WO2015118978A1 - Polyvinyl alcohol film - Google Patents

Polyvinyl alcohol film Download PDF

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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
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WO
WIPO (PCT)
Prior art keywords
film
mass
pva
parts
polyvinyl alcohol
Prior art date
Application number
PCT/JP2015/052003
Other languages
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 JP2015527715A priority Critical patent/JP6595913B2/en
Priority to KR1020167018455A priority patent/KR102229234B1/en
Priority to CN201580007431.3A priority patent/CN105940050B/en
Publication of WO2015118978A1 publication Critical patent/WO2015118978A1/en

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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.

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Abstract

[Problem] To provide: a polyvinyl alcohol film which quickly dissolves after being introduced into water and exhibits excellent spreadability for drugs packaged thereby; and a package using the same. [Solution] A polyvinyl alcohol film which comprises a polyvinyl alcohol, surface spreader, and plasticizer, wherein the content of the plasticizer is 10 to 40 parts by mass with respect to 100 parts by mass of the polyvinyl alcohol; and a package which is wrapped with the polyvinyl alcohol film. The content of the surface spreader is preferably 0.1 to 15 parts by mass with respect to 100 parts by mass of the polyvinyl alcohol, the surface spreader is preferably a dialkyl sulfosuccinic acid salt, and at least one of the alkyl groups in the dialkyl sulfosuccinic acid salt is preferably an alkyl group having 6 to 12 carbon atoms.

Description

ポリビニルアルコールフィルムPolyvinyl alcohol film
 本発明は、農薬や洗剤等の薬剤をユニット包装する際などにおいて有用なポリビニルアルコールフィルムと、これを用いた包装体に関する。 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.
 農薬や洗剤をはじめとする各種薬剤などを水溶性フィルムに単位量ずつ密封包装(ユニット包装)して、使用時にその包装形態のまま水中に投入し、内容物を水に溶解または分散して使用する方法がある。このユニット包装の利点は、危険な薬剤に直接触れることなく使用できること、一定量が包装されているために使用時に計量する必要がないこと、包装容器や袋などの後処理が不要または簡単なことなどである。 Various chemicals such as agricultural chemicals and detergents are sealed and packaged in unit quantities in water-soluble films (unit packaging), put into the water as it is when used, and dissolved or dispersed in water. There is a way to do it. The advantages of this unit packaging are that it can be used without direct contact with dangerous chemicals, that a certain amount is packaged, so there is no need to measure it at the time of use, and post-treatment such as packaging containers and bags is unnecessary or simple. Etc.
 例えば、水田用のジャンボ剤は、水田へ投入後にそれを包む水溶性フィルムが溶解し、包装体に内包されていたジャンボ剤が水面を浮遊するなどして水田全体に拡散することで農薬活性成分が行き渡ることになる。このとき、水溶性フィルムが速やかに溶解しなかったり、農薬活性成分の拡散性が不十分であったりすると、水田全体に農薬活性成分を行き渡らせることができなくなる。 For example, 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.
 ユニット包装に使用される水溶性フィルムとしてはポリビニルアルコールフィルム(以下、「ポリビニルアルコール」を「PVA」と略記することがある)が知られており、具体的には例えば、特定のスルホン酸基含有単位を有する変性PVAを用いたフィルム(特許文献1参照)や、PVAと水溶性スルホン酸塩含有化合物とを含むフィルム(特許文献2参照)などが知られている。 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.
特開平7-118407号公報Japanese Unexamined Patent Publication No. 7-118407 特開平9-40834号公報Japanese Patent Laid-Open No. 9-40834
 しかしながら従来公知の水溶性フィルムには、溶解性および包装した薬剤の拡散性の点でさらなる改良の余地があった。そこで本発明は、水中に投入後に速やかに溶解するとともに、包装した薬剤の拡散性に優れるPVAフィルムと、これを用いた包装体を提供することを目的とする。 However, conventionally known water-soluble films have room for further improvement in terms of solubility and diffusibility of packaged drugs. Therefore, 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.
