WO2018155389A1 - Coating agent composition for agricultural film and modified thermoplastic polymer film for agriculture - Google Patents

Coating agent composition for agricultural film and modified thermoplastic polymer film for agriculture Download PDF

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Publication number
WO2018155389A1
WO2018155389A1 PCT/JP2018/005785 JP2018005785W WO2018155389A1 WO 2018155389 A1 WO2018155389 A1 WO 2018155389A1 JP 2018005785 W JP2018005785 W JP 2018005785W WO 2018155389 A1 WO2018155389 A1 WO 2018155389A1
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Prior art keywords
mass
agricultural
thermoplastic polymer
film
water
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PCT/JP2018/005785
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French (fr)
Japanese (ja)
Inventor
和史 潮谷
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竹本油脂株式会社
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Application filed by 竹本油脂株式会社 filed Critical 竹本油脂株式会社
Priority to CN201880012209.6A priority Critical patent/CN110300516A/en
Priority to KR1020197027304A priority patent/KR102131398B1/en
Publication of WO2018155389A1 publication Critical patent/WO2018155389A1/en

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Classifications

    • 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
    • A01G13/00—Protecting plants
    • A01G13/02—Protective coverings for plants; Coverings for the ground; Devices for laying-out or removing coverings
    • 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
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B23/00—Layered products comprising a layer of cellulosic plastic substances, i.e. substances obtained by chemical modification of cellulose, e.g. cellulose ethers, cellulose esters, viscose
    • B32B23/04—Layered products comprising a layer of cellulosic plastic substances, i.e. substances obtained by chemical modification of cellulose, e.g. cellulose ethers, cellulose esters, viscose comprising such cellulosic plastic substance as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • B32B23/08—Layered products comprising a layer of cellulosic plastic substances, i.e. substances obtained by chemical modification of cellulose, e.g. cellulose ethers, cellulose esters, viscose comprising such cellulosic plastic substance as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B23/00—Layered products comprising a layer of cellulosic plastic substances, i.e. substances obtained by chemical modification of cellulose, e.g. cellulose ethers, cellulose esters, viscose
    • B32B23/14—Layered products comprising a layer of cellulosic plastic substances, i.e. substances obtained by chemical modification of cellulose, e.g. cellulose ethers, cellulose esters, viscose characterised by containing special compounding ingredients
    • B32B23/18—Fillers
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B23/00—Layered products comprising a layer of cellulosic plastic substances, i.e. substances obtained by chemical modification of cellulose, e.g. cellulose ethers, cellulose esters, viscose
    • B32B23/22—Layered products comprising a layer of cellulosic plastic substances, i.e. substances obtained by chemical modification of cellulose, e.g. cellulose ethers, cellulose esters, viscose comprising ethers
    • 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
    • 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
    • C08J7/12—Chemical modification
    • C08J7/16—Chemical modification with polymerisable compounds
    • C08J7/18—Chemical modification with polymerisable compounds using wave energy or particle radiation
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L1/00—Compositions of cellulose, modified cellulose or cellulose derivatives
    • C08L1/02—Cellulose; Modified cellulose
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L1/00—Compositions of cellulose, modified cellulose or cellulose derivatives
    • C08L1/08—Cellulose derivatives
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L83/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon only; Compositions of derivatives of such polymers
    • C08L83/10—Block- or graft-copolymers containing polysiloxane sequences
    • C08L83/12—Block- or graft-copolymers containing polysiloxane sequences containing polyether sequences
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D1/00—Coating compositions, e.g. paints, varnishes or lacquers, based on inorganic substances
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D101/00—Coating compositions based on cellulose, modified cellulose, or cellulose derivatives
    • C09D101/08—Cellulose derivatives
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
    • C09D5/02—Emulsion paints including aerosols
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
    • C09D7/40—Additives
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02A—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE
    • Y02A40/00—Adaptation technologies in agriculture, forestry, livestock or agroalimentary production
    • Y02A40/10—Adaptation technologies in agriculture, forestry, livestock or agroalimentary production in agriculture
    • Y02A40/25—Greenhouse technology, e.g. cooling systems therefor

Definitions

  • the present invention relates to a coating composition for agricultural films used as a covering material for agricultural houses and a modified thermoplastic polymer film for agriculture to which such a coating composition is attached.
  • thermoplastic polymer film is widely used as a covering material for agricultural houses.
  • thermoplastic polymer film itself has a hydrophobic property, there is a problem that it is likely to cause clouding and decrease the transmission of sunlight, resulting in poor growth of crops.
  • agricultural films added with an antifogging agent or coated with a dropping agent have been used (see, for example, Patent Documents 1 to 3).
  • these conventional means after being stretched on an agricultural house, are able to obtain initial dripping properties, but repeatedly contact the house aggregate during long-term use, and such contact is dry. When it is carried out under conditions where the state and the wet state are repeated, there is a problem that the drip property is lost.
  • the conventional means is inferior in actual durability.
  • JP-A-9-298954 Japanese Patent Laid-Open No. 11-10784 Japanese Patent Laid-Open No. 2004-255807
  • the problem to be solved by the present invention is that after being stretched on an agricultural house, the initial drip property is good, and it repeatedly contacts with the aggregate of the agricultural house during long-term use.
  • a coating composition for agricultural film capable of maintaining good drip properties even when such contact is repeated in a dry state and a wet state, and agricultural use using such a composition It is in providing a modified thermoplastic polymer film.
  • a coating composition for agricultural films comprising an inorganic colloidal sol, a specific cellulose derivative, and a water-soluble crosslinking agent in a specific ratio. It was found to be correct and suitable.
  • the present invention is characterized in that the inorganic colloidal sol contains 30 to 70% by mass in terms of solid content, 20 to 60% by mass of the following cellulose derivative, and 1 to 30% by mass of a water-soluble crosslinking agent.
  • the present invention relates to an agricultural film coating agent composition.
  • the present invention also relates to an agricultural modified thermoplastic polymer film to which the agricultural film coating composition is attached.
  • the composition of the present invention comprises an inorganic colloidal sol in a proportion of 30 to 70% by mass in terms of solid content, 20 to 60% by mass of the above cellulose derivative, and 1 to 30% by mass of a water-soluble crosslinking agent.
  • the inorganic colloidal sol contains 40 to 67% by mass in terms of solid content, 30 to 50% by mass of the above cellulose derivative, and 3 to 25% by mass of a water-soluble crosslinking agent.
  • Crosslinker is preferably contained at a ratio of 10/1 to 10/5 (mass ratio).
  • silica sol and alumina sol examples include so-called silica sol and alumina sol. Commercially available water dispersions may be used, and these may be used alone or in combination.
  • Silica sols include cationic acidic silica sols such as Snowtex AK and Snowtex AK-L (all are trade names manufactured by Nissan Chemical Co., Ltd.), Snowtex 30, Snowtex 30L and Snowtex ZL (all are Nissan) Chemical product name), Cataloid SI-30, Cataloid SI-45P, Cataloid SI-80P (all of which are trade names made by JGC Catalysts & Chemicals), etc., anionic alkaline silica sol, Snowtex O, Snowtex OL (All are trade names manufactured by Nissan Chemical Co., Ltd.) and anionic acidic silica sols such as Cataloid SN (trade name manufactured by JGC Catalysts & Chemicals) are listed.
  • alumina sol examples include alumina sol 100, alumina sol 200, alumina sol 520 (and above). , Both are product names manufactured by Nissan Chemical Co., Ltd.), Cataloid A -1, Cataloid AS-2 (above all are JGC Catalysts and Chemicals Co., trade name) and cationic acidic alumina sol and the like.
  • a silanol-forming organic silane compound is hydrolyzed in the presence of the inorganic colloid sol, the resulting silanol compound is condensed and polymerized, and the condensation polymer is adhered to the surface of solid particles of the inorganic colloid sol.
  • a modified inorganic colloid sol can also be used.
  • the silanol-forming organosilane compound used for modifying the inorganic colloid sol include 1) trialkoxysilanes, 2) dialkoxysilanes, and 3) monoalkoxysilanes.
  • trialkoxysilanes include methyltrimethoxysilane, methyltriethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, ⁇ -chloropropyltripropoxysilane, ⁇ -mercaptopropyltriethoxysilane, ⁇ -glycidoxypropyltri Examples include methoxysilane, ⁇ -methacryloxypropyltriethoxysilane, ⁇ -ureidopropyltrimethoxysilane, and phenyltrimethoxysilane.
  • dialkoxysilanes examples include dimethyldimethoxysilane, ⁇ -chloropropylmethyldimethoxysilane, and ⁇ -glycol.
  • Sidoxypropylmethyldimethoxysilane and the like, and monoalkoxysilanes include trimethylmethoxysilane and the like.
  • ⁇ -glycidoxypropyltrimethoxysilane, ⁇ -ureidopropyltrimethoxysilane, and methyltriethoxysilane are preferable as the silanol-forming organosilane compound.
  • Such a silanol-forming organosilane compound is preferably used at a ratio of 1 to 30 parts by mass with respect to 100 parts by mass in terms of solid content of the inorganic colloid sol.
  • the cellulose derivative used for the composition of the present invention is at least one selected from carboxymethylcellulose metal salt, hydroxyethylcellulose, hydroxypropylmethylcellulose and methylcellulose. These can be used alone or in combination.
