WO2019004007A1 - Agent antibuée de type revêtement pour films à usage agricole, et film à usage agricole - Google Patents

Agent antibuée de type revêtement pour films à usage agricole, et film à usage agricole Download PDF

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Publication number
WO2019004007A1
WO2019004007A1 PCT/JP2018/023279 JP2018023279W WO2019004007A1 WO 2019004007 A1 WO2019004007 A1 WO 2019004007A1 JP 2018023279 W JP2018023279 W JP 2018023279W WO 2019004007 A1 WO2019004007 A1 WO 2019004007A1
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WO
WIPO (PCT)
Prior art keywords
antifogging
film
mass
water
synthetic resin
Prior art date
Application number
PCT/JP2018/023279
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English (en)
Japanese (ja)
Inventor
佐藤　弘一
勇 田口
Original Assignee
理研ビタミン株式会社
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Publication date
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Priority to JP2019526826A priority Critical patent/JPWO2019004007A1/ja
Publication of WO2019004007A1 publication Critical patent/WO2019004007A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
    • C08J7/04—Coating
    • C08J7/043—Improving the adhesiveness of the coatings per se, e.g. forming primers
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01G—HORTICULTURE; CULTIVATION OF VEGETABLES, FLOWERS, RICE, FRUIT, VINES, HOPS OR SEAWEED; FORESTRY; WATERING
    • A01G9/00—Cultivation in receptacles, forcing-frames or greenhouses; Edging for beds, lawn or the like
    • A01G9/14—Greenhouses
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
    • C08J7/04—Coating
    • C08J7/054—Forming anti-misting or drip-proofing coatings
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/01—Use of inorganic substances as compounding ingredients characterized by their specific function
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/34—Silicon-containing compounds
    • 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
    • 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
    • C09K3/00—Materials not provided for elsewhere

