WO2015118978A1 - ポリビニルアルコールフィルム - Google Patents

ポリビニルアルコールフィルム Download PDF

Info

Publication number
WO2015118978A1
WO2015118978A1 PCT/JP2015/052003 JP2015052003W WO2015118978A1 WO 2015118978 A1 WO2015118978 A1 WO 2015118978A1 JP 2015052003 W JP2015052003 W JP 2015052003W WO 2015118978 A1 WO2015118978 A1 WO 2015118978A1
Authority
WO
WIPO (PCT)
Prior art keywords
film
mass
pva
parts
polyvinyl alcohol
Prior art date
Application number
PCT/JP2015/052003
Other languages
English (en)
French (fr)
Japanese (ja)
Inventor
勝啓 高藤
磯▲ざき▼ 孝徳
Original Assignee
株式会社クラレ
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by 株式会社クラレ filed Critical 株式会社クラレ
Priority to KR1020167018455A priority Critical patent/KR102229234B1/ko
Priority to JP2015527715A priority patent/JP6595913B2/ja
Priority to CN201580007431.3A priority patent/CN105940050B/zh
Publication of WO2015118978A1 publication Critical patent/WO2015118978A1/ja

Links

Classifications

    • AHUMAN NECESSITIES
    • A01AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01NPRESERVATION 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
    • A01N25/00Biocides, 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
    • A01N25/34Shaped forms, e.g. sheets, not provided for in any other sub-group of this main group
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08LCOMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L29/00Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an alcohol, ether, aldehydo, ketonic, acetal or ketal radical; Compositions of hydrolysed polymers of esters of unsaturated alcohols with saturated carboxylic acids; Compositions of derivatives of such polymers
    • C08L29/02Homopolymers or copolymers of unsaturated alcohols
    • C08L29/04Polyvinyl alcohol; Partially hydrolysed homopolymers or copolymers of esters of unsaturated alcohols with saturated carboxylic acids
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B65CONVEYING; PACKING; STORING; HANDLING THIN OR FILAMENTARY MATERIAL
    • B65DCONTAINERS FOR STORAGE OR TRANSPORT OF ARTICLES OR MATERIALS, e.g. BAGS, BARRELS, BOTTLES, BOXES, CANS, CARTONS, CRATES, DRUMS, JARS, TANKS, HOPPERS, FORWARDING CONTAINERS; ACCESSORIES, CLOSURES, OR FITTINGS THEREFOR; PACKAGING ELEMENTS; PACKAGES
    • B65D65/00Wrappers or flexible covers; Packaging materials of special type or form
    • B65D65/02Wrappers or flexible covers
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B65CONVEYING; PACKING; STORING; HANDLING THIN OR FILAMENTARY MATERIAL
    • B65DCONTAINERS FOR STORAGE OR TRANSPORT OF ARTICLES OR MATERIALS, e.g. BAGS, BARRELS, BOTTLES, BOXES, CANS, CARTONS, CRATES, DRUMS, JARS, TANKS, HOPPERS, FORWARDING CONTAINERS; ACCESSORIES, CLOSURES, OR FITTINGS THEREFOR; PACKAGING ELEMENTS; PACKAGES
    • B65D65/00Wrappers or flexible covers; Packaging materials of special type or form
    • B65D65/38Packaging materials of special type or form
    • B65D65/46Applications of disintegrable, dissolvable or edible materials
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08JWORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J5/00Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/18Manufacture of films or sheets
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08KUse of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00Use of organic ingredients
    • C08K5/0008Organic ingredients according to more than one of the "one dot" groups of C08K5/01 - C08K5/59
    • C08K5/0016Plasticisers
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08KUse of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00Use of organic ingredients
    • C08K5/36Sulfur-, selenium-, or tellurium-containing compounds
    • C08K5/41Compounds containing sulfur bound to oxygen
    • C08K5/42Sulfonic acids; Derivatives thereof
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08JWORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2329/00Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an alcohol, ether, aldehydo, ketonic, acetal, or ketal radical; Hydrolysed polymers of esters of unsaturated alcohols with saturated carboxylic acids; Derivatives of such polymer
    • C08J2329/02Homopolymers or copolymers of unsaturated alcohols
    • C08J2329/04Polyvinyl alcohol; Partially hydrolysed homopolymers or copolymers of esters of unsaturated alcohols with saturated carboxylic acids