  • Such a cellulose derivative preferably has a viscosity of 1 to 600 mPa ⁇ s at 20 ° C. in a 2% by weight aqueous solution, more preferably 1 to 400 mPa ⁇ s.
  • water-soluble crosslinking agent to be used in the composition of the present invention examples include water-soluble melamine, water-soluble epoxy, water-soluble oxazoline, water-soluble aziridin, and the like, but water-soluble melamine is preferable.
  • water-soluble melamine commercially available products can be used.
  • composition of the present invention can further contain a polyether-modified silicone.
  • a polyether-modified silicone is used at a ratio of 0.1 to 50 parts by mass with respect to 100 parts by mass in terms of solid content of the inorganic colloidal sol.
  • a commercially available product can be used as it is.
  • examples of such commercial products include TSF4440, TSF4441, TSF4445, TSF4446, TSF4452, and TSF4460 (all of which are trade names of Momentive Performance Materials Japan), X22-4952, X-22-4272, KF-6123, KF-351A, KF-352A, KF-353, KF-354L, KF-355A, KF-615A, KF-945, KF-640, KF-642, KF-643, KF-644, KF- 6204, X-22-4515, KF-6004 (all are trade names manufactured by Shin-Etsu Silicone), SH8700, SH8410, SH8400, L-7002, FZ-2104, FZ-77, L-7604, FZ-2203 , FZ-2208 (above, either Although manufactured by Dow Corning Toray Co., Ltd. under the trade name) and the like, and among
  • the film of the present invention is such that the above-described composition of the present invention adheres in a solid content of 0.15 to 0.5 g / m 2 on the surface-treated surface of a thermoplastic polymer film.
  • thermoplastic resin used in the film of the present invention examples include 1) polyolefin resin, 2) polyvinyl chloride resin, and 3) polyester resin.
  • polyolefin resins include homopolymers of ⁇ -olefins such as polyethylene and polypropylene, ethylene-propylene copolymers, ethylene / 1-butene copolymers, ethylene / 4-methyl-1-pentene copolymers, ethylene ⁇ -olefin copolymer such as 1-hexene copolymer, ethylene / 1-octene copolymer, ethylene / vinyl acetate copolymer, ethylene / methyl methacrylate copolymer, ethylene / vinyl acetate / methyl methacrylate copolymer Copolymers and copolymers with different monomers mainly composed of ⁇ -olefin such as ionomer resins.
  • polyvinyl chloride resins include polyvinyl chloride, vinyl chloride / ethylene copolymers, vinyl chloride / acetic acid. Examples include vinyl copolymers, vinyl chloride / methyl methacrylate copolymers, and polyvinylidene chloride. As the polyester-based resin and polyethylene terephthalate. These may be used by blending a plurality of types of thermoplastic resins. Of these, polyolefin resins are preferred as the thermoplastic resin.
  • the ⁇ -olefin copolymer in the polyolefin resin is more preferably obtained by a gas phase method, a solution polymerization method, etc., using a known homogeneous catalyst such as a highly active Ziegler catalyst or a metallocene catalyst. Is particularly preferably 0.86 to 0.94 g / cm 3 and MFR 0.01 to 20 g / 10 min.
  • the polyolefin resin can be used by mixing two or more polyolefin resins. These thermoplastic resins contain commonly used antioxidants, weathering agents, ultraviolet absorbers, infrared absorbers, lubricants, antiblocking agents, antifogging agents, antifogging agents, heat retention agents, pigments, etc. as necessary. Can be contained.
  • the method for producing the thermoplastic polymer film used for the film of the present invention is not particularly limited, and examples thereof include an inflation molding method and a T-die molding method.
  • the film may be a single layer film or a multilayer film, and may be an unstretched film or a stretched film.
  • a thermoplastic polymer film made of the polyolefin resin formed by inflation molding is suitable.
  • the film of the present invention is preferably one in which the surface of the thermoplastic polymer film to be coated with the composition of the present invention is subjected to surface treatment and then the composition of the present invention is coated.
  • the surface treatment can be performed by a known method such as corona discharge treatment, atmospheric pressure plasma treatment, flame treatment, etc., but corona discharge treatment is preferred.
  • the wetting tension of the surface treated surface is preferably 35 mN / m or more, more preferably 35 to 70 mN / m. In the present invention, the wetting tension is a value measured according to the description of JIS-K6768.
  • a known coating method can be used as a method of applying the composition of the present invention to the thermoplastic polymer film.
  • a known coating method can be used as a method of applying the composition of the present invention to the thermoplastic polymer film.
  • examples thereof include a gravure coating method, a spray coating method, a dip coating method, a roll coating method, a doctor blade coating method, a wire bar coating method, and an air knife coating method.
  • the initial drip property is good, and repeatedly contacted with the aggregate of the agricultural house during long-term use, and such contact Even if it is a case where it is performed under the condition where a dry state and a wet state are repeated, there is an effect that a good drip property can be maintained.
  • Test Category 1 (Preparation of (modified) inorganic colloid sol) 39.10 parts of water and 59.61 parts of inorganic colloidal sol (A-1) (solid content: 23%) were mixed, and further ⁇ -glycidoxypropyltrimethoxysilane 1 as a silanol-forming organosilane compound (D-1). .29 parts (100% solid content) were mixed to prepare a liquid mixture having a solid content concentration of 15%, and then stirred at 50 ° C. for 5 hours to hydrolyze the silanol-forming organosilane compound (D-1). Further, the produced silanol compound was subjected to condensation polymerization to obtain a modified inorganic colloidal sol (K-1).
  • modified inorganic colloidal sol (K-1) had a silanol compound condensation polymer adhered to solid particles of the inorganic colloidal sol.
  • modified inorganic colloid sols (K-2) to (K-5) were prepared. Table 1 summarizes the contents of the modified inorganic colloid sol prepared in each of the above examples.
  • Ratio (part) Ratio (part) in terms of solid content
  • A-3 Anionic acidic silica sol
  • A-5 Anionic alkaline silica sol D-1: ⁇ -glycidoxypropyltrimethoxysilane
  • D-2 ⁇ -ureidopropyltrimethoxysilane
  • D-3 Methyltri Ethoxysilane Test Category 2 (Preparation of coating composition for agricultural film)
  • Example 1 26.5 parts of modified inorganic colloid sol (K-1) having a solid content concentration of 15%, 467 parts of water, 5 parts of cellulose derivative (B-1), water-soluble crosslinking agent (C-1) 1 having
  • Examples 2 to 27 and Comparative Examples 1 to 5 In the same manner as in Example 1, the agricultural film coating agent compositions (X-2) to (X-27) and (rx-1) to (rx-) of Examples 2 to 27 and Comparative Examples 1 to 5 were used. 5) was obtained. The contents of the agricultural film coating composition prepared in each of the above examples are summarized in Table 2.
  • (Modified) Ratio of inorganic colloid sol, cellulose derivative and water-soluble crosslinking agent parts by mass as solid content
  • Mass ratio Cellulose derivative / water-soluble crosslinking agent
  • Ratio of polyether-modified silicone (Modified) Conversion of solid content of inorganic colloid sol K-1 to K-5: Modified inorganic colloidal sol described in Table 1 A-1 to A-5: Inorganic colloidal sol described in Table 1 B-1: Hydroxypropylmethylcellulose (2% aqueous solution) (Viscosity at 20 ° C 50 mPa ⁇ s)
  • B-2 Hydroxypropyl methylcellulose (viscosity of 2% aqueous solution at 20 ° C.
  • B-3 Hydroxypropyl methylcellulose (viscosity of 2% aqueous solution at 20 ° C. 400 mPa ⁇ s)
  • B-4 Methyl cellulose (viscosity of 2% aqueous solution at 20 ° C. 4 mPa ⁇ s)
  • B-5 Sodium carboxymethylcellulose (viscosity of 2% aqueous solution at 20 ° C. 150 mPa ⁇ s)
  • B-6 Hydroxyethyl cellulose (2% aqueous solution viscosity at 20 ° C.
  • this olefin polymer film was subjected to corona treatment discharge, the wet tension of the corona discharge treatment surface was set to 42 mN / m, and then the coating composition for agricultural film (X -1) was applied by a gravure coating method so that the solid content would be 0.3 g / m 2, and was allowed to stay in a warm air drying oven adjusted to 70 ° C. for 1 minute to produce an agricultural modified thermoplastic polymer film. Obtained.
  • F-1 Ethylene / 1-butene copolymer (ethylene copolymerization ratio 95%, density 0.920 g / cm 3 , MFR 2.1 g / 10 min)
  • F-2 Ethylene / 1-hexene copolymer (ethylene copolymerization ratio 96%, density 0.930 g / cm 3 , MFR 1.0 g / 10 min)
  • F-3 Ethylene / vinyl acetate copolymer (ethylene copolymer ratio 93%, MFR 1.5 g / 10 min)
  • F-4 Polyethylene (density 0.927 g / cm 3 , MFR 4.0 g / 10 min)
  • F-5 ethylene-propylene copolymer (ethylene copolymerization ratio 4%, density 0.90 g / cm 3 , MFR 8.0 g / 10 min)
  • X-1 to X-27, rx-1 to rx-5 Coating agent composition for agricultural film described in Table 2 Test category 5 (
  • the time required for the water droplet adhesion area to be less than 10% was measured as the initial flowability, and evaluated according to the following criteria. Moreover, the adhesion state of the water drop after having been placed for 30 days continuously was visually observed and evaluated according to the following criteria.