 本発明者らが上記の目的を達成すべく鋭意検討を重ねた結果、特定量の可塑剤を含むPVAフィルムにおいてジアルキルスルホコハク酸塩等の水面拡展剤をさらに含有させると、水中に投入後に速やかに溶解するとともに、包装した薬剤の拡散性にも優れるPVAフィルムとなることを見出し、当該知見に基づいてさらに検討を重ねて本発明を完成させた。 As a result of intensive studies by the present inventors to achieve the above object, when a PVA film containing a specific amount of a plasticizer further contains a water surface spreading agent such as a dialkylsulfosuccinate, it is promptly introduced into water. It was found that the PVA film was excellent in diffusibility of the packaged drug as well as dissolved in the solution, and further studies were made based on the findings to complete the present invention.
 すなわち、本発明は、
[1]PVA、水面拡展剤および可塑剤を含み、可塑剤の含有量がPVA100質量部に対して10~40質量部であるPVAフィルム;
[2]水面拡展剤の含有量がPVA100質量部に対して0.1~15質量部である、[1]に記載のPVAフィルム;
[3]水面拡展剤がジアルキルスルホコハク酸塩である、[1]または[2]に記載のPVAフィルム;
[4]ジアルキルスルホコハク酸塩におけるアルキル基の少なくとも一方が炭素数6~12のアルキル基である、[3]に記載のPVAフィルム;
[5]ジアルキルスルホコハク酸塩におけるアルキル基の少なくとも一方が直鎖状のアルキル基である、[3]または[4]に記載のPVAフィルム;
[6]薬剤包装用フィルムである、[1]~[5]のいずれか1つに記載のPVAフィルム;
[7]薬剤が農薬または洗剤である、[6]に記載のPVAフィルム;
[8]薬剤を[6]または[7]に記載のPVAフィルムで包装してなる包装体;
に関する。
That is, 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.
[4] The PVA film according to [3], wherein at least one of the alkyl groups in the dialkylsulfosuccinate is an alkyl group having 6 to 12 carbon atoms;
[5] The PVA film according to [3] or [4], wherein at least one of the alkyl groups in the dialkylsulfosuccinate is a linear alkyl group;
[6] The PVA film according to any one of [1] to [5], which is a film for drug packaging;
[7] The PVA film according to [6], wherein the drug is an agrochemical or a detergent;
[8] A package formed by packaging the drug with the PVA film according to [6] or [7];
About.
 本発明によれば、水中に投入後に速やかに溶解するとともに、包装した薬剤の拡散性に優れるPVAフィルムと、これを用いた包装体が提供される。 According to the present invention, there are provided 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.
 本発明のPVAフィルムは、PVA、水面拡展剤および可塑剤を含む。そして、本発明のPVAフィルムにおいて可塑剤の含有量はPVA100質量部に対して10~40質量部である。可塑剤を上記の含有量で含む場合において水面拡展剤をさらに含むことにより、水中に投入後に速やかに溶解するとともに、包装した薬剤の拡散性に優れるPVAフィルムとなる。 The PVA film of the present invention contains PVA, a water surface spreading agent and a plasticizer. In the PVA film of the present invention, the plasticizer content is 10 to 40 parts by mass with respect to 100 parts by mass of PVA. In the case where 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.
〔PVA〕
 上記のPVAとしては、酢酸ビニル、ギ酸ビニル、プロピオン酸ビニル、酪酸ビニル、ピバリン酸ビニル、バーサティック酸ビニル、ラウリン酸ビニル、ステアリン酸ビニル、安息香酸ビニル、酢酸イソプロペニル等のビニルエステルの1種または2種以上を重合して得られるポリビニルエステルをけん化することにより得られるものを使用することができる。上記のビニルエステルの中でも、PVAの製造の容易性、入手容易性、コスト等の点から、酢酸ビニルが好ましい。
[PVA]
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 | polymerizing 2 or more types can be used. Among the above vinyl esters, vinyl acetate is preferable from the viewpoints of ease of production of PVA, availability, cost and the like.
 上記のポリビニルエステルは、単量体として1種または2種以上のビニルエステルのみを用いて得られたものであってもよいが、本発明の効果を損なわない範囲内であれば、1種または2種以上のビニルエステルと、これと共重合可能な他の単量体との共重合体であってもよい。 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.