Definitions

  • the present invention relates to an antifogging agent to be used by applying to a film for agricultural use, and a film having an antifogging property which is sustained for a long time by applying the antifogging agent.
  • an antifogging agent composition containing an aqueous emulsion of a specific acrylic resin and an inorganic colloidal sol in a specific amount Patent Document 1
  • Method of preparing an anti-fogging agent composition containing a specific amount of a colloidal sol and a surfactant Patent Document 2
  • a composition for forming an antifogging coating film comprising a specific ratio of colloidal silica particles of a specific average particle size and at least one selected from colloidal alumina particles
  • An antifogging coating layer comprising a synthetic resin binder and chain-like colloidal silica is provided on one side of a synthetic resin-coated material base layer, which has good storage stability.
  • Antifogging agricultural coating material (Patent Document 4), characterized by containing a (meth) acrylic acid copolymer and a hydrophilic substance produced using an emulsifier having a specific reactive polymerization group.
  • Antifogging paint composition (Patent Document 5), a monomer mixture containing at least (A) (meth) acrylic acid alkyl ester and (meth) acrylic acid as monomers in the presence of a reactive nonionic emulsifier
  • a film-forming resin composition containing a (meth) acrylic copolymer obtained by emulsion polymerization, (B) inorganic colloid sol, (C) aliphatic alcohol having 1 to 10 carbon atoms, and (D) water Composition containing a component and having a minimum film forming temperature of -25.degree.
  • Patent Document 6 necklace-like colloidal silica in which primary particles of colloidal silica are bound cyclically, primary particles of colloidal silica Form a chain
  • the chain colloidal silica, and antifogging composition characterized by containing a binder resin in a specific ratio (Patent Document 7), and the like have been disclosed.
  • the coating film may be detached from the surface of the film after a certain period of time, and the antifogging property may not be maintained. Therefore, there has been a demand for an antifogging agent which can impart long-lasting antifogging properties (hereinafter referred to as "long-term antifogging property").
  • JP-A-62-246984 Japanese Patent Application Laid-Open No. 63-150369 Unexamined-Japanese-Patent No. 6-122851 Japanese Patent Application Laid-Open No. 7-327522 JP, 2006-16578, A JP, 2008-50492, A JP, 2015-168692, A
  • the present inventors have made it possible to obtain an antifogging agent comprising an inorganic inorganic fine particle, a water-soluble alkali metal silicate and a synthetic resin in a specific ratio to an agricultural film. It discovered that the said subject was solved by apply
  • the present invention also includes the following inventions and the like.
  • the film By applying the coating type antifogging agent for agricultural films of the present invention (hereinafter referred to as “the antifogging agent of the present invention") to an agricultural film, the film has an initial antifogging property (immediate effect of antifogging effect) As well as long-term anti-fog can be imparted.
  • the agricultural film coated with the antifogging agent of the present invention has the transparency required for the agricultural film.
  • Evaluation box for evaluating anti-fogging property and thermostatic water tank 1: Evaluation box 2: Window of evaluation box 3: 3: Constant-temperature water tank. A constant temperature water tank equipped with an evaluation box for evaluating the antifogging property. 1: Evaluation box 3: 3: Constant-temperature water tank 4: 4: A film attached to the window of the evaluation box.
  • the (A) colloidal inorganic fine particles (hereinafter also referred to as “component (A)”) used for the antifogging agent of the present invention are inorganic fine particles.
  • the inorganic substance include silica, alumina, titanium oxide, iron hydroxide, tin hydroxide or barium sulfate and the like, with preference given to silica or alumina. These inorganic substances may be used alone or in combination of two or more.
  • the shape of the fine particles is not particularly limited, and examples thereof include chains, spheres, and necklaces.
  • colloidal inorganic fine particles include, for example, silica sol (trade name: Snowtex; solid content 20% by mass; Nissan Chemical Industries, Ltd.) or alumina sol (trade name: AS-520; solid) 20% by mass (manufactured by Nissan Chemical Industries, Ltd.) and the like, and these can be used in the present invention.
  • the (B) water-soluble alkali metal silicate (hereinafter also referred to as “component (B)”) used for the antifogging agent of the present invention is a compound represented by M 2 O ⁇ nSiO 2 .
  • M include Li (lithium), Na (sodium), K (potassium) and the like, preferably Li (lithium) or Na (sodium), and particularly preferably Li (lithium).
  • n means SiO 2 / M 2 O (molar ratio), and the numerical value is not particularly limited as long as the alkali metal silicate becomes water soluble, but in the case where M is Li (lithium) , Preferably 3.5 to 7.5, when M is Na (sodium), preferably 2.0 to 4.0, and when M is K (potassium), preferably 2.0 to 4.0. It is.
  • (B) water-soluble alkali metal silicate is water-soluble, it is distinguished from colloidal inorganic fine particles.
  • water-soluble alkali metal silicate examples include lithium silicate, sodium silicate and potassium silicate, preferably lithium silicate or sodium silicate, particularly preferably silicic acid. It is lithium.
  • the (C) synthetic resin (hereinafter also referred to as "(C) component") used for the antifogging agent of the present invention is particularly limited as long as it is a resin capable of bringing the antifogging agent of the present invention into close contact with agricultural films.