  • Evaluation criteria for initial dropability A Less than 15 minutes after spreading (very excellent initial dropability). ⁇ : 15 minutes or more and less than 30 minutes after spreading (excellent initial drop property).
  • Adhesion area of water droplets is less than 10% and excellent in droplet sustainability.
  • Water droplet adhesion area is 10% or more and less than 50%, which is inferior in the flowability.
  • X Adhesion area of water droplets is 50% or more, and the droplet sustainability is remarkably inferior.
  • Evaluation criteria for dry scratch resistance A The coating film is not peeled off, and the scratch resistance is very excellent.
  • ⁇ The peeled area of the coating film is less than 10%, and the scratch resistance is excellent.
  • ⁇ The peeled area of the coating film is 10% to less than 50%, and the scratch resistance is poor.
  • X The peeling area of the coating film is 50% or more, and the scratch resistance is remarkably inferior.
  • ⁇ Evaluation of wet scratch resistance 100 cm 2 of the coated surface of the modified thermoplastic polymer film for agricultural use of each example produced in Test Category 4 was wetted with water, and a friction tester (Gakushin dyeing fastness) The test piece, manufactured by Daiei Kagaku Seiki Seisakusho Co., Ltd.) was subjected to 10 reciprocating frictions on the wet coated surface with a 300 g load applied with a vinyl tape on the friction surface of the arm, and then the rubbed part. The degree of peeling of the coating film was observed by the cloudy part formed by applying steam to the water droplets, and the peeling resistance strength of the coating film was evaluated as the wet scratch resistance according to the following criteria.
  • Wet scratch resistance evaluation criteria A There is no peeling of the coating film, and the scratch resistance is very excellent.
  • ⁇ The peeled area of the coating film is less than 10%, and the scratch resistance is excellent.
  • ⁇ The peeled area of the coating film is 10% to less than 50%, and the scratch resistance is poor.
  • X The peeling area of the coating film is 50% or more, and the scratch resistance is remarkably inferior.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Wood Science & Technology (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Toxicology (AREA)
  • Environmental Sciences (AREA)
  • General Health & Medical Sciences (AREA)
  • Inorganic Chemistry (AREA)
  • Dispersion Chemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Protection Of Plants (AREA)
  • Coating Of Shaped Articles Made Of Macromolecular Substances (AREA)
  • Manufacturing & Machinery (AREA)
  • Greenhouses (AREA)
  • Laminated Bodies (AREA)
  • Paints Or Removers (AREA)
  • Compositions Of Macromolecular Compounds (AREA)

Abstract

Provided are: a coating agent composition for an agricultural film, which exhibits a favorable initial antisticking property after being set on an agricultural greenhouse and which is capable of retaining a favorable antisticking property even after repeatedly making contact with a frame material of the agricultural greenhouse during long-term use in a situation where such contact takes place in an environment where a dry state and a wet state recurrently occur; and a modified thermoplastic polymer film using such a composition. The coating agent composition for an agricultural film contains, in a specific proportion, an inorganic colloidal sol, a specific cellulose derivative, and a water-soluble crosslinking agent.

Description

農業フィルム用コーティング剤組成物及び農業用改質熱可塑性高分子フィルムAgricultural film coating composition and agricultural modified thermoplastic polymer film
　本発明は、農業用ハウスの被覆材として用いられる農業フィルム用のコーティング剤組成物及びかかるコーティング剤組成物を付着させた農業用改質熱可塑性高分子フィルムに関する。 The present invention relates to a coating composition for agricultural films used as a covering material for agricultural houses and a modified thermoplastic polymer film for agriculture to which such a coating composition is attached.
　農業用ハウスの被覆材として、熱可塑性高分子フィルムが広く使用されている。しかし、熱可塑性高分子フィルムそれ自体は疎水性の性質を持つため、曇りを生じて日光の透過を低下し易く、結果として農作物の生育不良を引き起こすという問題があり、また付着した水滴が落下して農作物に病害を発生させるという問題もある。このため、従来から、農業フィルムには防曇剤を添加したものや流滴剤をコーティングしたものが使用されている（例えば特許文献１～３参照）。しかし、これらの従来手段には、農業用ハウスに張られた後において、初期の流滴性は得られるものの、長期間使用される間にハウスの骨材と繰り返し接触し、しかもかかる接触が乾燥状態と湿潤状態とが繰り返される状況下で行なわれると、流滴性が失われていくという問題がある。従来手段では実際の耐用性に劣るのである。 A thermoplastic polymer film is widely used as a covering material for agricultural houses. However, since the thermoplastic polymer film itself has a hydrophobic property, there is a problem that it is likely to cause clouding and decrease the transmission of sunlight, resulting in poor growth of crops. There is also a problem of causing diseases to crops. For this reason, conventionally, agricultural films added with an antifogging agent or coated with a dropping agent have been used (see, for example, Patent Documents 1 to 3). However, these conventional means, after being stretched on an agricultural house, are able to obtain initial dripping properties, but repeatedly contact the house aggregate during long-term use, and such contact is dry. When it is carried out under conditions where the state and the wet state are repeated, there is a problem that the drip property is lost. The conventional means is inferior in actual durability.
特開平９－２９８９５４号公報JP-A-9-298954 特開平１１－１０７８３号公報Japanese Patent Laid-Open No. 11-10784 特開２００４－２５５８０７号公報Japanese Patent Laid-Open No. 2004-255807
　本発明が解決しようとする課題は、農業用ハウスに張られた後において、初期の流滴性が良好であり、且つ長期間使用される間に農業用ハウスの骨材と繰り返し接触し、しかもかかる接触が乾燥状態と湿潤状態とが繰り返される状況下で行なわれた場合であっても良好な流滴性を維持することができる農業フィルム用コーティング剤組成物及びかかる組成物を用いた農業用改質熱可塑性高分子フィルムを提供する処にある。 The problem to be solved by the present invention is that after being stretched on an agricultural house, the initial drip property is good, and it repeatedly contacts with the aggregate of the agricultural house during long-term use. A coating composition for agricultural film capable of maintaining good drip properties even when such contact is repeated in a dry state and a wet state, and agricultural use using such a composition It is in providing a modified thermoplastic polymer film.
　本発明者らは、前記の課題を解決するべく研究した結果、無機コロイドゾルと、特定のセルロース誘導体と、水溶性架橋剤とを特定割合で含有して成るものが農業フィルム用コーティング剤組成物として正しく好適であることを見出した。 As a result of studies conducted by the present inventors to solve the above-mentioned problems, a coating composition for agricultural films comprising an inorganic colloidal sol, a specific cellulose derivative, and a water-soluble crosslinking agent in a specific ratio. It was found to be correct and suitable.
　すなわち本発明は、無機コロイドゾルを固形分換算で３０～７０質量％、下記のセルロース誘導体を２０～６０質量％及び水溶性架橋剤を１～３０質量％の割合で含有してなることを特徴とする農業フィルム用コーティング剤組成物に係る。また本発明は、かかる農業フィルム用コーティング剤組成物を付着させた農業用改質熱可塑性高分子フィルムに係る。 That is, the present invention is characterized in that the inorganic colloidal sol contains 30 to 70% by mass in terms of solid content, 20 to 60% by mass of the following cellulose derivative, and 1 to 30% by mass of a water-soluble crosslinking agent. The present invention relates to an agricultural film coating agent composition. The present invention also relates to an agricultural modified thermoplastic polymer film to which the agricultural film coating composition is attached.
　セルロース誘導体：カルボキシメチルセルロース金属塩、ヒドロキシエチルセルロース、ヒドロキシプロピルメチルセルロース、メチルセルロースから選ばれる少なくとも一つ
　先ず、本発明に係る農業フィルム用コーティング剤組成物（以下、本発明の組成物という）について説明する。本発明の組成物は、無機コロイドゾルを固形分換算で３０～７０質量％、前記のセルロース誘導体を２０～６０質量％及び水溶性架橋剤を１～３０質量％の割合で含有してなるものであるが、無機コロイドゾルを固形分換算で４０～６７質量％、前記のセルロース誘導体を３０～５０質量％及び水溶性架橋剤を３～２５質量％の割合で含有しており、且つセルロース誘導体／水溶性架橋剤＝１０／１～１０／５（質量比）の比率で含有してなるものが好ましい。 Cellulose derivative: at least one selected from carboxymethylcellulose metal salt, hydroxyethylcellulose, hydroxypropylmethylcellulose, and methylcellulose First, the coating composition for agricultural films according to the present invention (hereinafter referred to as the composition of the present invention) will be described. The composition of the present invention comprises an inorganic colloidal sol in a proportion of 30 to 70% by mass in terms of solid content, 20 to 60% by mass of the above cellulose derivative, and 1 to 30% by mass of a water-soluble crosslinking agent. However, the inorganic colloidal sol contains 40 to 67% by mass in terms of solid content, 30 to 50% by mass of the above cellulose derivative, and 3 to 25% by mass of a water-soluble crosslinking agent. Crosslinker is preferably contained at a ratio of 10/1 to 10/5 (mass ratio).