 上記のビニルエステルと共重合可能な他の単量体としては、例えば、エチレン、プロピレン、1-ブテン、イソブテン等の炭素数2~30のα-オレフィン;(メタ)アクリル酸またはその塩;(メタ)アクリル酸メチル、(メタ)アクリル酸エチル、(メタ)アクリル酸n-プロピル、(メタ)アクリル酸i-プロピル、(メタ)アクリル酸n-ブチル、(メタ)アクリル酸i-ブチル、(メタ)アクリル酸t-ブチル、(メタ)アクリル酸2-エチルへキシル、(メタ)アクリル酸ドデシル、(メタ)アクリル酸オクタデシル等の(メタ)アクリル酸エステル;(メタ)アクリルアミド、N-メチル(メタ)アクリルアミド、N-エチル(メタ)アクリルアミド、N,N-ジメチル(メタ)アクリルアミド、ジアセトン(メタ)アクリルアミド、(メタ)アクリルアミドプロパンスルホン酸またはその塩、(メタ)アクリルアミドプロピルジメチルアミンまたはその塩、N-メチロール(メタ)アクリルアミドまたはその誘導体等の(メタ)アクリルアミド誘導体;N-ビニルホルムアミド、N-ビニルアセトアミド、N-ビニルピロリドン等のN-ビニルアミド;メチルビニルエーテル、エチルビニルエーテル、n-プロピルビニルエーテル、i-プロピルビニルエーテル、n-ブチルビニルエーテル、i-ブチルビニルエーテル、t-ブチルビニルエーテル、ドデシルビニルエーテル、ステアリルビニルエーテル等のビニルエーテル;(メタ)アクリロニトリル等のシアン化ビニル;塩化ビニル、塩化ビニリデン、フッ化ビニル、フッ化ビニリデン等のハロゲン化ビニル;酢酸アリル、塩化アリル等のアリル化合物;マレイン酸またはその塩、エステルもしくは酸無水物;イタコン酸またはその塩、エステルもしくは酸無水物;ビニルトリメトキシシラン等のビニルシリル化合物;不飽和スルホン酸などを挙げることができる。上記のポリビニルエステルは、前記した他の単量体の1種または2種以上に由来する構造単位を有することができる。 Examples of the other monomer copolymerizable with the vinyl ester include α-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, N-dimethyl (meth) acrylamide, diacetone (meth) acryl (Meth) acrylamide derivatives such as amides, (meth) acrylamide propanesulfonic acid or salts thereof, (meth) acrylamide propyldimethylamine or salts thereof, N-methylol (meth) acrylamide or derivatives thereof; N-vinylformamide, N-vinyl N-vinylamides such as acetamide and N-vinylpyrrolidone; methyl vinyl ether, ethyl vinyl ether, n-propyl vinyl ether, i-propyl vinyl ether, n-butyl vinyl ether, i-butyl vinyl ether, t-butyl vinyl ether, dodecyl vinyl ether, stearyl vinyl ether, etc. 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.
 上記のポリビニルエステルに占める前記した他の単量体に由来する構造単位の割合は、ポリビニルエステルを構成する全構造単位のモル数に基づいて、25モル%以下であることが好ましく、15モル%以下であることがより好ましく、5モル%以下であることがさらに好ましい。 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.
 上記のPVAは、本発明の効果を損なわない範囲内であれば、1種または2種以上のグラフト共重合可能な単量体によって変性されたものであってもよい。当該グラフト共重合可能な単量体としては、例えば、不飽和カルボン酸またはその誘導体;不飽和スルホン酸またはその誘導体;炭素数2~30のα-オレフィンなどが挙げられる。PVAにおけるグラフト共重合可能な単量体に由来する構造単位(グラフト変性部分における構造単位)の割合は、PVAを構成する全構造単位のモル数に基づいて、5モル%以下であることが好ましい。 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. Examples of the graft copolymerizable monomer include unsaturated carboxylic acids or derivatives thereof; unsaturated sulfonic acids or derivatives thereof; α-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. .