Definitions

  • the present invention relates to a polyvinyl alcohol film useful for unit packaging of chemicals such as agricultural chemicals and detergents, and a package using the same.
  • a jumbo agent for paddy fields is an agrochemical active ingredient by dissolving the water-soluble film that wraps it in the paddy field and diffusing it throughout the paddy field by floating the jumbo agent contained in the package. Will spread. At this time, if the water-soluble film does not dissolve quickly or the diffusibility of the pesticidal active ingredient is insufficient, the pesticidal active ingredient cannot be distributed throughout the paddy field.
  • a polyvinyl alcohol film As a water-soluble film used for unit packaging, a polyvinyl alcohol film (hereinafter, “polyvinyl alcohol” may be abbreviated as “PVA”) is known. Specifically, for example, a specific sulfonic acid group-containing film is used. A film using modified PVA having a unit (see Patent Document 1), a film containing PVA and a water-soluble sulfonate-containing compound (see Patent Document 2), and the like are known.
  • an object of the present invention is to provide a PVA film that dissolves quickly after being poured into water and has excellent diffusibility of the packaged drug, and a package using the PVA film.
  • the present invention [1] A PVA film containing PVA, a water surface spreading agent and a plasticizer, wherein the plasticizer content is 10 to 40 parts by mass with respect to 100 parts by mass of PVA; [2] The PVA film according to [1], wherein the content of the water surface spreading agent is 0.1 to 15 parts by mass with respect to 100 parts by mass of PVA; [3] The PVA film according to [1] or [2], wherein the water surface spreading agent is a dialkyl sulfosuccinate.
  • a PVA film that dissolves rapidly after being poured into water and is excellent in diffusibility of the packaged medicine, and a package using the PVA film.
  • the PVA film of the present invention contains PVA, a water surface spreading agent and a plasticizer.
  • the plasticizer content is 10 to 40 parts by mass with respect to 100 parts by mass of PVA.
  • the plasticizer is contained in the above-described content, it further becomes a PVA film that dissolves rapidly after being put into water and is excellent in diffusibility of the packaged medicine by containing the plasticizer.
  • the PVA is one of vinyl esters such as vinyl acetate, vinyl formate, vinyl propionate, vinyl butyrate, vinyl pivalate, vinyl versatate, vinyl laurate, vinyl stearate, vinyl benzoate, and isopropenyl acetate. Or what is obtained by saponifying the polyvinyl ester obtained by superposing
  • the above-mentioned polyvinyl ester may be obtained using only one or two or more kinds of vinyl esters as a monomer. It may be a copolymer of two or more kinds of vinyl esters and other monomers copolymerizable therewith.
  • Examples of the other monomer copolymerizable with the vinyl ester include ⁇ -olefins having 2 to 30 carbon atoms such as ethylene, propylene, 1-butene, and isobutene; (meth) acrylic acid or a salt thereof; (Meth) methyl acrylate, (meth) ethyl acrylate, (meth) acrylate n-propyl, (meth) acrylate i-propyl, (meth) acrylate n-butyl, (meth) acrylate i-butyl, ( (Meth) acrylic acid esters such as t-butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, dodecyl (meth) acrylate, octadecyl (meth) acrylate; (meth) acrylamide, N-methyl ( (Meth) acrylamide, N-ethyl (meth) acrylamide, N,
  • Vinyl ether vinyl cyanide such as (meth) acrylonitrile
  • vinyl halide such as vinyl chloride, vinylidene chloride, vinyl fluoride, vinylidene fluoride
  • Allyl compounds such as allyl acetate and allyl chloride; maleic acid or its salts, esters or acid anhydrides; itaconic acid or its salts, esters or acid anhydrides
  • vinylsilyl compounds such as vinyltrimethoxysilane; unsaturated sulfonic acids be able to.
  • Said polyvinyl ester can have a structural unit derived from 1 type, or 2 or more types of an above described other monomer.
  • the proportion of structural units derived from the other monomers described above in the polyvinyl ester is preferably 25 mol% or less based on the number of moles of all structural units constituting the polyvinyl ester, and is 15 mol%. More preferably, it is more preferably 5 mol% or less.
  • the above PVA may be modified with one or two or more types of graft copolymerizable monomers as long as the effects of the present invention are not impaired.
  • the graft copolymerizable monomer include unsaturated carboxylic acids or derivatives thereof; unsaturated sulfonic acids or derivatives thereof; ⁇ -olefins having 2 to 30 carbon atoms, and the like.
  • the proportion of structural units derived from the graft copolymerizable monomer in PVA (structural units in the graft modified portion) is preferably 5 mol% or less based on the number of moles of all structural units constituting PVA. .
  • the PVA described above may be partially or not crosslinked in the hydroxyl group. Moreover, said PVA may react with aldehyde compounds, such as acetaldehyde and a butyraldehyde, etc. to form an acetal structure, and the said PVA does not react with these compounds and does not form an acetal structure. May be.
  • aldehyde compounds such as acetaldehyde and a butyraldehyde, etc.
  • the degree of polymerization of the PVA is not particularly limited, but is preferably 300 or more, more preferably 500 or more, further preferably 800 or more, particularly preferably 1,000 or more, It is preferably 10,000 or less, more preferably 8,000 or less, further preferably 5,000 or less, and particularly preferably 2,000 or less.
