic rubber is a polysiloxane type compound (for example, polydimethylsiloxane (silicone) (silicone), defoaming agent such as cyclomethicone), polyether Compounds (such as polyoxypropylene glycerol ether), mineral oil defoamers (such as polyether mineral oil defoamer, non-silicone mineral oil defoamer, polyether silicone oil mineral oil defoamer) Foaming agent.
- polysiloxane type compound for example, polydimethylsiloxane (silicone) (silicone), defoaming agent such as cyclomethicone), polyether Compounds (such as polyoxypropylene glycerol ether), mineral oil defoamers (such as polyether mineral oil defoamer, non-silicone mineral oil defoamer, polyether silicone oil mineral oil defoamer) Foaming agent.
- the above-mentioned biomimetic rubber may further contain at least one of the following components: a fluorescent substance or an insect pheromone. 1% ⁇ The pheromone is added in a ratio of 0. 01 ⁇ 0.
- the fluorescent substance is a long-lasting luminous powder, such as an alkaline earth aluminate base, a silicate-based light-storing luminescent material, a zinc sulfide or a calcium sulfide series phosphor, etc., preferably a rare earth aluminate group or a rare earth silicate group.
- Luminous powder such as an alkaline earth aluminate base, a silicate-based light-storing luminescent material, a zinc sulfide or a calcium sulfide series phosphor, etc., preferably a rare earth aluminate group or a rare earth silicate group.
- the insect pheromones are at least one of an insect pheromone, an aggregate pheromone or a warning pheromone.
- the preparation method of the above biomimetic rubber comprises the following steps:
- Reactor 2 is cooled to 40 ⁇ 50 °C, preservative, defoamer, nonionic emulsifier is added to the reaction kettle 2, stirred for 10 ⁇ 15 min, filtered by 80 ⁇ 100 mesh, and the filtrate is collected.
- the filtrate is a biomimetic glue.
- the amount of deionized water added in the above step (1) of the preparation method is preferably 10 to 15% by mass based on the total amount of deionized water.
- the anionic emulsifier described in the above production method step (1) is preferably sodium dodecyl sulfate or sodium dodecylbenzenesulfonate.
- the anionic emulsifier described in the above production method step (1) is preferably added in an amount of 80% by mass based on the total amount of the anionic emulsifier.
- the acrylic soft monomer described in the above production method step (1) is preferably butyl acrylate and/or isooctyl acrylate.
- the acrylic monomer described in the above production method step (1) is preferably acrylic acid.
- the anionic emulsifier added in the above step (2) of the production method is preferably added in an amount of 20% by mass based on the total amount thereof.
- the reaction temperature described in the above step (2) of the production method is preferably 80 to 85 °C.
- the mass percentage of the emulsion extracted in the above step (3) of the preparation method is preferably 10 to 15%.
- the mass percentage of the emulsion extracted in the above step (4) of the preparation method is preferably 85 to 90%.
- the holding time in the step (4) of the above preparation method is preferably 60 min.
- a fluorescent substance is added to the above-mentioned bionic rubber in a ratio of 0.1 to 5% by mass, stirred uniformly, filtered through a 100-mesh filter, and sealed for storage.
- the fluorescent substance described in the above production method is preferably a rare earth aluminate-based luminous powder.
- the biomimetic glue of the invention can be sprayed directly on the branches and leaves of the target plant by spraying, and viscous glue droplets are formed on the branches and leaves, and the glue droplets can remain sticky for dozens of days or even months, forming a "ray” which can be sticky at any time.
- "Region” which causes obstacles to the normal feeding, reproduction, and habitat of pests, thereby inhibiting the development of pest populations, thereby achieving the purpose of protecting plants from pests.
- the long-lasting phosphor contained in the bionic rubber of the invention absorbs sunlight energy during the day, emits light of different colors (bands) at night, synergizes with the plant odor to enhance the attracting effect of the pest, and improves the efficiency of the bionic gum.
- the bionic rubber of the invention can be sprayed on the wintering and summering places of the pests, and the adhesion to the wintering and the summery insects can not reach the normal wintering and summering places, and the wintering and the summering base are reduced, thereby reducing the pests.