 上記のPVAは、その水酸基の一部が架橋されていてもよいし、架橋されていなくてもよい。また上記のPVAは、その水酸基の一部がアセトアルデヒド、ブチルアルデヒド等のアルデヒド化合物などと反応してアセタール構造を形成していてもよいし、これらの化合物と反応せずアセタール構造を形成していなくてもよい。 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.
 上記のPVAの重合度は特に限定されないが、300以上であることが好ましく、500以上であることがより好ましく、800以上であることがさらに好ましく、1,000以上であることが特に好ましく、また、10,000以下であることが好ましく、8,000以下であることがより好ましく、5,000以下であることがさらに好ましく、2,000以下であることが特に好ましい。当該重合度が300以上であることにより、フィルムの強度が向上し、取り扱い性に優れる。一方、当該重合度が10,000以下であることにより、当該PVAの工業的な製造が容易になる。なお、本明細書におけるPVAの重合度は、JIS K6726-1994の記載に準じて測定した平均重合度を意味する。 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. By the said polymerization degree being 300 or more, the intensity | strength of a film improves and it is excellent in handleability. On the other hand, when the degree of polymerization is 10,000 or less, industrial production of the PVA becomes easy. In this specification, the degree of polymerization of PVA means the average degree of polymerization measured according to the description of JIS K6726-1994.
 上記のPVAのけん化度は特に限定されないが、得られるPVAフィルムの強度、腰および製袋性の点から80モル%以上であることが好ましく、82モル%以上であることがより好ましく、84モル%以上であることがさらに好ましく、また、99.9モル%以下であることが好ましく、99モル%以下であることがより好ましく、98モル%以下であることがさらに好ましい。PVAのけん化度が80モル%以上であることにより、フィルムに十分な腰を付与することができて形態安定性が向上し、また、フィルムにアルカリ性物質または酸性物質を包装して保管する場合に、フィルムの水溶性の低下をより効果的に防止できる。一方、けん化度が99.9モル%以下であることにより、PVAの工業的および安定的な製造が容易になる。なお、本明細書におけるPVAのけん化度とは、PVAが有する、けん化によってビニルアルコール単位に変換され得る構造単位(典型的にはビニルエステル単位)とビニルアルコール単位との合計モル数に対して当該ビニルアルコール単位のモル数が占める割合(モル%)をいう。けん化度はJIS-K6726-1994の記載に準じて測定することができる。 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. When the degree of saponification of PVA is 80 mol% or more, sufficient elasticity can be imparted to the film, and the form stability is improved. In addition, when 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. On the other hand, when the degree of saponification is 99.9 mol% or less, industrial and stable production of PVA becomes easy. In this specification, 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 proportion (mol%) occupied by the number of moles of vinyl alcohol units. The degree of saponification can be measured according to the description of JIS-K6726-1994.
〔水面拡展剤〕
 水面拡展剤の種類は特に制限されないが、本発明の効果がより顕著に奏されることなどからジアルキルスルホコハク酸塩が好ましい。当該ジアルキルスルホコハク酸塩は、スルホコハク酸塩における2つのカルボキシル基がそれぞれアルキルエステルに変換された構造に相当する構造を有する化合物であり、当該構造を有する限りどのような製造方法によって得られたものであってもよい。ジアルキルスルホコハク酸塩が有する2つのアルキルエステル部分における各アルキル基は互いに同じものであっても異なっていてもどちらでもよいが、製造が容易であることなどを考慮すると互いに同じものであることが好ましい。また、ジアルキルスルホコハク酸塩における上記アルキル基は、いずれか一方または両方が直鎖状のアルキル基であってもよいし、いずれか一方または両方が分岐鎖状のアルキル基であってもよい。当該アルキル基としては、例えば、メチル基、エチル基、プロピル基、イソプロピル基、ペンチル基、ヘキシル基、ヘプチル基、オクチル基、2-エチルヘキシル基、ノニル基、デカニル基、ウンデカニル基、ドデカニル基などが挙げられる。包装した薬剤の拡散性がより向上したPVAフィルムとなることなどから、ジアルキルスルホコハク酸塩におけるアルキル基の少なくとも一方(好ましくは両方)は、炭素数6~12のアルキル基であることが好ましく、炭素数7~10のアルキル基であることがより好ましい。また同様の理由により、ジアルキルスルホコハク酸塩におけるアルキル基の少なくとも一方(好ましくは両方)は、直鎖状のアルキル基であることが好ましい。
[Water surface spreading agent]
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. . Further, 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. Examples of 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. In order to obtain a PVA film in which the diffusibility of the packaged drug is further improved, 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. For the same reason, at least one (preferably both) of the alkyl groups in the dialkylsulfosuccinate is preferably a linear alkyl group.