　本発明に供する無機コロイドゾルとしては、いわゆるシリカゾルやアルミナゾル等が挙げられ、水分散液として市販されているものを使用することができ、これらは単独で用いても併用してもよい。シリカゾルとしては、スノーテックスＡＫ、スノーテックスＡＫ－Ｌ（以上、いずれも日産化学社製の商品名）等のカチオン性酸性シリカゾル、スノーテックス３０、スノーテックス３０Ｌ、スノーテックスＺＬ（以上、いずれも日産化学社製の商品名）、カタロイドＳＩ－３０、カタロイドＳＩ－４５Ｐ、カタロイドＳＩ－８０Ｐ（以上、いずれも日揮触媒化成社製の商品名）等のアニオン性アルカリ性シリカゾル、スノーテックスＯ、スノーテックスＯＬ（以上、いずれも日産化学社製の商品名）、カタロイドＳＮ（日揮触媒化成社製の商品名）等のアニオン性酸性シリカゾルが挙げられ、アルミナゾルとしては、アルミナゾル１００、アルミナゾル２００、アルミナゾル５２０（以上、いずれも日産化学社製の商品名）、カタロイドＡＳ－１、カタロイドＡＳ－２（以上、いずれも日揮触媒化成社製の商品名）等のカチオン性酸性アルミナゾルが挙げられる。 Examples of the inorganic colloid sol used in the present invention include so-called silica sol and alumina sol. Commercially available water dispersions may be used, and these may be used alone or in combination. Silica sols include cationic acidic silica sols such as Snowtex AK and Snowtex AK-L (all are trade names manufactured by Nissan Chemical Co., Ltd.), Snowtex 30, Snowtex 30L and Snowtex ZL (all are Nissan) Chemical product name), Cataloid SI-30, Cataloid SI-45P, Cataloid SI-80P (all of which are trade names made by JGC Catalysts & Chemicals), etc., anionic alkaline silica sol, Snowtex O, Snowtex OL (All are trade names manufactured by Nissan Chemical Co., Ltd.) and anionic acidic silica sols such as Cataloid SN (trade name manufactured by JGC Catalysts & Chemicals) are listed. Examples of the alumina sol include alumina sol 100, alumina sol 200, alumina sol 520 (and above). , Both are product names manufactured by Nissan Chemical Co., Ltd.), Cataloid A -1, Cataloid AS-2 (above all are JGC Catalysts and Chemicals Co., trade name) and cationic acidic alumina sol and the like.
　かかる無機コロイドゾルとしては、無機コロイドゾルの存在下に、シラノール形成性有機シラン化合物を加水分解し、生成したシラノール化合物を縮合重合して、無機コロイドゾルの固形分粒子の表面に縮合重合物を付着させたもの（以下、これを改質無機コロイドゾルという）を使用することもできる。無機コロイドゾルの改質に用いるシラノール形成性有機シラン化合物としては、１）トリアルコキシシラン類、２）ジアルコキシシラン類、３）モノアルコキシシラン類等が挙げられる。トリアルコキシシラン類としては、メチルトリメトキシシラン、メチルトリエトキシシラン、ビニルトリメトキシシラン、ビニルトリエトキシシラン、γ－クロロプロピルトリプロポキシシラン、γ－メルカプトプロピルトリエトキシシラン、γ－グリシドキシプロピルトリメトキシシラン、γ－メタクリロキシプロピルトリエトキシシラン、γ－ウレイドプロピルトリメトキシシラン、フェニルトリメトキシシラン等が挙げられ、ジアルコキシシラン類としてはジメチルジメトキシシラン、γ－クロロプロピルメチルジメトキシシラン、γ－グリシドキシプロピルメチルジメトキシシラン等が挙げられ、モノアルコキシシラン類としては、トリメチルメトキシシラン等が挙げられる。なかでもシラノール形成性有機シラン化合物としては、γ－グリシドキシプロピルトリメトキシシラン、γ－ウレイドプロピルトリメトキシシラン、メチルトリエトキシシランが好ましい。かかるシラノール形成性有機シラン化合物は、無機コロイドゾルの固形分換算１００質量部に対して、１～３０質量部の割合で用いるのが好ましい。 As such an inorganic colloid sol, a silanol-forming organic silane compound is hydrolyzed in the presence of the inorganic colloid sol, the resulting silanol compound is condensed and polymerized, and the condensation polymer is adhered to the surface of solid particles of the inorganic colloid sol. (Hereinafter referred to as a modified inorganic colloid sol) can also be used. Examples of the silanol-forming organosilane compound used for modifying the inorganic colloid sol include 1) trialkoxysilanes, 2) dialkoxysilanes, and 3) monoalkoxysilanes. Examples of trialkoxysilanes include methyltrimethoxysilane, methyltriethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, γ-chloropropyltripropoxysilane, γ-mercaptopropyltriethoxysilane, γ-glycidoxypropyltri Examples include methoxysilane, γ-methacryloxypropyltriethoxysilane, γ-ureidopropyltrimethoxysilane, and phenyltrimethoxysilane. Examples of dialkoxysilanes include dimethyldimethoxysilane, γ-chloropropylmethyldimethoxysilane, and γ-glycol. Sidoxypropylmethyldimethoxysilane and the like, and monoalkoxysilanes include trimethylmethoxysilane and the like. Of these, γ-glycidoxypropyltrimethoxysilane, γ-ureidopropyltrimethoxysilane, and methyltriethoxysilane are preferable as the silanol-forming organosilane compound. Such a silanol-forming organosilane compound is preferably used at a ratio of 1 to 30 parts by mass with respect to 100 parts by mass in terms of solid content of the inorganic colloid sol.
　本発明の組成物に供するセルロース誘導体は、カルボキシメチルセルロース金属塩、ヒドロキシエチルセルロース、ヒドロキシプロピルメチルセルロース及びメチルセルロースから選ばれる少なくとも一つである。これらは単独で用いることもできるし、併用することもできる。かかるセルロース誘導体としては、２質量％水溶液の２０℃での粘性率が１～６００ｍＰａ・ｓのものが好ましく、１～４００ｍＰａ・ｓのものがより好ましい。 The cellulose derivative used for the composition of the present invention is at least one selected from carboxymethylcellulose metal salt, hydroxyethylcellulose, hydroxypropylmethylcellulose and methylcellulose. These can be used alone or in combination. Such a cellulose derivative preferably has a viscosity of 1 to 600 mPa · s at 20 ° C. in a 2% by weight aqueous solution, more preferably 1 to 400 mPa · s.
　本発明の組成物に供する水溶性架橋剤としては、水溶性メラミン、水溶性エポキシ、水溶性オキサゾリン、水溶性アジリジン等が挙げられるが、水溶性メラミンが好ましい。水溶性メラミンとしては、市販されているものを使用することができ、これには例えば、ニカラックＭＸ－０３５、ニカラックＭＷ－２２、ニカラックＭＷ－１２ＬＦ（以上、いずれも三和ケミカル社製の商品名）、ベッカミンＭ－３、ベッカミンＭＡ－Ｓ、ベッカミンＪ－１０１（以上、いずれもＤＩＣ社製の商品名）が挙げられる。 Examples of the water-soluble crosslinking agent to be used in the composition of the present invention include water-soluble melamine, water-soluble epoxy, water-soluble oxazoline, water-soluble aziridin, and the like, but water-soluble melamine is preferable. As the water-soluble melamine, commercially available products can be used. For example, Nicalac MX-035, Nicalac MW-22, Nicalac MW-12LF (all of these are trade names manufactured by Sanwa Chemical Co., Ltd.) ), Becamine M-3, becamine MA-S, and becamine J-101 (all of which are trade names manufactured by DIC).
　本発明の組成物には更にポリエーテル変性シリコーンを含有することができる。かかるポリエーテル変性シリコーンは、前記無機コロイドゾルの固形分換算１００質量部に対し、０．１～５０質量部の割合で用いる。 The composition of the present invention can further contain a polyether-modified silicone. Such polyether-modified silicone is used at a ratio of 0.1 to 50 parts by mass with respect to 100 parts by mass in terms of solid content of the inorganic colloidal sol.
　かかるポリエーテル変性シリコーンとしては、市販されているものをそのまま使用することができる。そのような市販品としては例えば、ＴＳＦ４４４０、ＴＳＦ４４４１、ＴＳＦ４４４５、ＴＳＦ４４４６、ＴＳＦ４４５２、ＴＳＦ４４６０（以上、いずれもモメンティブ・パフォーマンス・マテリアルズ・ジャパン社製の商品名）、Ｘ２２－４９５２、Ｘ－２２－４２７２、ＫＦ－６１２３、ＫＦ－３５１Ａ、ＫＦ－３５２Ａ、ＫＦ－３５３、ＫＦ－３５４Ｌ、ＫＦ－３５５Ａ、ＫＦ－６１５Ａ、ＫＦ－９４５、ＫＦ－６４０、ＫＦ－６４２、ＫＦ－６４３、ＫＦ－６４４、ＫＦ－６２０４、Ｘ－２２－４５１５、ＫＦ－６００４（以上、いずれも信越シリコーン社製の商品名）、ＳＨ８７００、ＳＨ８４１０、ＳＨ８４００、Ｌ－７００２、ＦＺ－２１０４、ＦＺ－７７、Ｌ－７６０４、ＦＺ－２２０３、ＦＺ－２２０８（以上、いずれも東レダウコーニング社製の商品名）等が挙げられるが、なかでもＴＳＦ４４４０、ＫＦ－３５４Ｌ、ＫＦ－９４５、ＳＨ８４００、ＫＦ－６００４等、ＨＬＢが４～１６のものが好ましい。 As such a polyether-modified silicone, a commercially available product can be used as it is. Examples of such commercial products include TSF4440, TSF4441, TSF4445, TSF4446, TSF4452, and TSF4460 (all of which are trade names of Momentive Performance Materials Japan), X22-4952, X-22-4272, KF-6123, KF-351A, KF-352A, KF-353, KF-354L, KF-355A, KF-615A, KF-945, KF-640, KF-642, KF-643, KF-644, KF- 6204, X-22-4515, KF-6004 (all are trade names manufactured by Shin-Etsu Silicone), SH8700, SH8410, SH8400, L-7002, FZ-2104, FZ-77, L-7604, FZ-2203 , FZ-2208 (above, either Although manufactured by Dow Corning Toray Co., Ltd. under the trade name) and the like, and among them TSF4440, KF-354L, KF-945, SH8400, KF-6004, etc., HLB is preferably from 4 to 16.