- the biomimetic glue of the present invention can also be sprayed on various color plates to form viscous glue drops on the color plates to trap pests which are apt to color, thereby protecting the target plants from pests.
- the biomimetic glue of the invention has the following advantages: (1)
- the biomimetic glue of the invention is an aqueous glue, uses water as a solvent, completely avoids organic solvent, is safe, non-toxic and non-polluting; (2)
- the bionic rubber has high contact viscosity and good wettability, and the touched glue droplets of any part of the body such as the feet, tentacles and wings of the pest are adhered; (3)
- the bionic rubber of the invention is not afraid of wind, rain, sun, Anti-ultraviolet, anti-aging, can play the role of armyworm for a long time;
- the biomimetic glue of the invention has low viscosity at room temperature (10 ⁇ 40 °C), and can be directly sprayed on the surface of plant leaves by ordinary agricultural sprayer, and It will have adverse effects on photosynthesis and normal growth of plants, and the method of use is relatively simple; (5)
- the fluorescent substances or insect pheromones contained in the biomimetic rubber of the invention can enhance
- the raw material composition of the biomimetic rubber is: 25 kg of butyl acrylate, 20 kg of isooctyl acrylate, 1 kg of acrylic acid, 200 g of sodium decyl sulfate, 200 g of ammonium persulfate, and C25 (isothiazolone) 10 g, silicone defoamer 20 g, nonylphenol ethoxylate (OP-10) 100 g, go
- the ionized water is 53.47 kg; the blue-violet aluminate long afterglow luminous powder 1 Kg and the thrips sex pheromone 1 g are added.
- the pheromone sex pheromone lg was added to the phosphor-containing biomimetic gel prepared above before use, and the mixture was sufficiently stirred to obtain a biomimetic gel containing an insect sex pheromone.
- the raw material composition of the bionic rubber is: 30 kg of butyl acrylate, 16 kg of methyl methacrylate, 3 kg of methacrylic acid, 600 g of sodium decyl sulfate, 400 g of potassium persulfate, and Broll (BR0N0P0L) (bronol) anti-fungal agent 10 g, mineral oil defoamer 100 g, nonylphenol ethoxylate (OP-10) 300 g, deionized water 49. 59 kg o
- the raw material composition of the biomimetic rubber is: butyl methacrylate 30 kg, octyl acrylate 20 kg, acrylic acid 5 kg, mercapto ether sulfate 800 g, sodium persulfate 600 g, Huake-108 (2-n-octyl group- 4-isothiazolin-3-one) 10 g antifungal agent, silicone defoamer 200 g, nonylphenol ethoxylate (OP-10) 300 g, deionized water 43. 09 kg; additional silicon Aluminate long afterglow phosphor 4 kg.
- the key indicator of the performance of bionic rubber is the initial viscosity.
- the detection method refers to the "People's Republic of China National Standard GB/T 4852-2002 Pressure Sensitive Adhesive Tape Initial Adhesion Test Method (Rolling Ball Method)" Method B: Chute Rolling Ball Method ".
- the specific method is as follows:
- test piece Apply bionic rubber to a 25-inch wide, 150-inch-long hard paper (produced by Guangdong Junda Paper Co., Ltd.) with a thickness of 10-15 ⁇ m. The test was allowed to stand horizontally for 2 hours at 23 ° C and 50% relative humidity before the test. The test samples were the biomimetic gels prepared in Examples 1, 2, and 3.
- the test piece is glued face up and fixed flat on the position specified by the BF-NX-770 tape initial tack tester (manufactured by Dongguan Bell Test Equipment Co., Ltd.).
- the inclined groove ball device has an inclination angle of 21. 30'. Place the ball (14 fl steel ball (diameter 11.112 ⁇ )) at the specified starting position, operate the lever to roll the ball, and measure the distance the ball stops rolling. This distance is the length from the end of the inclined groove to the center point where the ball contacts the adhesive surface when the ball stops. Repeat 3 times. The initial viscosity of the bionic rubber was expressed by the average of 3 times.