 上記のジアルキルスルホコハク酸塩における塩としては無機塩を挙げることができ、ナトリウム塩、カリウム塩、アンモニウム塩が好ましく、ナトリウム塩がより好ましい。 Examples of the salt in the dialkylsulfosuccinate include inorganic salts, preferably sodium salt, potassium salt, and ammonium salt, and more preferably sodium salt.
 PVAフィルムにおける水面拡展剤の含有量は、本発明の効果がより顕著に奏されるとともに、高い機械的物性を維持できて取り扱い性が向上することから、PVA100質量部に対して、0.1質量部以上であることが好ましく、1質量部以上であることがより好ましく、3質量部以上であることがさらに好ましく、また、15質量部以下であることが好ましく、14質量部以下であることがより好ましく、12質量部以下であることがさらに好ましい。 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.
〔可塑剤〕
 上記の可塑剤としては、例えば多価アルコールが挙げられ、その具体例としては、エチレングリコール、グリセリン、プロピレングリコール、ジエチレングリコール、ジグリセリン、トリエチレングリコール、テトラエチレングリコール、トリメチロールプロパン、ポリエチレングリコールなどが挙げられる。PVAフィルムはこれらの可塑剤の1種または2種以上を含むことができる。これらの中でもグリセリン、ジグリセリンおよびポリエチレングリコールからなる群より選ばれる少なくとも1種が好ましい。ポリエチレングリコールの数平均分子量に特に制限はないが、PVAとの相容性や、またブリードアウトに起因したフィルムの水溶性低下を防止する観点から、100~1,000の範囲内であることが好ましい。
[Plasticizer]
Examples of the plasticizer 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.
 PVAフィルムにおける可塑剤の含有量は、水中に投入後に速やかに溶解するとともに、包装した薬剤の拡散性に優れるPVAフィルムとなることから、PVA100質量部に対して10~40質量%の範囲内であることが必要であり、当該含有量は、12質量部以上であることが好ましく、14質量部以上であることがより好ましく、また、38質量部以下であることが好ましく、36質量部以下であることがより好ましい。 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.
〔その他の成分〕
 機械的強度、取り扱う際の耐湿性、溶解する際の水の吸収による柔軟化の速度、水中での拡散に要する時間の調節などを目的として、PVAフィルムには、澱粉および/または上記PVA以外の他の水溶性高分子をさらに含有させてもよい。
[Other ingredients]
For the purpose of adjusting mechanical strength, moisture resistance during handling, speed of softening due to absorption of water when dissolving, time required for diffusion in water, etc., PVA films include starch and / or other than PVA. Another water-soluble polymer may be further contained.
 澱粉としては、例えば、コーンスターチ、馬鈴薯澱粉、甘藷澱粉、コムギ澱粉、コメ澱粉、タピオカ澱粉、サゴ澱粉等の天然澱粉類;エーテル化加工、エステル化加工、酸化加工等が施された加工澱粉類などを挙げることができ、特に加工澱粉類が好ましい。 Examples of the starch 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.
 PVAフィルムにおける澱粉の含有量は、PVA100質量部に対して、15質量部以下であることが好ましく、10質量部以下であることがより好ましい。当該含有量が15質量部以下であることにより、PVAフィルムの耐衝撃性が向上し、工程通過性が向上する。 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. When the content is 15 parts by mass or less, the impact resistance of the PVA film is improved and the process passability is improved.