  • the degree of polymerization degree being 300 or more, the intensity
  • the degree of polymerization is 10,000 or less, industrial production of the PVA becomes easy.
  • the degree of polymerization of PVA means the average degree of polymerization measured according to the description of JIS K6726-1994.
  • the degree of saponification of the above PVA is not particularly limited, but is preferably 80 mol% or more, more preferably 82 mol% or more, and 84 mol% from the viewpoint of strength, waist and bag-making property of the obtained PVA film. % Or more, more preferably 99.9 mol% or less, more preferably 99 mol% or less, and even more preferably 98 mol% or less.
  • degree of saponification of PVA is 80 mol% or more, sufficient elasticity can be imparted to the film, and the form stability is improved.
  • an alkaline substance or acidic substance is packaged and stored in the film Moreover, the water-soluble fall of a film can be prevented more effectively.
  • the degree of saponification of PVA refers to the total number of moles of structural units (typically vinyl ester units) that can be converted into vinyl alcohol units by saponification and the vinyl alcohol units of PVA.
  • the degree of saponification can be measured according to the description of JIS-K6726-1994.
  • the type of the water surface spreading agent is not particularly limited, but dialkylsulfosuccinate is preferable because the effects of the present invention are more remarkably exhibited.
  • the dialkylsulfosuccinate is a compound having a structure corresponding to a structure in which two carboxyl groups in the sulfosuccinate are each converted to an alkyl ester, and is obtained by any production method as long as it has the structure. There may be.
  • the alkyl groups in the two alkyl ester moieties of the dialkyl sulfosuccinate may be the same or different from each other, but are preferably the same from the viewpoint of ease of production. .
  • either one or both of the alkyl groups in the dialkyl sulfosuccinate may be a linear alkyl group, or one or both may be a branched alkyl group.
  • the alkyl group include methyl group, ethyl group, propyl group, isopropyl group, pentyl group, hexyl group, heptyl group, octyl group, 2-ethylhexyl group, nonyl group, decanyl group, undecanyl group, and dodecanyl group. Can be mentioned.
  • At least one (preferably both) of the alkyl groups in the dialkylsulfosuccinate is preferably an alkyl group having 6 to 12 carbon atoms.
  • An alkyl group of 7 to 10 is more preferable.
  • at least one (preferably both) of the alkyl groups in the dialkylsulfosuccinate is preferably a linear alkyl group.
  • Examples of the salt in the dialkylsulfosuccinate include inorganic salts, preferably sodium salt, potassium salt, and ammonium salt, and more preferably sodium salt.
  • the content of the water surface broadening agent in the PVA film is such that the effects of the present invention are more remarkably achieved, and the high mechanical properties can be maintained and the handleability is improved. It is preferably 1 part by mass or more, more preferably 1 part by mass or more, further preferably 3 parts by mass or more, and preferably 15 parts by mass or less, and 14 parts by mass or less. More preferably, the amount is 12 parts by mass or less.
  • plasticizer examples include polyhydric alcohols, and specific examples thereof include ethylene glycol, glycerin, propylene glycol, diethylene glycol, diglycerin, triethylene glycol, tetraethylene glycol, trimethylolpropane, and polyethylene glycol. Can be mentioned.
  • the PVA film can contain one or more of these plasticizers. Among these, at least one selected from the group consisting of glycerin, diglycerin and polyethylene glycol is preferable.
  • the number average molecular weight of polyethylene glycol is not particularly limited, but may be in the range of 100 to 1,000 from the viewpoint of compatibility with PVA and prevention of reduction in water solubility of the film due to bleeding out. preferable.
  • the content of the plasticizer in the PVA film dissolves quickly after being poured into water, and becomes a PVA film excellent in the diffusibility of the packaged medicine. Therefore, the content of the plasticizer is within the range of 10 to 40% by mass with respect to 100 parts by mass of PVA.
  • the content is preferably 12 parts by mass or more, more preferably 14 parts by mass or more, and preferably 38 parts by mass or less, and 36 parts by mass or less. More preferably.
  • PVA films include starch and / or other than PVA. Another water-soluble polymer may be further contained.
  • starch examples include natural starches such as corn starch, potato starch, sweet potato starch, wheat starch, rice starch, tapioca starch, and sago starch; processed starches subjected to etherification, esterification, oxidation, etc. In particular, modified starches are preferred.
  • the starch content in the PVA film is preferably 15 parts by mass or less and more preferably 10 parts by mass or less with respect to 100 parts by mass of PVA.
  • the content is 15 parts by mass or less, the impact resistance of the PVA film is improved and the process passability is improved.
  • water-soluble polymers other than PVA include, for example, dextrin, gelatin, glue, casein, shellac, gum arabic, polyacrylic acid amide, sodium polyacrylate, polyvinyl methyl ether, methyl vinyl ether and maleic anhydride.
  • examples thereof include a polymer, a copolymer of vinyl acetate and itaconic acid, polyvinyl pyrrolidone, cellulose, acetyl cellulose, acetyl butyl cellulose, carboxymethyl cellulose, methyl cellulose, ethyl cellulose, hydroxyethyl cellulose, and sodium alginate.