　次に、本発明に係る改質熱可塑性高分子フィルム（以下、本発明のフィルムという）について説明する。本発明のフィルムは、熱可塑性高分子フィルムの表面処理面に、前記した本発明の組成物が固形分として０．１５～０．５ｇ／ｍ２付着しているものである。 Next, the modified thermoplastic polymer film according to the present invention (hereinafter referred to as the film of the present invention) will be described. The film of the present invention is such that the above-described composition of the present invention adheres in a solid content of 0.15 to 0.5 g / m 2 on the surface-treated surface of a thermoplastic polymer film.
　本発明のフィルムに供する熱可塑性樹脂としては、１）ポリオレフィン系樹脂、２）ポリ塩化ビニル系樹脂、３）ポリエステル系樹脂等が挙げられる。ポリオレフィン系樹脂としては、ポリエチレン、ポリプロピレン等のα－オレフィンの単独重合体、エチレン－プロピレン共重合体、エチレン・１－ブテン共重合体、エチレン・４－メチル－１－ペンテン共重合体、エチレン・１－ヘキセン共重合体、エチレン・１－オクテン共重合体等のα－オレフィンの共重合体、エチレン・酢酸ビニル共重合体、エチレン・メチルメタクリレート共重合体、エチレン・酢酸ビニル・メチルメタクリレート共重合体、アイオノマー樹脂等α－オレフィンを主成分とする異種単量体との共重合体が挙げられ、ポリ塩化ビニル系樹脂としては、ポリ塩化ビニル、塩化ビニル・エチレン共重合体、塩化ビニル・酢酸ビニル共重合体、塩化ビニル・メチルメタクリレート共重合体、ポリ塩化ビニリデン等が挙げられ、ポリエステル系樹脂としてはポリエチレンテレフタレート等が挙げられる。これらは複数種類の熱可塑性樹脂をブレンドして使用することもできる。なかでも熱可塑性樹脂としては、ポリオレフィン系樹脂が好ましい。かかるポリオレフィン系樹脂におけるα－オレフィンの共重合体は、いずれも公知の高活性チーグラー触媒、メタロセン触媒等の均一系触媒を用い、気相法、溶液重合法等によって得られるものがより好ましく、密度が０．８６～０．９４ｇ／cm３、ＭＦＲが０．０１～２０ｇ／１０分であるものが特に好ましい。ポリオレフィン系樹脂は、二つ以上のポリオレフィン系樹脂を混合して用いることもできる。これらの熱可塑性樹脂には、通常使用される酸化防止剤、耐候剤、紫外線吸収剤、赤外線吸収剤、滑剤、アンチブロッキング剤、防曇剤、防霧剤、保温剤、顔料等を必要に応じて含有することができる。 Examples of the thermoplastic resin used in the film of the present invention include 1) polyolefin resin, 2) polyvinyl chloride resin, and 3) polyester resin. Examples of polyolefin resins include homopolymers of α-olefins such as polyethylene and polypropylene, ethylene-propylene copolymers, ethylene / 1-butene copolymers, ethylene / 4-methyl-1-pentene copolymers, ethylene Α-olefin copolymer such as 1-hexene copolymer, ethylene / 1-octene copolymer, ethylene / vinyl acetate copolymer, ethylene / methyl methacrylate copolymer, ethylene / vinyl acetate / methyl methacrylate copolymer Copolymers and copolymers with different monomers mainly composed of α-olefin such as ionomer resins. Examples of polyvinyl chloride resins include polyvinyl chloride, vinyl chloride / ethylene copolymers, vinyl chloride / acetic acid. Examples include vinyl copolymers, vinyl chloride / methyl methacrylate copolymers, and polyvinylidene chloride. As the polyester-based resin and polyethylene terephthalate. These may be used by blending a plurality of types of thermoplastic resins. Of these, polyolefin resins are preferred as the thermoplastic resin. The α-olefin copolymer in the polyolefin resin is more preferably obtained by a gas phase method, a solution polymerization method, etc., using a known homogeneous catalyst such as a highly active Ziegler catalyst or a metallocene catalyst. Is particularly preferably 0.86 to 0.94 g / cm 3 and MFR 0.01 to 20 g / 10 min. The polyolefin resin can be used by mixing two or more polyolefin resins. These thermoplastic resins contain commonly used antioxidants, weathering agents, ultraviolet absorbers, infrared absorbers, lubricants, antiblocking agents, antifogging agents, antifogging agents, heat retention agents, pigments, etc. as necessary. Can be contained.
　本発明のフィルムに供する熱可塑性高分子フィルムの製造方法としては、特に制限はなく、例えばインフレーション成形法、Ｔダイ成形法等が挙げられる。フィルムは単層フィルムでも多層フィルムでもよく、また未延伸フィルムでも延伸フィルムでもよい。農業用フィルムとしては、インフレーション成形により成形された前記ポリオレフィン系樹脂からなる熱可塑性高分子フィルムが好適である。 The method for producing the thermoplastic polymer film used for the film of the present invention is not particularly limited, and examples thereof include an inflation molding method and a T-die molding method. The film may be a single layer film or a multilayer film, and may be an unstretched film or a stretched film. As the agricultural film, a thermoplastic polymer film made of the polyolefin resin formed by inflation molding is suitable.
　本発明のフィルムは、前記熱可塑性高分子フィルムの本発明の組成物を塗布することとなる面に表面処理をした後、本発明の組成物を塗布したものが好ましい。表面処理としては、コロナ放電処理、大気圧プラズマ処理、火炎処理等、公知の方法で行うことができるが、コロナ放電処理が好ましい。表面処理した面のぬれ張力は３５ｍＮ／ｍ以上とするのが好ましく、３５～７０ｍＮ／ｍとするのがより好ましい。本発明において、ぬれ張力は、ＪＩＳ－Ｋ６７６８の記載に準じて測定される値である。 The film of the present invention is preferably one in which the surface of the thermoplastic polymer film to be coated with the composition of the present invention is subjected to surface treatment and then the composition of the present invention is coated. The surface treatment can be performed by a known method such as corona discharge treatment, atmospheric pressure plasma treatment, flame treatment, etc., but corona discharge treatment is preferred. The wetting tension of the surface treated surface is preferably 35 mN / m or more, more preferably 35 to 70 mN / m. In the present invention, the wetting tension is a value measured according to the description of JIS-K6768.
　本発明のフィルムにおいて、前記熱可塑性高分子フィルムに本発明の組成物を塗布する方法としては、公知の塗布法を用いることができる。これには例えば、グラビアコート法、スプレーコート法、浸漬コート法、ロールコート法、ドクターブレードコート法、ワイヤーバーコート法、エアナイフコート法等が挙げられる。 In the film of the present invention, a known coating method can be used as a method of applying the composition of the present invention to the thermoplastic polymer film. Examples thereof include a gravure coating method, a spray coating method, a dip coating method, a roll coating method, a doctor blade coating method, a wire bar coating method, and an air knife coating method.
　以上説明した本発明によると、農業用ハウスに張られた後において、初期の流滴性が良好であり、且つ長期間使用される間に農業用ハウスの骨材と繰り返し接触し、しかもかかる接触が乾燥状態と湿潤状態とが繰り返される状況下で行なわれた場合であっても良好な流滴性を維持することができるという効果がある。 According to the present invention described above, after being stretched on an agricultural house, the initial drip property is good, and repeatedly contacted with the aggregate of the agricultural house during long-term use, and such contact Even if it is a case where it is performed under the condition where a dry state and a wet state are repeated, there is an effect that a good drip property can be maintained.
　以下、本発明の構成及び効果をより具体的にするため、実施例等を挙げるが、本発明がこれらの実施例に限定されるというものではない。尚、以下の実施例及び比較例において、部は質量部を、また％は質量％を意味する。 Hereinafter, in order to make the configuration and effects of the present invention more specific, examples and the like will be described. However, the present invention is not limited to these examples. In the following Examples and Comparative Examples, “part” means “part by mass” and “%” means “% by mass”.