 PVA以外の他の水溶性高分子としては、例えば、デキストリン、ゼラチン、にかわ、カゼイン、シェラック、アラビアゴム、ポリアクリル酸アミド、ポリアクリル酸ナトリウム、ポリビニルメチルエーテル、メチルビニルエーテルと無水マレイン酸との共重合体、酢酸ビニルとイタコン酸との共重合体、ポリビニルピロリドン、セルロース、アセチルセルロース、アセチルブチルセルロース、カルボキシメチルセルロース、メチルセルロース、エチルセルロース、ヒドロキシエチルセルロース、アルギン酸ナトリウムなどが挙げられる。 Other 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.
 PVAフィルムにおけるPVA以外の他の水溶性高分子の含有量は、PVA100質量部に対して、15質量部以下であることが好ましく、10質量部以下であることがより好ましい。当該含有量が15質量部以下であることにより、PVAフィルムの水溶性および分散性が向上する。 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.
 PVAフィルムには、さらに、充填剤、銅化合物等の加工安定剤、耐候性安定剤、着色剤、紫外線吸収剤、光安定剤、酸化防止剤、帯電防止剤、難燃剤、他の熱可塑性樹脂、潤滑剤、香料、消泡剤、消臭剤、増量剤、剥離剤、離型剤、補強剤、架橋剤、防かび剤、防腐剤、結晶化速度遅延剤、後述する界面活性剤などの添加剤を、必要に応じて適宜含有させることができる。 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.
 PVAフィルムにおける、PVA、水面拡展剤、および、可塑剤の合計の占める割合は、PVAフィルムの質量に基づいて、80質量%以上であることが好ましく、90質量%以上であることがより好ましく、95質量%以上であることがさらに好ましい。 In the PVA film, 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.
 PVAフィルムの厚みは特に制限されないが、強度および水溶性の両立の観点から、1μm以上であることが好ましく、5μm以上であることがより好ましく、10μm以上であることがさらに好ましく、また、100μm以下であることが好ましく、75μm以下であることがより好ましく、60μm以下であることがさらに好ましい。 The thickness of the PVA film is not particularly limited, but it is preferably 1 μm or more, more preferably 5 μm or more, further preferably 10 μm or more, and 100 μm or less from the viewpoint of both strength and water solubility. Preferably, it is 75 μm or less, and more preferably 60 μm or less.
 PVAフィルムの形状は特に制限されず、四角形(例えば、長方形、正方形等)、円形、三角形などの形状が挙げられ、本発明のPVAフィルムの使用形態などに応じて適宜設定することができるが、連続的に製造することができ、ロール状に巻かれた状態で容易に保管や輸送ができることから、長尺のフィルムであることが好ましい。長尺のPVAフィルムの長さは特に制限されないが、加工時の生産性の観点などから、1m以上であることが好ましく、100m以上であることがより好ましく、1,000m以上であることがさらに好ましい。当該長さの上限としては例えば10,000mが挙げられる。一方、長尺のPVAフィルムの幅も特に制限されないが、加工時の生産性の観点などから、50cm以上であることが好ましく、80cm以上であることがより好ましく、100cm以上であることがさらに好ましい。当該幅の上限としては例えば5mが挙げられる。当該PVAフィルムは、使用する際に所望のサイズに裁断するなどして用いることができる。 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. On the other hand, 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.
 本発明のPVAフィルムの製造方法は特に限定されず、製膜後のPVAフィルムの厚みおよび幅がより均一になる製造方法を好ましく採用することができ、例えば、PVAフィルムを構成する上記したPVA、水面拡展剤、可塑剤ならびに必要に応じてさらに上記した澱粉、他の水溶性高分子および添加剤などのうちの1種または2種以上が液体媒体中に溶解した製膜原液や、PVA、水面拡展剤、可塑剤ならびに必要に応じてさらに澱粉、他の水溶性高分子、添加剤および液体媒体などのうちの1種または2種以上を含み、PVAが溶融している製膜原液を用いて製造することができる。当該製膜原液が澱粉、他の水溶性高分子および添加剤の少なくとも1種を含有する場合には、それらの成分が均一に混合されていることが好ましい。 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. For example, the above-described PVA constituting the PVA film, A film-forming stock solution in which one or two or more of the above-mentioned starch, other water-soluble polymer and additives are dissolved in a liquid medium, PVA, A film-forming stock solution containing one or more of a water surface spreading agent, a plasticizer and, if necessary, starch, other water-soluble polymers, additives, and a liquid medium, in which PVA is melted Can be used. When 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.