  • the content of the water-soluble polymer other than PVA in the PVA film is preferably 15 parts by mass or less and more preferably 10 parts by mass or less with respect to 100 parts by mass of PVA. When the content is 15 parts by mass or less, the water solubility and dispersibility of the PVA film are improved.
  • the PVA film further includes a filler, a processing stabilizer such as a copper compound, a weather resistance stabilizer, a colorant, an ultraviolet absorber, a light stabilizer, an antioxidant, an antistatic agent, a flame retardant, and other thermoplastic resins. , Lubricants, fragrances, antifoaming agents, deodorants, extenders, release agents, mold release agents, reinforcing agents, crosslinking agents, fungicides, preservatives, crystallization rate retarders, surfactants described later, etc. Additives can be appropriately contained as necessary.
  • a processing stabilizer such as a copper compound, a weather resistance stabilizer, a colorant, an ultraviolet absorber, a light stabilizer, an antioxidant, an antistatic agent, a flame retardant, and other thermoplastic resins.
  • Lubricants Lubricants, fragrances, antifoaming agents, deodorants, extenders, release agents, mold release agents, reinforcing agents, crosslinking agents, fungicides, preservatives
  • the proportion of the total of the PVA, the water surface spreading agent and the plasticizer is preferably 80% by mass or more, more preferably 90% by mass or more based on the mass of the PVA film. And more preferably 95% by mass or more.
  • the thickness of the PVA film is not particularly limited, but it is preferably 1 ⁇ m or more, more preferably 5 ⁇ m or more, further preferably 10 ⁇ m or more, and 100 ⁇ m or less from the viewpoint of both strength and water solubility. Preferably, it is 75 ⁇ m or less, and more preferably 60 ⁇ m or less.
  • the shape of the PVA film is not particularly limited, and examples thereof include a quadrangle (for example, a rectangle, a square, etc.), a circle, a triangle, and the like, and can be appropriately set according to the usage form of the PVA film of the present invention.
  • a long film is preferable because it can be continuously produced and can be easily stored and transported in a rolled state.
  • the length of the long PVA film is not particularly limited, but is preferably 1 m or more, more preferably 100 m or more, and more preferably 1,000 m or more from the viewpoint of productivity during processing. preferable.
  • the upper limit of the length is, for example, 10,000 m.
  • the width of the long PVA film is not particularly limited, but is preferably 50 cm or more, more preferably 80 cm or more, and further preferably 100 cm or more from the viewpoint of productivity during processing. .
  • An example of the upper limit of the width is 5 m.
  • the PVA film can be used by cutting into a desired size when used.
  • the production method of the PVA film of the present invention is not particularly limited, and a production method in which the thickness and width of the PVA film after film formation are more uniform can be preferably adopted.
  • the film-forming stock solution contains at least one of starch, other water-soluble polymers and additives, it is preferable that these components are uniformly mixed.
  • liquid medium used for the preparation of the membrane forming stock solution examples include water, dimethyl sulfoxide, dimethylformamide, dimethylacetamide, N-methylpyrrolidone, ethylene glycol, glycerin, propylene glycol, diethylene glycol, triethylene glycol, and tetraethylene glycol. , Trimethylolpropane, ethylenediamine, diethylenetriamine and the like, and one or more of them can be used. Among these, water is preferable from the viewpoint of environmental load and recoverability.
  • the volatile fraction of the film-forming stock solution (content ratio in the film-forming stock solution of volatile components such as liquid media removed by volatilization or evaporation during film formation) varies depending on the film-forming method, film-forming conditions, etc. Specifically, it is preferably in the range of 50 to 95% by mass, more preferably in the range of 55 to 90% by mass, and still more preferably in the range of 60 to 85% by mass.
  • the volatile fraction of the film-forming stock solution is 50% by mass or more, the viscosity of the film-forming stock solution does not become too high, and filtration and defoaming are smoothly performed during preparation of the film-forming stock solution, and there are few foreign matters and defects. Film production is facilitated.
  • the volatile fraction of the film-forming stock solution is 95% by mass or less, the concentration of the film-forming stock solution does not become too low, and the production of an industrial PVA film becomes easy.
  • the film forming stock solution preferably contains a surfactant.
  • a surfactant By including the surfactant, the film-forming property is improved and the occurrence of uneven thickness of the PVA film is suppressed, and the PVA film is easily peeled off from the metal roll or belt used for film formation.
  • the PVA film may contain a surfactant.
  • the kind of said surfactant is not specifically limited, From a viewpoint of the peelability from a metal roll or a belt, an anionic surfactant or a nonionic surfactant is preferable.
  • anionic surfactant for example, a carboxylic acid type such as potassium laurate; a sulfuric acid ester type such as polyoxyethylene lauryl ether sulfate and octyl sulfate; and a sulfonic acid type such as dodecylbenzene sulfonate are suitable.
  • a carboxylic acid type such as potassium laurate