- Example 1 The bionic rubber of Example 1 had the shortest rolling distance and the highest initial tack, while the bionic rubber prepared in Example 3 had the longest rolling distance and a low initial tack.
- the smaller the detection value the larger the initial viscosity of the biomimetic rubber, the higher the sensitivity, and the pest insects are gently contacted with the glue droplets to be stuck, and the small insects of the insect body can also exert the armyworm effect.
- Biomimetic glue prepared in Example 3 65 mm Example 5. Comparison of bionic rubber in the control of thrips and hibiscus in the garden
- Example 1 The biomimetic rubber prepared in Example 1 was added to the Hummer sex pheromone (manufactured by Zhangzhou Yinggeer Technology Development Co., Ltd.) before use, and mixed uniformly.
- the dosage is 40 kg/667m 2 .
- Control 1 Deionized water; dosage 50 kg/667m
- Control 2 Myxoplasma liquid: Prepared according to the method described in the patent "A Blotting Liquid and Its Application” (CN200610025325.0). The formula is 5% polyacrylamide and 95% Taikoo oil. The dosage is 40Kg/667m 2 .
- Test method Select the normal-managed 5-year-old garden, and randomly select 20 trees for each treatment. Spray in the eucalyptus canopy with ordinary agricultural sprayer in late May, starting from the first day after spraying, every day at 10:00 am 00-11:00 test the net photosynthetic rate (P) of functional leaves in the middle of different treatments with LI-6400 photosynthetic apparatus (produced by LI-C0R, USA), measure 20 leaves per treatment, and measure for 7 days continuously. . Two weeks after the spraying, 10 trees were investigated for each treatment, and each tree was investigated for five leaves in the canopy according to the east, west, south and north directions. The Lima stuck on each leaf was counted ⁇ Psilothrips in icusB afti) Para trioza sinica Yang & Li, calculate the average number and standard deviation of pests on each leaf
- Control Mythimna, prepared according to the method of Example 1 disclosed in Patent CN 99120025.
- X the composition and ratio thereof are: 5% polyvinyl alcohol, 2% calcium 12-dodecylbenzenesulfonate, silicon Sodium 15%, polyvinylpyrrolidone 1%, water 77%. Diluted 200 times when used.
- biomimetic adhesive of the invention has good effect on the armyworm, and when it is kept sticky The length is long.
- Example 3 The biomimetic rubber prepared in Example 3 was sprayed on both sides of a commercially available yellow paperboard (color wax paper, manufactured by Guangdong Junda Paper Co., Ltd.) with a hand held sprayer.
- a commercially available yellow paperboard color wax paper, manufactured by Guangdong Junda Paper Co., Ltd.
- Control A commercially available yellow armyworm paper (double-sided film-adhesive board, CN 200820141844. 8 Zhangzhou Jiahe Biotechnology Co., Ltd.) was used as a control.
- Test method Cut the bionic rubber-treated yellow cardboard and the control yellow armyworm paper into lOcm X 10cm paper and hang it in the severely grown cucumber greenhouse (Trialeurodes vaporarioru (Westwood)). Hang 9 pieces, the height of the suspension is 10cm from the new shoot of cucumber, and 2 days after hanging, check the number of sticky white meal.
- results See Table 4
- the amount of yellow paperboard sprayed with the bionic rubber of the present invention was twice as high as that of the commercially available yellow armyworm paper.
- the bionic rubber of the invention can not only kill the whitefly in the daytime, but also emit yellow fluorescence at night, and has a stronger attracting effect.
- the results show that the bionic gummy insect of the present invention has a good effect.