 製膜原液の調製に使用される上記液体媒体としては、例えば、水、ジメチルスルホキシド、ジメチルホルムアミド、ジメチルアセトアミド、N-メチルピロリドン、エチレングリコール、グリセリン、プロピレングリコール、ジエチレングリコール、トリエチレングリコール、テトラエチレングリコール、トリメチロールプロパン、エチレンジアミン、ジエチレントリアミンなどを挙げることができ、これらのうちの1種または2種以上を使用することができる。そのうちでも、環境に与える負荷や回収性の点から水が好ましい。 Examples of the liquid medium used for the preparation of the membrane forming stock solution 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.
 製膜原液の揮発分率(製膜時に揮発や蒸発によって除去される液体媒体などの揮発性成分の製膜原液中における含有割合)は、製膜方法、製膜条件などによっても異なるが、一般的には、50~95質量%の範囲内であることが好ましく、55~90質量%の範囲内であることがより好ましく、60~85質量%の範囲内であることがさらに好ましい。製膜原液の揮発分率が50質量%以上であることにより、製膜原液の粘度が高くなり過ぎず、製膜原液調製時の濾過や脱泡が円滑に行われ、異物や欠点の少ないPVAフィルムの製造が容易になる。一方、製膜原液の揮発分率が95質量%以下であることにより、製膜原液の濃度が低くなり過ぎず、工業的なPVAフィルムの製造が容易になる。 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. When 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. On the other hand, when 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.
 製膜原液は界面活性剤を含むことが好ましい。界面活性剤を含むことにより、製膜性が向上してPVAフィルムの厚み斑の発生が抑制されると共に、製膜に使用する金属ロールやベルトからのPVAフィルムの剥離が容易になる。界面活性剤を含む製膜原液からPVAフィルムを製造した場合には、当該PVAフィルム中には界面活性剤が含有され得る。上記の界面活性剤の種類は特に限定されないが、金属ロールやベルトからの剥離性の観点などから、アニオン性界面活性剤またはノニオン性界面活性剤が好ましい。 The film forming stock solution preferably contains 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. When a PVA film is produced from a film-forming stock solution containing a surfactant, the PVA film may contain a surfactant. Although 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.
 アニオン性界面活性剤としては、例えば、ラウリン酸カリウム等のカルボン酸型;ポリオキシエチレンラウリルエーテル硫酸塩、オクチルサルフェート等の硫酸エステル型;ドデシルベンゼンスルホネート等のスルホン酸型などが好適である。 As the 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.
 ノニオン性界面活性剤としては、例えば、ポリオキシエチレンオレイルエーテル等のアルキルエーテル型;ポリオキシエチレンオクチルフェニルエーテル等のアルキルフェニルエーテル型;ポリオキシエチレンラウレート等のアルキルエステル型;ポリオキシエチレンラウリルアミノエーテル等のアルキルアミン型;ポリオキシエチレンラウリン酸アミド等のアルキルアミド型;ポリオキシエチレンポリオキシプロピレンエーテル等のポリプロピレングリコールエーテル型;ラウリン酸ジエタノールアミド、オレイン酸ジエタノールアミド等のアルカノールアミド型;ポリオキシアルキレンアリルフェニルエーテル等のアリルフェニルエーテル型などが好適である。 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.
 これらの界面活性剤は1種を単独でまたは2種以上を組み合わせて使用することができる。 These surfactants can be used alone or in combination of two or more.
 製膜原液が界面活性剤を含む場合、その含有量は、製膜原液に含まれるPVA100質量部に対して、0.01~5質量部の範囲内であることが好ましく、0.02~4質量部の範囲内であることがより好ましく、0.05~3質量部の範囲内であることが特に好ましい。当該含有量が0.01質量部以上であることにより製膜性および剥離性がより向上する。一方、当該含有量が5質量部以下であることにより、界面活性剤がPVAフィルムの表面にブリードアウトしてブロッキングが生じ取り扱い性が低下するのを抑制することができる。 When the film-forming stock solution contains a surfactant, 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. When the content is 0.01 parts by mass or more, the film forming property and the peelability are further improved. On the other hand, when 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.