　試験区分１（（改質）無機コロイドゾルの調製）
　水３９．１０部、無機コロイドゾル（Ａ－１）５９．６１部（固形分２３％）を混合し、更にシラノール形成性有機シラン化合物（Ｄ－１）としてγ－グリシドキシプロピルトリメトキシシラン１．２９部（固形分１００％）を混合して固形分濃度１５％の混合液を調製した後、５０℃で５時間撹拌してシラノール形成性有機シラン化合物（Ｄ－１）を加水分解処理し、更に生成したシラノール化合物を縮合重合させて改質無機コロイドゾル（Ｋ－１）を得た。この改質無機コロイドゾル（Ｋ－１）は、前記の無機コロイドゾルの固形分粒子にシラノール化合物の縮合重合物が付着しているものであった。同様にして、改質無機コロイドゾル（Ｋ－２）～（Ｋ－５）を調製した。以上の各例で調製した改質無機コロイドゾルの内容を表１にまとめて示した。 Test Category 1 (Preparation of (modified) inorganic colloid sol)
39.10 parts of water and 59.61 parts of inorganic colloidal sol (A-1) (solid content: 23%) were mixed, and further γ-glycidoxypropyltrimethoxysilane 1 as a silanol-forming organosilane compound (D-1). .29 parts (100% solid content) were mixed to prepare a liquid mixture having a solid content concentration of 15%, and then stirred at 50 ° C. for 5 hours to hydrolyze the silanol-forming organosilane compound (D-1). Further, the produced silanol compound was subjected to condensation polymerization to obtain a modified inorganic colloidal sol (K-1). This modified inorganic colloidal sol (K-1) had a silanol compound condensation polymer adhered to solid particles of the inorganic colloidal sol. Similarly, modified inorganic colloid sols (K-2) to (K-5) were prepared. Table 1 summarizes the contents of the modified inorganic colloid sol prepared in each of the above examples.
Figure JPOXMLDOC01-appb-T000001
 　表１において、
　割合（部）：固形分換算の割合（部）
　Ａ－１：カチオン性酸性シリカゾル
　Ａ－２：カチオン性酸性シリカゾル／カチオン性酸性アルミナゾル＝５０／５０（質量比）の混合物
　Ａ－３：アニオン性酸性シリカゾル
　Ａ－４：アニオン性酸性シリカゾル／カチオン性酸性アルミナゾル＝７５／２５（質量比）の混合物
　Ａ－５：アニオン性アルカリ性シリカゾル
　Ｄ－１：γ－グリシドキシプロピルトリメトキシシラン
　Ｄ－２：γ－ウレイドプロピルトリメトキシシラン
　Ｄ－３：メチルトリエトキシシラン
　試験区分２（農業フィルム用コーティング剤組成物の調製）
　・実施例１
　固形分濃度１５％の改質無機コロイドゾル（Ｋ－１）２６．５部、水４６７部、セルロース誘導体（Ｂ－１）５部、固形分濃度７０％の水溶性架橋剤（Ｃ－１）１．４部及びポリエーテル変性シリコーン（Ｓ－１）０．０１部を撹拌し、固形分濃度２％の農業フィルム用コーティング剤組成物（Ｘ－１）を得た。
Figure JPOXMLDOC01-appb-T000001
 In Table 1,
Ratio (part): Ratio (part) in terms of solid content
A-1: Cationic acidic silica sol A-2: Mixture of cationic acidic silica sol / cationic acidic alumina sol = 50/50 (mass ratio) A-3: Anionic acidic silica sol A-4: Anionic acidic silica sol / cationic Acidic alumina sol = 75/25 (mass ratio) mixture A-5: Anionic alkaline silica sol D-1: γ-glycidoxypropyltrimethoxysilane D-2: γ-ureidopropyltrimethoxysilane D-3: Methyltri Ethoxysilane Test Category 2 (Preparation of coating composition for agricultural film)
Example 1
26.5 parts of modified inorganic colloid sol (K-1) having a solid content concentration of 15%, 467 parts of water, 5 parts of cellulose derivative (B-1), water-soluble crosslinking agent (C-1) 1 having a solid content concentration of 70% .4 parts and 0.01 parts of polyether-modified silicone (S-1) were stirred to obtain an agricultural film coating composition (X-1) having a solid content concentration of 2%.
　・実施例２～２７及び比較例１～５
　実施例１の場合と同様にして、実施例２～２７及び比較例１～５の農業フィルム用コーティング剤組成物（Ｘ－２）～（Ｘ－２７）及び（ｒｘ－１）～（ｒｘ－５）を得た。以上の各例で調製した農業フィルム用コーティング剤組成物の内容を表２にまとめて示した。 Examples 2 to 27 and Comparative Examples 1 to 5
In the same manner as in Example 1, the agricultural film coating agent compositions (X-2) to (X-27) and (rx-1) to (rx-) of Examples 2 to 27 and Comparative Examples 1 to 5 were used. 5) was obtained. The contents of the agricultural film coating composition prepared in each of the above examples are summarized in Table 2.
Figure JPOXMLDOC01-appb-T000002
 　表２において、
　（改質）無機コロイドゾル、セルロース誘導体及び水溶性架橋剤の割合：固形分としての質量部
　質量比：セルロース誘導体／水溶性架橋剤
　ポリエーテル変性シリコーンの割合：（改質）無機コロイドゾルの固形分換算１００質量部に対する質量部
　Ｋ－１～Ｋ－５：表１に記載の改質無機コロイドゾル
　Ａ－１～Ａ－５：表１に記載の無機コロイドゾル
　Ｂ－１：ヒドロキシプロピルメチルセルロース（２％水溶液の２０℃での粘性率５０ｍＰａ・ｓ）
　Ｂ－２：ヒドロキシプロピルメチルセルロース（２％水溶液の２０℃での粘性率３ｍＰａ・ｓ）
　Ｂ－３：ヒドロキシプロピルメチルセルロース（２％水溶液の２０℃での粘性率４００ｍＰａ・ｓ）
　Ｂ－４：メチルセルロース（２％水溶液の２０℃での粘性率４ｍＰａ・ｓ）
　Ｂ－５：カルボキシメチルセルロースナトリウム（２％水溶液の２０℃での粘性率１５０ｍＰａ・ｓ）
　Ｂ－６：ヒドロキシエチルセルロース（２％水溶液の２０℃での粘性率１００ｍＰａ・ｓ）
　Ｃ－１：水溶性メラミン（三和ケミカル製の商品名ニカラックＭＸ－０３５）
　Ｃ－２：水溶性メラミン（ＤＩＣ製の商品名ベッカミンＭＡ－Ｓ）
　Ｃ－３：水溶性メラミン（ＤＩＣ製の商品名ベッカミンＭ－３）
　ｒｃ－１：非水溶性メラミン（三和ケミカル製の商品名ニカラックＭＸ－７５０）
　Ｓ－１：ポリエーテル変性シリコーン（ＨＬＢ＝１４）
　Ｓ－２：ポリエーテル変性シリコーン（ＨＬＢ＝１６）
　Ｓ－３：ポリエーテル変性シリコーン（ＨＬＢ＝４）
　試験区分３（農業フィルム用コーティング剤組成物の評価）
　試験区分２で調製した各例の農業フィルム用コーティング剤組成物の混合性を以下の方法で評価した。結果を表３にまとめて示した。
Figure JPOXMLDOC01-appb-T000002
 In Table 2,
(Modified) Ratio of inorganic colloid sol, cellulose derivative and water-soluble crosslinking agent: parts by mass as solid content Mass ratio: Cellulose derivative / water-soluble crosslinking agent Ratio of polyether-modified silicone: (Modified) Conversion of solid content of inorganic colloid sol K-1 to K-5: Modified inorganic colloidal sol described in Table 1 A-1 to A-5: Inorganic colloidal sol described in Table 1 B-1: Hydroxypropylmethylcellulose (2% aqueous solution) (Viscosity at 20 ° C 50 mPa · s)
B-2: Hydroxypropyl methylcellulose (viscosity of 2% aqueous solution at 20 ° C. 3 mPa · s)
B-3: Hydroxypropyl methylcellulose (viscosity of 2% aqueous solution at 20 ° C. 400 mPa · s)
B-4: Methyl cellulose (viscosity of 2% aqueous solution at 20 ° C. 4 mPa · s)
B-5: Sodium carboxymethylcellulose (viscosity of 2% aqueous solution at 20 ° C. 150 mPa · s)
B-6: Hydroxyethyl cellulose (2% aqueous solution viscosity at 20 ° C. 100 mPa · s)
C-1: Water-soluble melamine (trade name Nikalac MX-035 manufactured by Sanwa Chemical)
C-2: Water-soluble melamine (trade name Becamine MA-S manufactured by DIC)
C-3: Water-soluble melamine (trade name Becamine M-3 manufactured by DIC)
rc-1: Water-insoluble melamine (trade name Nikalac MX-750 manufactured by Sanwa Chemical)
S-1: Polyether-modified silicone (HLB = 14)
S-2: Polyether-modified silicone (HLB = 16)
S-3: Polyether-modified silicone (HLB = 4)
Test category 3 (Evaluation of coating composition for agricultural film)
The mixing property of the coating composition for agricultural film of each example prepared in Test Category 2 was evaluated by the following method. The results are summarized in Table 3.
　・混合性の評価
　試験区分２で調製した各例の農業フィルム用コーティング剤組成物を沈降管に１００ｍｌ入れ、２０℃、２４時間の条件で静置した後、農業フィルム用コーティング剤組成物の状態を以下の基準で評価した。 ・ Evaluation of Mixability 100 ml of the agricultural film coating composition of each example prepared in Test Category 2 was placed in a settling tube and allowed to stand at 20 ° C. for 24 hours, and then the state of the agricultural film coating composition. Was evaluated according to the following criteria.