  • water-insoluble synthetic resins or water-soluble synthetic resins can be used alone or in combination.
  • water-insoluble synthetic resin examples include acrylic resin, acrylic styrene resin, vinyl acetate resin, vinyl acetate acrylic resin, vinyl acetate beige resin, ethylene vinyl acetate resin, urethane resin, epoxy resin, epoxy resin, phenol resin, alkyd resin or polyester resin or These copolymer resins, hybrid resins, modified resins, etc. are mentioned, Preferably they are an acrylic resin or a urethane resin. These water-insoluble synthetic resins may be used alone or in combination of two or more.
  • acrylic resin examples include polymers or copolymers of acrylic acid monomers, and copolymers of acrylic acid monomers and other monomers.
  • acrylic acid type monomer acrylic acid, acrylic acid ester, methacrylic acid, methacrylic acid ester, maleic acid, maleic anhydride, fumaric acid, crotonic acid, itaconic acid, ethylenesulfonic acid, 2-acrylamido-2-, for example Methylpropanoic acid, hydroxyl group-containing vinyl monomer of acrylic acid derivative, hydroxyl group-containing vinyl monomer of methacrylic acid derivative, acrylonitriles, acrylamides, glycidyl (meth) acrylate, glycidyl esters of acrylic acid or glycidyl of methacrylic acid Esters etc. are mentioned.
  • Examples of the other monomers include vinyl acetate, N-vinyl pyrrolidone or a derivative thereof, N-vinyl acetamide, ethylene-vinyl acetate and the like.
  • the urethane resin is a polymer compound obtained by reacting polyisocyanate and polyol.
  • the polyisocyanate include aliphatic isocyanates such as hexamethylene diisocyanate and isophorone diisocyanate
  • polyols include polyether polyols such as polyethylene glycol or polypropylene glycol, and polyesters such as polyethylene adipate glycol or polybutylene adipate glycol.
  • Polyol or polycarbonate polyol such as polybutylene carbonate diol or polyhexamethylene carbonate diol, etc. may be mentioned.
  • the water-insoluble synthetic resin is preferably used in the form of an emulsion in which the water-insoluble synthetic resin is dispersed in the form of particles in water and / or a water-soluble dispersion medium.
  • emulsions of water-insoluble synthetic resins include acrylic resin emulsions (trade name: NeoCryl A-6057; solid content 35% by mass; Kushimoto Chemical Co., Ltd.) or urethane resin emulsions (trade name: NeoRez) R-986; solid content 35% by mass; manufactured by Kushimoto Chemical Co., Ltd.) and the like, and these can be used in the present invention.
  • water-soluble synthetic resin examples include polyvinyl alcohol, polyethylene oxide, polyacrylic acid, polyvinyl pyrrolidone, carboxymethyl cellulose, methyl cellulose, hydroxyethyl cellulose, carboxyvinyl polymer and the like, with preference given to polyvinyl alcohol or polyethylene oxide. These water-soluble synthetic resins may be used alone or in combination of two or more.
  • polyvinyl alcohol (trade name: KL-03; manufactured by Nippon Synthetic Chemical Co., Ltd.) or polyethylene oxide (trade name: L-6; manufactured by Meisei Chemical Industry Co., Ltd.), etc.
  • KL-03 manufactured by Nippon Synthetic Chemical Co., Ltd.
  • polyethylene oxide trade name: L-6; manufactured by Meisei Chemical Industry Co., Ltd.
  • the antifogging agent of the present invention may contain (D) a solvent or a dispersion medium (hereinafter simply referred to as "solvent etc.”).
  • solvent etc. a solvent or a dispersion medium
  • the (D) solvent and the like (hereinafter also referred to as "(D) component") used for the antifogging agent of the present invention the (A) to (C) components contained in the antifogging agent of the present invention can be dissolved and dispersed.
  • the ratio of water to the entire component (D) is, for example, 10% by mass or more (for example, 20% by mass or more), preferably 30% by mass or more (for example, 40% by mass) More preferably, it may be about 50 mass% or more (for example, 60 mass% or more), or more than 70 mass% (for example, 75 mass% or more, 80 mass% or more, 85 mass% or more, 90 mass%) The above may be 95% by mass or more.
  • the antifogging agent of the present invention may contain any additive which is generally used for a coating type antifogging agent as long as the object of the present invention is not impaired.
  • antifoaming agent plasticizer, coalescent agent Agents, thickeners, pigments, pigment dispersants, weatherability improvers, heat stabilizers, leveling agents, crosslinking agents, dispersants and the like.
  • the solid content of the (C) synthetic resin is 30 to 150 parts by mass, preferably 50 to 150 parts by mass, and the solid content of the synthetic resin (C) is 30 to 150 parts by mass, preferably 60 to 150 parts by mass.
  • the compounding amount of the solvent (D) and the like contained in the antifogging agent of the present invention is not particularly limited as long as it can dissolve and disperse the components (A) to (C).
  • the total solid concentration of the components (A) to (C) in 100% by mass of the clouding agent is adjusted so as to be usually 0.5 to 10% by mass, preferably 1 to 5% by mass.
  • the solid content in the present invention is the residual amount when a 10 mg sample is heated at 105 ° C. for 2 hours under a nitrogen atmosphere using a residual amount thermogravimeter (model: TGA 55; manufactured by TA Instruments).
  • the antifogging agent of the present invention can be obtained by uniformly mixing each component [at least (A) to (C) components, such as (A) to (D) components].
  • each component at least (A) to (C) components, such as (A) to (D) components.
  • a well-known stirrer, a mixer, etc. can be used.