  • a sulfuric acid ester type such as polyoxyethylene lauryl ether sulfate and octyl sulfate
  • a sulfonic acid type such as dodecylbenzene sulfonate
  • Nonionic surfactants include, for example, alkyl ether types such as polyoxyethylene oleyl ether; alkylphenyl ether types such as polyoxyethylene octylphenyl ether; alkyl ester types such as polyoxyethylene laurate; polyoxyethylene laurylamino Alkylamine type such as ether; alkylamide type such as polyoxyethylene lauric acid amide; polypropylene glycol ether type such as polyoxyethylene polyoxypropylene ether; alkanolamide type such as lauric acid diethanolamide and oleic acid diethanolamide; polyoxy An allyl phenyl ether type such as alkylene allyl phenyl ether is preferred.
  • surfactants can be used alone or in combination of two or more.
  • the content thereof is preferably in the range of 0.01 to 5 parts by mass with respect to 100 parts by mass of PVA contained in the film-forming stock solution, and 0.02 to 4 It is more preferably in the range of parts by mass, and particularly preferably in the range of 0.05 to 3 parts by mass.
  • the content is 0.01 parts by mass or more, the film forming property and the peelability are further improved.
  • the content is 5 parts by mass or less, it can be suppressed that the surfactant bleeds out to the surface of the PVA film to cause blocking and lower the handleability.
  • Examples of the film forming method for forming a PVA film using the above-described film forming stock solution include a cast film forming method, an extrusion film forming method, a wet film forming method, and a gel film forming method. These film forming methods may be used alone or in combination of two or more. Among these film forming methods, the cast film forming method and the extrusion film forming method are preferable because a PVA film having uniform thickness and width and good physical properties can be obtained. The formed PVA film can be dried or heat-treated as necessary.
  • a T-type slit die, a hopper plate, an I-die, a lip coater die or the like is used to rotate the above film forming stock solution on the most upstream side.
  • the volatile component is uniformly discharged or cast on the peripheral surface of the first roll (or belt) and the volatile component is discharged from one surface of the film discharged or cast on the peripheral surface of the first roll (or belt).
  • the method of winding with a winding device can be preferably employed industrially. Drying with a heated roll and drying with a hot air dryer may be performed in an appropriate combination.
  • the surface of the PVA film is preferably matted for the purpose of improving the slip property of the surface.
  • the mat treatment method include an on-line mat treatment method in which the surface of a mat on a roll or belt is transferred to a film during film formation, and a method in which an emboss treatment is performed after the formed film is once wound on a roll.
  • the arithmetic average height (Ra) of the mat-treated surface is preferably 0.5 ⁇ m or more, and more preferably 1 ⁇ m or more.
  • the upper limit of the arithmetic average height (Ra) is, for example, 10 ⁇ m from the viewpoint of pinhole resistance. When the arithmetic average height (Ra) is less than 0.5 ⁇ m, it is difficult to obtain sufficient slip properties.
  • the maximum height (Rz) is preferably 1 ⁇ m or more, and more preferably 3 ⁇ m or more.
  • the upper limit of the maximum height (Rz) is, for example, 20 ⁇ m from the viewpoint of pinhole resistance.
  • the maximum height (Rz) is less than 0.5 ⁇ m, it is difficult to obtain sufficient slip properties.
  • the arithmetic average height (Ra) and the maximum height (Rz) are defined by JIS B 0601: 2001.
  • the PVA film of the present invention is preferably used as a drug packaging film because it dissolves quickly after being poured into water and has excellent diffusibility of the packaged drug.
  • the medicine to be packaged include agricultural chemicals and detergents (including bleaching agents), and agricultural chemicals are preferable.
  • the specific type of pesticide but it is preferably a jumbo agent because the effects of the present invention are more prominent.
  • the form of the drug include powder, lump, gel, liquid and the like.
  • the unit packaging which packages a chemical
  • Model test for drug packaging The PVA film produced in the following examples or comparative examples was conditioned at 20 ° C. and 65% RH for 24 hours. Subsequently, 2.5 g of 3-4 mm ⁇ polyethylene pellets were hermetically packaged with a conditioned PVA film. Specifically, a bag is prepared by heat-sealing three sides so that the shape of the part containing the polyethylene pellets is a 30 mm ⁇ 30 mm square, and then the polyethylene pellets are put into this, and the remaining one is heat-sealed. And packaged. Next, 15 ° C.
  • the water was introduced to a depth of 2 cm in an 18 cm ⁇ 25 cm bat, and the above-mentioned bag in which polyethylene pellets were packaged was floated on the water surface at the center of the bat.
  • the time from when the bag floats on the surface of the water until the PVA film dissolves and the polyethylene pellets in the bag begin to diffuse into the surface of the water is defined as the bag breakage time. (Good) and the case where it exceeded 80 second was determined as solubility "x" (poor).
  • solubility "x" solubility "x”
  • the state of 180 seconds after the bag was floated on the surface of the water was photographed with a camera from above, and when the polyethylene pellet was diffused by 80% or more with respect to the area of the bat (450 cm 2 ), the diffusivity was “ ⁇ ”.