　溶液混合性の評価基準
　◎：沈降物及び不溶物が認められず、混合性に優れる
　×：沈降物及び不溶物が認められ、混合性に劣る
　試験区分４（農業用改質熱可塑性高分子フィルムの製造）
　・実施例２８
　エチレン・１－ブテン共重合体（エチレン共重合比率９５％、密度０．９２０ｇ／cm３、ＭＦＲ２．１ｇ／１０分）を、直径７５ｍｍでリップ間隙３ｍｍのダイを取り付けたインフレーション成形機に供し、樹脂押し出し温度２００℃及びＢＵＲ＝１．８の条件下でインフレーション成形を行ない、厚さ１５０μｍのオレフィン重合体フィルムを作製した。次いで、このオレフィン重合体フィルムにコロナ処理放電を施し、コロナ放電処理面のぬれ張力を４２ｍＮ／ｍとした後、かかるコロナ放電処理面に試験区分２で調製した農業フィルム用コーティング剤組成物（Ｘ－１）を固形分として０．３ｇ／ｍ２となるようグラビアコート法により塗布し、７０℃に温調した温風乾燥炉に１分間滞留させて、農業用改質熱可塑性高分子フィルムを得た。 Evaluation criteria for solution mixability ◎: Sediment and insoluble matter are not recognized, and mixability is excellent ×: Sediment and insoluble matter are found, and mixability is poor Test Category 4 (Agricultural modified thermoplastic polymer film Manufacturing of)
Example 28
An ethylene / 1-butene copolymer (ethylene copolymerization ratio 95%, density 0.920 g / cm3, MFR 2.1 g / 10 min) was supplied to an inflation molding machine equipped with a die having a diameter of 75 mm and a lip gap of 3 mm, and resin Inflation molding was performed under the conditions of an extrusion temperature of 200 ° C. and BUR = 1.8 to prepare an olefin polymer film having a thickness of 150 μm. Next, this olefin polymer film was subjected to corona treatment discharge, the wet tension of the corona discharge treatment surface was set to 42 mN / m, and then the coating composition for agricultural film (X -1) was applied by a gravure coating method so that the solid content would be 0.3 g / m 2, and was allowed to stay in a warm air drying oven adjusted to 70 ° C. for 1 minute to produce an agricultural modified thermoplastic polymer film. Obtained.
　・実施例２９～５４及び比較例６～１０
　実施例１の場合と同様にして、実施例２９～５４及び比較例６～１０の農業用改質熱可塑性高分子フィルムを得た。以上の各例で製造した改質熱可塑性高分子フィルムの内容を表３にまとめて示した。 Examples 29 to 54 and Comparative Examples 6 to 10
In the same manner as in Example 1, agricultural modified thermoplastic polymer films of Examples 29 to 54 and Comparative Examples 6 to 10 were obtained. The contents of the modified thermoplastic polymer film produced in each of the above examples are shown together in Table 3.
Figure JPOXMLDOC01-appb-T000003
 　表３において、
　Ｆ－１：エチレン・１－ブテン共重合体（エチレン共重合比率９５％、密度０．９２０ｇ／ｃｍ３、ＭＦＲ２．１ｇ／１０分）
　Ｆ－２：エチレン・１－ヘキセン共重合体（エチレン共重合比率９６％、密度０．９３０ｇ／ｃｍ３、ＭＦＲ１．０ｇ／１０分）
　Ｆ－３：エチレン・酢酸ビニル共重合体（エチレン共重合比率９３％、ＭＦＲ１．５ｇ／１０分）
　Ｆ－４：ポリエチレン（密度０．９２７ｇ／ｃｍ３、ＭＦＲ４．０ｇ／１０分）
　Ｆ－５：エチレン－プロピレン共重合体（エチレン共重合比率４％、密度０．９０ｇ／ｃｍ３、ＭＦＲ８．０ｇ／１０分）
　Ｘ－１～Ｘ－２７，ｒｘ－１～ｒｘ－５：表２に記載の農業フィルム用コーティング剤組成物
　試験区分５（農業用改質熱可塑性高分子フィルムの評価）
　試験区分４で製造した各例の農業用改質熱可塑性高分子フィルムについて、農業フィルム用コーティング剤組成物の塗布性、初期流滴性、流滴持続性、Ｄｒｙ耐擦傷性、Ｗｅｔ耐擦傷性について下記に示す評価を行った。結果を表４にまとめて示した。
Figure JPOXMLDOC01-appb-T000003
 In Table 3,
F-1: Ethylene / 1-butene copolymer (ethylene copolymerization ratio 95%, density 0.920 g / cm 3 , MFR 2.1 g / 10 min)
F-2: Ethylene / 1-hexene copolymer (ethylene copolymerization ratio 96%, density 0.930 g / cm 3 , MFR 1.0 g / 10 min)
F-3: Ethylene / vinyl acetate copolymer (ethylene copolymer ratio 93%, MFR 1.5 g / 10 min)
F-4: Polyethylene (density 0.927 g / cm 3 , MFR 4.0 g / 10 min)
F-5: ethylene-propylene copolymer (ethylene copolymerization ratio 4%, density 0.90 g / cm 3 , MFR 8.0 g / 10 min)
X-1 to X-27, rx-1 to rx-5: Coating agent composition for agricultural film described in Table 2 Test category 5 (Evaluation of modified thermoplastic polymer film for agriculture)
About the agricultural modified thermoplastic polymer film of each example manufactured in Test Category 4, the coating property of the agricultural film coating agent composition, the initial droplet resistance, the droplet durability, the Dry scratch resistance, and the wet scratch resistance. The following evaluation was performed. The results are summarized in Table 4.
　・塗布性の評価
　試験区分４で製造した各例の改質熱可塑性高分子フィルムにおいて、コーティング剤組成物の付着状況を目視観察し、塗布性を以下の基準で評価した。 -Evaluation of applicability In the modified thermoplastic polymer film of each example produced in Test Category 4, the adhesion state of the coating composition was visually observed, and applicability was evaluated according to the following criteria.
　塗布性の評価基準
　◎：塗布むらは発生せず、均一に付着状態が観察され塗布性に非常に優れる。
　○：一部に塗布むらが発生しているものの、ほぼ均一に付着しており塗布性に優れる。 Evaluation standard for applicability ◎: Application unevenness does not occur, the adhesion state is observed uniformly and the applicability is very excellent.
○: Although coating unevenness occurs in part, it adheres almost uniformly and has excellent coating properties.
　△：一部にはじきが発生し、付着していない部分が観察され塗布性に劣る。
　×：全体にはじきが発生し、付着していない事が観察され塗布性に著しく劣る。
　・初期流滴性及び流滴持続性の評価
　試験区分４で製造した各例の農業用改質熱可塑性高分子フィルムを、塗布面が内側となるようテストハウスに張り、ハウスの内温３０℃、ハウスの外温１０℃及び１５度の傾斜面の条件で、水滴付着状況を観察し、水滴防止効果すなわち流滴性を評価した。初期流滴性として水滴の付着面積が１０％未満となるまでに要した時間を測定し以下の基準で評価した。また、流滴持続性として３０日間連続で置いた後の水滴の付着状態を目視観察し以下の基準で評価した。 (Triangle | delta): A part generate | occur | produces and the part which has not adhered is observed and is inferior to applicability | paintability.
X: Repelling occurs on the whole, and it is observed that it is not attached, and the coating property is remarkably inferior.
・ Evaluation of initial drop property and drop duration The agricultural modified thermoplastic polymer film of each example produced in Test Category 4 was stretched on a test house so that the coated surface was on the inside, and the internal temperature of the house was 30 ° C. The water droplet adhesion was observed under the conditions of the outside temperature of the house of 10 ° C. and the inclined surface of 15 degrees, and the water droplet prevention effect, that is, the droplet property was evaluated. The time required for the water droplet adhesion area to be less than 10% was measured as the initial flowability, and evaluated according to the following criteria. Moreover, the adhesion state of the water drop after having been placed for 30 days continuously was visually observed and evaluated according to the following criteria.
　初期流滴性評価基準
　◎：展張後１５分未満（初期流滴性に非常に優れる）。
　○：展張後１５分以上３０分未満（初期流滴性に優れる）。 Evaluation criteria for initial dropability A: Less than 15 minutes after spreading (very excellent initial dropability).
○: 15 minutes or more and less than 30 minutes after spreading (excellent initial drop property).
　△：展張後３０分以上６０分未満（初期流滴性に劣る）。
　×：展張後６０分の水滴の付着面積が１０％以上（初期流滴性に著しく劣る）。
　流滴持続性評価基準
　◎：水滴の付着が無く、流滴持続性に非常に優れる。 (Triangle | delta): 30 minutes or more and less than 60 minutes after extension (it is inferior to initial drop property).
X: Adhering area of water droplets 60 minutes after stretching is 10% or more (remarkably inferior to initial droplet property).
Evaluation criteria for drop durability ◎: No drop adhesion, very excellent drop durability.
　○：水滴の付着面積が１０％未満であり、流滴持続性に優れる。
　△：水滴の付着面積が１０％以上～５０％未満であり、流滴持続性に劣る。
　×：水滴の付着面積が５０％以上であり、流滴持続性に著しく劣る。 ○: Adhesion area of water droplets is less than 10% and excellent in droplet sustainability.