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- Life Sciences & Earth Sciences (AREA)
- Health & Medical Sciences (AREA)
- General Health & Medical Sciences (AREA)
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Zoology (AREA)
- Pest Control & Pesticides (AREA)
- Plant Pathology (AREA)
- Agronomy & Crop Science (AREA)
- Dentistry (AREA)
- Wood Science & Technology (AREA)
- Environmental Sciences (AREA)
- Organic Chemistry (AREA)
- Toxicology (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Agricultural Chemicals And Associated Chemicals (AREA)
- Insects & Arthropods (AREA)
- Biotechnology (AREA)
- Microbiology (AREA)
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- Catching Or Destruction (AREA)
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Abstract
Description
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Priority Applications (3)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN201080041740.XA CN102712835B (zh) | 2010-11-29 | 2010-11-29 | 一种仿生胶及其制备方法与应用 |
US13/989,873 US9226496B2 (en) | 2010-11-29 | 2010-11-29 | Biomimetic adhesive and preparation method and application thereof |
PCT/CN2010/079249 WO2012071698A1 (zh) | 2010-11-29 | 2010-11-29 | 一种仿生胶及其制备方法与应用 |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
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PCT/CN2010/079249 WO2012071698A1 (zh) | 2010-11-29 | 2010-11-29 | 一种仿生胶及其制备方法与应用 |
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WO2012071698A1 true WO2012071698A1 (zh) | 2012-06-07 |
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Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
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PCT/CN2010/079249 WO2012071698A1 (zh) | 2010-11-29 | 2010-11-29 | 一种仿生胶及其制备方法与应用 |
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US (1) | US9226496B2 (zh) |
CN (1) | CN102712835B (zh) |
WO (1) | WO2012071698A1 (zh) |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN103254855A (zh) * | 2013-05-21 | 2013-08-21 | 苏州富通高新材料科技股份有限公司 | 一种防虫地板粘合剂 |
Families Citing this family (8)
Publication number | Priority date | Publication date | Assignee | Title |
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CN105766494A (zh) * | 2014-12-24 | 2016-07-20 | 中国医学科学院药用植物研究所 | 一种用于预防植物冻害和虫草害的用品、及其用途 |
CN105038291A (zh) * | 2015-05-29 | 2015-11-11 | 安徽美翔塑业有限公司 | 一种驱虫地膜及其制作工艺 |
CN106359337A (zh) * | 2016-10-17 | 2017-02-01 | 广州瑞丰生物科技有限公司 | 一种新型纸质粘虫板 |
CN106634729A (zh) * | 2016-11-02 | 2017-05-10 | 吴迪 | 一种室外持粘性诱食性粘虫胶的制备方法 |
CN107251910B (zh) * | 2017-06-27 | 2020-04-07 | 北京林业大学 | 一种防治美国白蛾的增效性拒食剂及其使用方法 |
CN109181589A (zh) * | 2018-08-31 | 2019-01-11 | 黄旭东 | 一种环保粘虫胶板及其制备方法 |
EP4133940A4 (en) * | 2020-04-06 | 2024-06-05 | Nichiban Co.,Ltd. | PRESSURE-SENSITIVE ADHESIVE TAPE CONTAINING AN AGROCHEMICAL PRODUCT |
EP4356732A1 (en) | 2022-10-20 | 2024-04-24 | Wageningen Universiteit | Method for producing an aqueous suspension of adhesive particles for trapping plant pests |
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- 2010-11-29 CN CN201080041740.XA patent/CN102712835B/zh not_active Expired - Fee Related
- 2010-11-29 WO PCT/CN2010/079249 patent/WO2012071698A1/zh active Application Filing
- 2010-11-29 US US13/989,873 patent/US9226496B2/en active Active
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KR100959909B1 (ko) * | 2009-10-01 | 2010-05-26 | 일진테이프(주) | 수용성 축광 점착 스프레이장치 및 이의 사용방법 |
CN101845282A (zh) * | 2010-01-18 | 2010-09-29 | 宝鸡市广仁生物科技有限公司 | 粘虫胶粘剂的组成及其制备方法 |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
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CN103254855A (zh) * | 2013-05-21 | 2013-08-21 | 苏州富通高新材料科技股份有限公司 | 一种防虫地板粘合剂 |
Also Published As
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CN102712835A (zh) | 2012-10-03 |
CN102712835B (zh) | 2014-10-15 |
US9226496B2 (en) | 2016-01-05 |
US20140186286A1 (en) | 2014-07-03 |
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