  • the diffusivity was determined as “ ⁇ ” (slightly good), and when the diffusion was less than 60%, the diffusivity was “x” (bad) ).
  • the bat is divided into 25 equal parts (one area is 3.6 cm ⁇ 5 cm), and if there is at least one polyethylene pellet in the equally divided area, the area is diffused. It was done by judging.
  • Example 1 100 parts by mass of PVA (saponified product of vinyl acetate homopolymer) having a polymerization degree of 1,700 and a saponification degree of 88 mol%, 20 parts by mass of glycerin, 0.1 parts by mass of sodium polyoxyethylene lauryl ether sulfate, and Then, an aqueous solution containing 5 parts by mass of sodium dioctyl sulfosuccinate as a water surface spreading agent and having a PVA content of 10% by mass was prepared. This aqueous solution was dried and peeled off on a metal roll at 80 ° C. and then heat treated at 100 ° C. for 1 minute to produce a PVA film having a thickness of 40 ⁇ m. Using the obtained PVA film, a drug packaging model test was carried out by the method described above. The obtained results are shown in Table 1.
  • Example 2 A PVA film having a thickness of 40 ⁇ m was produced in the same manner as in Example 1 except that the amount of sodium dioctylsulfosuccinate was changed to 1 part by mass. Using the obtained PVA film, a drug packaging model test was carried out by the method described above. The obtained results are shown in Table 1.
  • Example 3 A PVA film having a thickness of 40 ⁇ m was produced in the same manner as in Example 1 except that the amount of sodium dioctylsulfosuccinate was changed to 10 parts by mass. Using the obtained PVA film, a drug packaging model test was carried out by the method described above. The obtained results are shown in Table 1.
  • Example 4 A PVA film having a thickness of 40 ⁇ m was prepared in the same manner as in Example 1 except that 5 parts by mass of sodium di (2-ethylhexyl) sulfosuccinate was used as the water surface spreading agent in place of 5 parts by mass of sodium dioctyl sulfosuccinate. Manufactured. Using the obtained PVA film, a drug packaging model test was carried out by the method described above. The obtained results are shown in Table 1.
  • Example 5 A PVA film having a thickness of 40 ⁇ m was produced in the same manner as in Example 3 except that the amount of glycerin used was changed to 35 parts by mass. Using the obtained PVA film, a drug packaging model test was carried out by the method described above. The obtained results are shown in Table 1.
  • Example 6 Instead of 100 parts by mass of PVA (saponified vinyl acetate homopolymer) having a polymerization degree of 1,700 and a saponification degree of 88 mol%, a polymerization degree of 1,700, a saponification degree of 88 mol%, 2-acrylamido-2-methyl Example 1 except that 100 parts by mass of PVA (saponified copolymer of vinyl acetate and sodium 2-acrylamido-2-methylpropanesulfonate) having a sodium propanesulfonate unit content of 2 mol% was used. Similarly, a PVA film having a thickness of 40 ⁇ m was produced. Using the obtained PVA film, a drug packaging model test was carried out by the method described above. The obtained results are shown in Table 1.
  • Example 7 A PVA film having a thickness of 40 ⁇ m was produced in the same manner as in Example 6 except that 10 parts by mass of glycerin and 10 parts by mass of diglycerin were used instead of 20 parts by mass of glycerin. Using the obtained PVA film, a drug packaging model test was carried out by the method described above. The obtained results are shown in Table 1.
  • Example 8 A PVA film having a thickness of 40 ⁇ m was obtained in the same manner as in Example 6 except that 10 parts by mass of glycerin, 10 parts by mass of diglycerin and 5 parts by mass of polyethylene glycol having a number average molecular weight of 400 were used instead of 20 parts by mass of glycerin. Manufactured. Using the obtained PVA film, a drug packaging model test was carried out by the method described above. The obtained results are shown in Table 1.
  • Example 1 A PVA film having a thickness of 40 ⁇ m was produced in the same manner as in Example 1 except that sodium dioctyl sulfosuccinate was not used. Using the obtained PVA film, a drug packaging model test was carried out by the method described above. The obtained results are shown in Table 1.
  • Example 2 A PVA film having a thickness of 40 ⁇ m was produced in the same manner as in Example 1 except that 10 parts by mass of sodium allyl sulfonate was used instead of 5 parts by mass of sodium dioctyl sulfosuccinate. Using the obtained PVA film, a drug packaging model test was carried out by the method described above. The obtained results are shown in Table 1.
  • Example 3 A PVA film having a thickness of 40 ⁇ m was produced in the same manner as in Example 1 except that the amount of glycerin used was changed to 5 parts by mass. Using the obtained PVA film, a drug packaging model test was carried out by the method described above. The obtained results are shown in Table 1.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Manufacturing & Machinery (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Mechanical Engineering (AREA)
  • Materials Engineering (AREA)
  • General Health & Medical Sciences (AREA)
  • Agronomy & Crop Science (AREA)
  • Plant Pathology (AREA)
  • Toxicology (AREA)
  • Dentistry (AREA)
  • Wood Science & Technology (AREA)
  • Zoology (AREA)
  • Environmental Sciences (AREA)
  • Pest Control & Pesticides (AREA)
  • Manufacture Of Macromolecular Shaped Articles (AREA)
  • Wrappers (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
PCT/JP2015/052003 2014-02-06 2015-01-26 ポリビニルアルコールフィルム WO2015118978A1 (ja)