  • the mixing conditions are not particularly limited as long as each component [for example, the components (A) to (D)] can be uniformly mixed, but, for example, a method of mixing at 25 to 60 ° C. for 180 to 360 minutes Can be mentioned.
  • An agricultural film formed by applying the antifogging agent of the present invention on at least one surface of a synthetic resin film surface is also one of the embodiments of the present invention.
  • the synthetic resin used for the above synthetic resin film is not particularly limited, and examples thereof include polyethylene, polypropylene, ethylene-propylene copolymer, ethylene-butene copolymer, ethylene-4-methyl-1-pentene copolymer, etc.
  • Polyolefin resins, ethylene-vinyl acetate copolymers, ethylene-acrylic acid copolymers, polyvinyl chloride and the like may be mentioned, and one or more of these may be used in combination.
  • the above-mentioned synthetic resin film may contain, in addition to the above-mentioned synthetic resin, any additive generally used in the synthetic resin film.
  • any additive generally used in the synthetic resin film for example, an antioxidant, a weathering agent, an ultraviolet absorber, an infrared absorber, a lubricant, Antiblocking agents, antifog agents, heat retaining agents, pigments and the like can be mentioned.
  • the synthetic resin film is not particularly limited as long as the synthetic resin or the synthetic resin composition in which the additive is blended into the synthetic resin is molded into a film, and, for example, an inflation molding method, a T-die molding method, etc. What was shape
  • the synthetic resin film may be a single layer or a multilayer.
  • the thickness of the synthetic resin film is not particularly limited as long as it is a thickness suitable for agricultural use, but in consideration of film strength, weight and the like, it is usually 50 to 200 ⁇ m, preferably 80 to 150 ⁇ m.
  • the surface of the synthetic resin film is preferably subjected to pretreatment such as plasma discharge treatment and corona discharge treatment in advance in order to improve the coating properties and adhesion of the antifogging agent of the present invention.
  • the antifogging agent of the present invention containing a solvent or the like is applied to at least one surface of a synthetic resin film surface, and the solvent or the like in the antifogging agent is removed An antifogging layer is formed on at least one surface of the synthetic resin film surface.
  • the coating method is not particularly limited, and examples thereof include blade coating method, roll coating method, dip coating method, bar coating method, spray coating method, rod coating method, knife coating method and brush coating method.
  • the coating amount of the antifogging agent of the present invention on the synthetic resin film is usually 0.1 to 2 g / l converted to the amount of the antifogging layer from which the solvent (D) and the like have been removed after application to the synthetic resin film surface.
  • m 2 preferably 0.2 to 1 g / m 2 .
  • the method of drying is mentioned.
  • the drying method is not particularly limited, and examples thereof include a natural drying method or a forced drying method such as a hot air drying method, an infrared drying method or a far infrared drying method.
  • the drying temperature is usually 50 to 120 ° C. , Preferably 55 to 75 ° C.
  • Formulations of coating type antifogging agents (hereinafter simply referred to as “antifogging agents") 1 to 13 for agricultural films produced using the above-mentioned raw materials are shown in Tables 1 to 5.
  • the antifogging agents 1 to 9 are examples of the present invention, and the antifogging agents 10 to 13 are comparative examples to them.
  • Tables 1 to 5 (A) colloidal inorganic fine particles, (B) water-soluble alkali metal silicate, (C) synthetic resin and (D) solvent, etc. are simply referred to as (A), (B), It described as (C) and (D).
  • the kneaded product is formed into a 100 ⁇ m thick film by inflation molding, and then the film is treated with a corona processor (type: ASA-4; corona treatment) Corona treatment was performed using an intensity of 36 dyne (manufactured by Shinko Electric Instruments Co., Ltd.).
  • the container was placed in the tank and the initial antifogging property was evaluated.
  • the initial antifogging property the state of agricultural films 1 to 14 was visually observed, and the time until the film surface was uniformly wet (water became thin and water was not removed) was measured. The measured time was symbolized by the following evaluation criteria. The results are shown in Table 6. In addition, it can be said that it is excellent in initial stage antifogging property that a result is (circle), and it can be said that it is especially excellent if it is (double-circle). :: Less than 15 minutes ⁇ : More than 15 minutes, less than 30 minutes ⁇ : More than 30 minutes, less than 45 minutes ⁇ : More than 45 minutes
  • agricultural films 1 to 9 coated with the antifogging agents 1 to 9, which are examples of antifogging agents, have not only initial antifogging properties but also long-term antifogging properties.
  • agricultural films 10 and 11 coated with antifogging agents 10 and 11 which are comparative examples had initial antifogging properties but did not have long-term antifogging properties.
  • the agricultural films 12 and 13 coated with the antifogging agents 12 and 13 not only did not have long-term antifogging properties, but also did not have initial antifogging properties.
  • novel antifogging agents and the like can be provided.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Environmental Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Coating Of Shaped Articles Made Of Macromolecular Substances (AREA)
  • Paints Or Removers (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Protection Of Plants (AREA)
  • Greenhouses (AREA)