Δ: Water droplet adhesion area is 10% or more and less than 50%, which is inferior in the flowability.
X: Adhesion area of water droplets is 50% or more, and the droplet sustainability is remarkably inferior.
　・Ｄｒｙ耐擦傷性の評価
　試験区分４で製造した各例の農業用改質熱可塑性高分子フィルムについて、摩擦試験機（学振型染色堅牢度試験機、大栄科学精機製作所社製）のアームの摩擦面にビニールテープを貼って３００ｇの荷重をかけた状態で農業用改質熱可塑性高分子フィルムの塗布面１００ｃｍ２に１０往復摩擦させた後、摩擦させた部分に湯気を当て、水滴が付着して生じる曇り部分により、塗膜の剥離程度を観察し、塗膜の耐剥離強度をＤｒｙ耐擦傷性として以下の基準で評価した。 -Evaluation of Dry scratch resistance For the modified thermoplastic polymer film for agriculture of each example manufactured in Test Category 4, the arm of a friction tester (Gakushin type dyeing fastness tester, manufactured by Daiei Kagaku Seiki Seisakusho) Affixed with vinyl tape on the friction surface and applied a load of 300 g. After 10 reciprocations on the 100 cm 2 coated surface of the modified thermoplastic polymer film for agriculture, steam was applied to the rubbed part and water droplets adhered. Then, the degree of peeling of the coating film was observed by the cloudy portion generated, and the peeling resistance strength of the coating film was evaluated as Dry scratch resistance according to the following criteria.
　Ｄｒｙ耐擦傷性の評価基準
　◎：塗膜の剥がれがなく、耐擦傷性に非常に優れる。
　○：塗膜の剥がれ面積が１０％未満であり、耐擦傷性に優れる。 Evaluation criteria for dry scratch resistance A: The coating film is not peeled off, and the scratch resistance is very excellent.
○: The peeled area of the coating film is less than 10%, and the scratch resistance is excellent.
　△：塗膜の剥がれ面積が１０％以上～５０％未満であり、耐擦傷性に劣る。
　×：塗膜の剥がれ面積が５０％以上であり、耐擦傷性に著しく劣る。
　・Ｗｅｔ耐擦傷性の評価
　試験区分４で製造した各例の農業用改質熱可塑性高分子フィルムの塗布面１００ｃｍ２に水をたらして濡れた状態とし、摩擦試験機（学振型染色堅牢度試験機、大栄科学精機製作所社製）のアームの摩擦面にビニールテープを貼って３００ｇの荷重をかけた状態で前記の濡れた状態の塗布面に１０往復摩擦させた後、摩擦させた部分に湯気を当て、水滴が付着して生じる曇り部分により、塗膜の剥離程度を観察し、塗膜の耐剥離強度をＷｅｔ耐擦傷性として以下の基準で評価した。 Δ: The peeled area of the coating film is 10% to less than 50%, and the scratch resistance is poor.
X: The peeling area of the coating film is 50% or more, and the scratch resistance is remarkably inferior.
・ Evaluation of wet scratch resistance 100 cm 2 of the coated surface of the modified thermoplastic polymer film for agricultural use of each example produced in Test Category 4 was wetted with water, and a friction tester (Gakushin dyeing fastness) The test piece, manufactured by Daiei Kagaku Seiki Seisakusho Co., Ltd.) was subjected to 10 reciprocating frictions on the wet coated surface with a 300 g load applied with a vinyl tape on the friction surface of the arm, and then the rubbed part. The degree of peeling of the coating film was observed by the cloudy part formed by applying steam to the water droplets, and the peeling resistance strength of the coating film was evaluated as the wet scratch resistance according to the following criteria.
　Ｗｅｔ耐擦傷性の評価基準
　◎：塗膜の剥がれ無しがなく、耐擦傷性に非常に優れる。
　○：塗膜の剥がれ面積が１０％未満であり、耐擦傷性に優れる。 Wet scratch resistance evaluation criteria A: There is no peeling of the coating film, and the scratch resistance is very excellent.
○: The peeled area of the coating film is less than 10%, and the scratch resistance is excellent.
　△：塗膜の剥がれ面積が１０％以上～５０％未満であり、耐擦傷性に劣る。
　×：塗膜の剥がれ面積が５０％以上であり、耐擦傷性に著しく劣る。 Δ: The peeled area of the coating film is 10% to less than 50%, and the scratch resistance is poor.
X: The peeling area of the coating film is 50% or more, and the scratch resistance is remarkably inferior.
Figure JPOXMLDOC01-appb-T000004
 　表１～表３に対応する表４の結果からも明らかなように、本発明によると、農業用ハウスに張られた後において、初期の流滴性が良好であり、且つ長期間使用される間に農業用ハウスの骨材と繰り返し接触し、しかもかかる接触が乾燥状態と湿潤状態とが繰り返される状況下で行なわれた場合であっても良好な流滴性を維持することがわかる。
Figure JPOXMLDOC01-appb-T000004
 As is clear from the results of Table 4 corresponding to Tables 1 to 3, according to the present invention, after being stretched on an agricultural house, the initial drip property is good and it is used for a long time. It can be seen that even when the contact is repeatedly made with the aggregate of the agricultural house in the meantime and the contact is made in a state where the dry state and the wet state are repeated, good drip properties are maintained.

Claims (8)

  1. 　無機コロイドゾルを固形分換算で３０～７０質量％、下記のセルロース誘導体を２０～６０質量％及び水溶性架橋剤を１～３０質量％の割合で含有してなることを特徴とする農業フィルム用コーティング剤組成物。
    　セルロース誘導体：カルボキシメチルセルロース金属塩、ヒドロキシエチルセルロース、ヒドロキシプロピルメチルセルロース及びメチルセルロースから選ばれる少なくとも一つ     Agricultural film coating characterized by containing an inorganic colloidal sol in a proportion of 30 to 70% by mass in terms of solid content, 20 to 60% by mass of the following cellulose derivative and 1 to 30% by mass of a water-soluble crosslinking agent. Agent composition.
    Cellulose derivative: at least one selected from carboxymethylcellulose metal salt, hydroxyethylcellulose, hydroxypropylmethylcellulose and methylcellulose
  2. 　セルロース誘導体が、２質量％水溶液の２０℃での粘性率が１～６００ｍＰａ・ｓのものである請求項１記載の農業フィルム用コーティング剤組成物。 2. The agricultural film coating composition according to claim 1, wherein the cellulose derivative has a viscosity of 1 to 600 mPa · s at 20 ° C. in a 2 mass% aqueous solution.
  3. 　水溶性架橋剤が、水溶性メラミンである請求項１又は２記載の農業フィルム用コーティング剤組成物。 The agricultural film coating composition according to claim 1 or 2, wherein the water-soluble crosslinking agent is water-soluble melamine.
  4. 　無機コロイドゾルを固形分換算で４０～６７質量％、セルロース誘導体を３０～５０質量％及び水溶性架橋剤を３～２５質量％の割合で含有しており、且つセルロース誘導体／水溶性架橋剤＝１０／１～１０／５（質量比）の比率で含有する請求項１～３のいずれか一つの項記載の農業フィルム用コーティング剤組成物。 The inorganic colloidal sol contains 40 to 67% by mass in terms of solid content, 30 to 50% by mass of cellulose derivative and 3 to 25% by mass of water-soluble crosslinking agent, and cellulose derivative / water-soluble crosslinking agent = 10. The agricultural film coating composition according to any one of claims 1 to 3, which is contained at a ratio of / 1 to 10/5 (mass ratio).
  5. 　無機コロイドゾルを固形分換算で１００質量部に対し、更にポリエーテル変性シリコーンを０．１～５０質量部の割合で含有する請求項１～４のいずれか一つの項記載の農業フィルム用コーティング剤組成物。 The agricultural film coating agent composition according to any one of claims 1 to 4, further comprising 0.1 to 50 parts by mass of a polyether-modified silicone with respect to 100 parts by mass of the inorganic colloidal sol. object.
  6. 　熱可塑性高分子フィルムの表面処理面に、請求項１～５のいずれか一つの項記載のコーティング剤組成物が固形分として０．１５～０．５ｇ／ｍ２付着していることを特徴とする農業用改質熱可塑性高分子フィルム。 A coating agent composition according to any one of claims 1 to 5 is adhered to a surface-treated surface of a thermoplastic polymer film in an amount of 0.15 to 0.5 g / m 2 as a solid content. A modified thermoplastic polymer film for agriculture.
  7. 　表面処理が、コロナ放電処理である請求項６記載の農業用改質熱可塑性高分子フィルム。 The modified thermoplastic polymer film for agriculture according to claim 6, wherein the surface treatment is a corona discharge treatment.
  8. 　熱可塑性高分子フィルムが、ポリオレフィン系樹脂フィルムである請求項６又は７記載の農業用改質熱可塑性高分子フィルム。 The agricultural modified thermoplastic polymer film according to claim 6 or 7, wherein the thermoplastic polymer film is a polyolefin resin film.
PCT/JP2018/005785 2017-02-22 2018-02-19 Coating agent composition for agricultural film and modified thermoplastic polymer film for agriculture WO2018155389A1 (en)

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