Priority Applications (3)

Application Number Priority Date Filing Date Title
KR1020167018455A KR102229234B1 (ko) 2014-02-06 2015-01-26 폴리비닐알코올 필름
JP2015527715A JP6595913B2 (ja) 2014-02-06 2015-01-26 ポリビニルアルコールフィルム
CN201580007431.3A CN105940050B (zh) 2014-02-06 2015-01-26 聚乙烯醇膜

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
JP2014-021165 2014-02-06
JP2014021165 2014-02-06
JP2014-044531 2014-03-07
JP2014044531 2014-03-07

Publications (1)

Publication Number Publication Date
WO2015118978A1 true WO2015118978A1 (ja) 2015-08-13

Family

ID=53777785

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/JP2015/052003 WO2015118978A1 (ja) 2014-02-06 2015-01-26 ポリビニルアルコールフィルム

Country Status (5)

Country Link
JP (1) JP6595913B2 (zh)
KR (1) KR102229234B1 (zh)
CN (1) CN105940050B (zh)
TW (1) TWI639510B (zh)
WO (1) WO2015118978A1 (zh)

Cited By (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2017119434A (ja) * 2015-12-25 2017-07-06 日本合成化学工業株式会社 水溶性フィルム、薬剤包装体及び水溶性フィルムの製造方法
WO2019124310A1 (ja) * 2017-12-22 2019-06-27 株式会社クラレ ポリビニルアルコールフィルム、フィルムロールおよびフィルムロールの製造方法
WO2020031969A1 (ja) * 2018-08-07 2020-02-13 積水化学工業株式会社 水溶性包装用フィルム、及び包装体
JP2020070372A (ja) * 2018-10-31 2020-05-07 三菱ケミカル株式会社 フィルムコーティング組成物、固形製剤及び固形製剤の製造方法
WO2020138439A1 (ja) * 2018-12-28 2020-07-02 株式会社クラレ 水溶性フィルムおよび包装体
CN113227224A (zh) * 2018-12-28 2021-08-06 株式会社可乐丽 水溶性膜以及包装体
WO2022004342A1 (ja) * 2020-06-29 2022-01-06 株式会社クラレ 水溶性フィルムおよび包装体
WO2022004345A1 (ja) * 2020-06-29 2022-01-06 株式会社クラレ 水溶性フィルムおよび包装体
CN114945522A (zh) * 2020-01-14 2022-08-26 株式会社爱赛璐 水溶性薄膜及具有相同功能的药物封装胶囊材料

Families Citing this family (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP7326670B2 (ja) * 2018-04-10 2023-08-16 株式会社アイセロ 水溶性フィルム
WO2019208618A1 (ja) * 2018-04-27 2019-10-31 株式会社クラレ ポリビニルアルコールフィルム及びそれを用いた偏光フィルムの製造方法
WO2020138442A1 (ja) * 2018-12-28 2020-07-02 株式会社クラレ 水溶性フィルムおよび包装体
WO2023054721A1 (ja) * 2021-10-01 2023-04-06 株式会社クラレ 水溶性フィルム、製造方法及び包装体

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2002012504A (ja) * 2000-04-28 2002-01-15 Sankyo Co Ltd 高吸油能を有する生分解性水面浮遊発泡体、その製造方法及びそれを含有する組成物
JP2002020507A (ja) * 2000-07-13 2002-01-23 Kuraray Co Ltd ポリビニルアルコール系水溶性フィルムおよびその製造法
JP2004155922A (ja) * 2002-11-07 2004-06-03 Nippon Synthetic Chem Ind Co Ltd:The ポリビニルアルコール系フィルム及びその製造方法
JP2010012778A (ja) * 2008-06-30 2010-01-21 Lg Chem Ltd ポリビニルアルコール系フィルムの製造方法、それから形成されたポリビニルアルコール系フィルム、及びこれを備えた偏光板

Family Cites Families (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS5615202A (en) * 1979-07-13 1981-02-14 Kureha Chem Ind Co Ltd Agricultural drug composition
JP3118352B2 (ja) 1993-10-27 2000-12-18 株式会社クラレ 農薬包装用水溶性フィルム
JPH0940834A (ja) 1995-07-28 1997-02-10 Unitika Chem Kk ポリビニルアルコール系フィルム
JPH10265302A (ja) * 1997-03-27 1998-10-06 Nissan Chem Ind Ltd 水面施用農薬粒剤
JP2003026504A (ja) * 2001-05-10 2003-01-29 Sds Biotech:Kk 尿素含有農薬固形剤ならびにその製造方法
CN102286183B (zh) * 2011-06-17 2013-09-11 包头市恒瑞新材料科技有限公司 可塑性pva树脂及其制备方法

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2002012504A (ja) * 2000-04-28 2002-01-15 Sankyo Co Ltd 高吸油能を有する生分解性水面浮遊発泡体、その製造方法及びそれを含有する組成物
JP2002020507A (ja) * 2000-07-13 2002-01-23 Kuraray Co Ltd ポリビニルアルコール系水溶性フィルムおよびその製造法
JP2004155922A (ja) * 2002-11-07 2004-06-03 Nippon Synthetic Chem Ind Co Ltd:The ポリビニルアルコール系フィルム及びその製造方法
JP2010012778A (ja) * 2008-06-30 2010-01-21 Lg Chem Ltd ポリビニルアルコール系フィルムの製造方法、それから形成されたポリビニルアルコール系フィルム、及びこれを備えた偏光板