Abstract

La présente invention concerne un agent antibuée qui est susceptible de conférer à un film à usage agricole des propriétés antibuées à long terme. L'agent antibuée de type revêtement pour films à usage agricole contient : (A) de fines particules inorganiques colloïdales, (B) un sel de silicate de métal alcalin soluble dans l'eau et (C) une résine synthétique. Cet agent antibuée de type revêtement pour films à usage agricole est conçu de sorte que, par rapport à 100 parties en masse de la teneur en matières solides des fines particules inorganiques colloïdales (A), la teneur en matières solides du sel de silicate de métal alcalin soluble dans l'eau (B) est de 30 à 150 parties en masse et la teneur en matières solides de la résine synthétique (C) est de 30 à 150 parties en masse.
PCT/JP2018/023279 2017-06-26 2018-06-19 Agent antibuée de type revêtement pour films à usage agricole, et film à usage agricole WO2019004007A1 (fr)

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Application Number Priority Date Filing Date Title
JP2019526826A JPWO2019004007A1 (ja) 2017-06-26 2018-06-19 農業用フィルム用塗布型防曇剤及び農業用フィルム

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JP2017-124394 2017-06-26

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN116904077A (zh) * 2023-09-13 2023-10-20 山东森博斯特塑胶科技有限公司 一种po膜涂覆液及其制备方法

Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH06122851A (ja) * 1991-05-29 1994-05-06 C I Kasei Co Ltd 防曇性塗膜形成用組成物及びこれを用いた農業用防曇性塩化ビニル系樹脂フイルム
JPH06145389A (ja) * 1991-08-14 1994-05-24 Toray Gosei Film Kk 農業用被覆フィルム及びその製造方法
JP2000256579A (ja) * 1999-03-08 2000-09-19 Nippon Light Metal Co Ltd 親水性塗料組成物及びその組成物からなる親水性皮膜
JP2001031907A (ja) * 1999-07-23 2001-02-06 Toto Ltd 水性塗料組成物およびその塗装膜
JP2003089760A (ja) * 2001-09-18 2003-03-28 Toto Ltd 水性塗料組成物、およびその塗膜を形成した部材
JP2003096394A (ja) * 2001-09-19 2003-04-03 Toto Ltd 水性塗料組成物、およびその塗膜を形成した部材
JP2011513513A (ja) * 2008-02-21 2011-04-28 デュポン・テイジン・フィルムズ・ユー・エス・リミテッド・パートナーシップ シリケートを含有する防曇コーティング

Patent Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH06122851A (ja) * 1991-05-29 1994-05-06 C I Kasei Co Ltd 防曇性塗膜形成用組成物及びこれを用いた農業用防曇性塩化ビニル系樹脂フイルム
JPH06145389A (ja) * 1991-08-14 1994-05-24 Toray Gosei Film Kk 農業用被覆フィルム及びその製造方法
JP2000256579A (ja) * 1999-03-08 2000-09-19 Nippon Light Metal Co Ltd 親水性塗料組成物及びその組成物からなる親水性皮膜
JP2001031907A (ja) * 1999-07-23 2001-02-06 Toto Ltd 水性塗料組成物およびその塗装膜
JP2003089760A (ja) * 2001-09-18 2003-03-28 Toto Ltd 水性塗料組成物、およびその塗膜を形成した部材
JP2003096394A (ja) * 2001-09-19 2003-04-03 Toto Ltd 水性塗料組成物、およびその塗膜を形成した部材
JP2011513513A (ja) * 2008-02-21 2011-04-28 デュポン・テイジン・フィルムズ・ユー・エス・リミテッド・パートナーシップ シリケートを含有する防曇コーティング

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN116904077A (zh) * 2023-09-13 2023-10-20 山东森博斯特塑胶科技有限公司 一种po膜涂覆液及其制备方法
CN116904077B (zh) * 2023-09-13 2023-11-24 山东森博斯特塑胶科技有限公司 一种po膜涂覆液及其制备方法

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