Cited By (16)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2017119434A (ja) * 2015-12-25 2017-07-06 日本合成化学工業株式会社 水溶性フィルム、薬剤包装体及び水溶性フィルムの製造方法
WO2019124310A1 (ja) * 2017-12-22 2019-06-27 株式会社クラレ ポリビニルアルコールフィルム、フィルムロールおよびフィルムロールの製造方法
JP7223709B2 (ja) 2017-12-22 2023-02-16 株式会社クラレ ポリビニルアルコールフィルム、フィルムロールおよびフィルムロールの製造方法
JPWO2019124310A1 (ja) * 2017-12-22 2020-12-24 株式会社クラレ ポリビニルアルコールフィルム、フィルムロールおよびフィルムロールの製造方法
WO2020031969A1 (ja) * 2018-08-07 2020-02-13 積水化学工業株式会社 水溶性包装用フィルム、及び包装体
JPWO2020031969A1 (ja) * 2018-08-07 2021-08-10 積水化学工業株式会社 水溶性包装用フィルム、及び包装体
JP2020070372A (ja) * 2018-10-31 2020-05-07 三菱ケミカル株式会社 フィルムコーティング組成物、固形製剤及び固形製剤の製造方法
JP7119913B2 (ja) 2018-10-31 2022-08-17 三菱ケミカル株式会社 フィルムコーティング組成物、固形製剤及び固形製剤の製造方法
JPWO2020138439A1 (ja) * 2018-12-28 2021-11-11 株式会社クラレ 水溶性フィルムおよび包装体
CN113227224A (zh) * 2018-12-28 2021-08-06 株式会社可乐丽 水溶性膜以及包装体
WO2020138439A1 (ja) * 2018-12-28 2020-07-02 株式会社クラレ 水溶性フィルムおよび包装体
JP7344907B2 (ja) 2018-12-28 2023-09-14 株式会社クラレ 水溶性フィルムおよび包装体
CN113227224B (zh) * 2018-12-28 2023-09-19 株式会社可乐丽 水溶性膜以及包装体
CN114945522A (zh) * 2020-01-14 2022-08-26 株式会社爱赛璐 水溶性薄膜及具有相同功能的药物封装胶囊材料
WO2022004342A1 (ja) * 2020-06-29 2022-01-06 株式会社クラレ 水溶性フィルムおよび包装体
WO2022004345A1 (ja) * 2020-06-29 2022-01-06 株式会社クラレ 水溶性フィルムおよび包装体

Also Published As

Publication number Publication date
TW201534473A (zh) 2015-09-16
KR20160118226A (ko) 2016-10-11
JP6595913B2 (ja) 2019-10-23
CN105940050A (zh) 2016-09-14
KR102229234B1 (ko) 2021-03-17
CN105940050B (zh) 2018-07-10
JPWO2015118978A1 (ja) 2017-03-23
TWI639510B (zh) 2018-11-01

Similar Documents

Publication Publication Date Title
JP6595913B2 (ja) ポリビニルアルコールフィルム
JP7240420B2 (ja) 水溶性フィルム、その製造方法および包装体
WO2018230583A1 (ja) 水溶性フィルム及び薬剤包装体、ならびに水溶性フィルムの製造方法
JP7162077B2 (ja) 水溶性フィルムおよび包装体
JP7323018B2 (ja) 水溶性フィルム及び薬剤包装体
WO2015020045A1 (ja) フィルム
JP2024069259A (ja) 水溶性フィルムおよび包装体
JP7240421B2 (ja) 水溶性フィルム、その製造方法および包装体
WO2020138440A1 (ja) 水溶性フィルムおよび包装体
JP7344907B2 (ja) 水溶性フィルムおよび包装体
WO2020138442A1 (ja) 水溶性フィルムおよび包装体
JP7493507B2 (ja) 水溶性フィルムおよび包装体
JP4601735B2 (ja) ポリビニルアルコールフィルム
JP7343732B2 (ja) 水溶性フィルム、製造方法及び包装体
WO2022004346A1 (ja) 水溶性フィルムおよび包装体
US11939441B2 (en) Water-soluble film, manufacturing method, and package
WO2022004343A1 (ja) 水溶性フィルムおよび包装体
JP4070186B2 (ja) ポリビニルアルコール系樹脂フイルム積層体およびその用途
WO2022004342A1 (ja) 水溶性フィルムおよび包装体
WO2022004345A1 (ja) 水溶性フィルムおよび包装体

Legal Events

Date Code Title Description
ENP Entry into the national phase

Ref document number: 2015527715

Country of ref document: JP

Kind code of ref document: A

121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 15746184

Country of ref document: EP

Kind code of ref document: A1

ENP Entry into the national phase

Ref document number: 20167018455

Country of ref document: KR

Kind code of ref document: A

NENP Non-entry into the national phase

Ref country code: DE

122 Ep: pct application non-entry in european phase

Ref document number: 15746184

Country of ref document: EP

Kind code of ref document: A1