 上記した製膜原液を用いてPVAフィルムを製膜する際の製膜方法としては、例えば、キャスト製膜法、押出製膜法、湿式製膜法、ゲル製膜法などが挙げられる。これらの製膜方法は1種のみを採用しても2種以上を組み合わせて採用してもよい。これらの製膜方法の中でもキャスト製膜法、押出製膜法が、厚みおよび幅が均一で物性の良好なPVAフィルムが得られることから好ましい。製膜したPVAフィルムには必要に応じて乾燥や熱処理を行うことができる。 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.
 PVAフィルムの具体的な製造方法の例としては、例えば、T型スリットダイ、ホッパープレート、I-ダイ、リップコーターダイ等を用いて、上記の製膜原液を最上流側に位置する回転する加熱した第1ロール(あるいはベルト)の周面上に均一に吐出または流延し、この第1ロール(あるいはベルト)の周面上に吐出または流延された膜の一方の面から揮発性成分を蒸発させて乾燥し、続いてその下流側に配置した1個または複数個の回転する加熱したロールの周面上でさらに乾燥するか、または熱風乾燥装置の中を通過させてさらに乾燥した後、巻き取り装置により巻き取る方法を工業的に好ましく採用することができる。加熱したロールによる乾燥と熱風乾燥装置による乾燥とは、適宜組み合わせて実施してもよい。 As an example of a specific method for producing a PVA film, for example, 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). Evaporate to dry, then further dry on the circumference of one or more rotating heated rolls located downstream, or pass through a hot air dryer and further dry, 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.
 PVAフィルムは、その表面のスリップ性を向上させるなどの目的のために、表面にマット処理が施されていることが好ましい。マット処理の方法として、製膜時にロールまたはベルト上のマット表面をフィルムに転写させるオンラインマット処理法、製膜されたフィルムを一旦ロールに巻き取った後にエンボス処理を施す方法などが挙げられる。マット処理が施された面の算術平均高さ(Ra)は、0.5μm以上であることが好ましく、1μm以上であることがより好ましい。算術平均高さ(Ra)の上限としては、例えば、耐ピンホール性の観点から10μmである。算術平均高さ(Ra)が0.5μm未満であると十分なスリップ性が得られにくい。また、最大高さ(Rz)で1μm以上であることが好ましく、3μm以上であることがより好ましい。最大高さ(Rz)の上限としては、例えば、耐ピンホール性の観点から20μmである。最大高さ(Rz)が0.5μm未満であると十分なスリップ性が得られにくい。なお、本明細書において算術平均高さ(Ra)および最大高さ(Rz)はJIS B 0601:2001で定義されるものである。 The surface of the PVA film is preferably matted for the purpose of improving the slip property of the surface. Examples of 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 μm or more, and more preferably 1 μm or more. The upper limit of the arithmetic average height (Ra) is, for example, 10 μm from the viewpoint of pinhole resistance. When the arithmetic average height (Ra) is less than 0.5 μm, it is difficult to obtain sufficient slip properties. Further, the maximum height (Rz) is preferably 1 μm or more, and more preferably 3 μm or more. The upper limit of the maximum height (Rz) is, for example, 20 μm from the viewpoint of pinhole resistance. When the maximum height (Rz) is less than 0.5 μm, it is difficult to obtain sufficient slip properties. In this specification, the arithmetic average height (Ra) and the maximum height (Rz) are defined by JIS B 0601: 2001.
 本発明のPVAフィルムは水中に投入後に速やかに溶解するとともに包装した薬剤の拡散性に優れることから薬剤包装用フィルムとして使用するのが好ましい。包装される薬剤としては、農薬、洗剤(漂白剤含む)などが挙げられ、農薬が好ましい。農薬の具体的な種類に特に制限はないが、本発明の効果がより顕著に奏されることからジャンボ剤であることが好ましく、特に散布後に水面に浮遊する浮遊タイプのジャンボ剤であることが好ましい。本発明のPVAフィルムで包装される薬剤の物性に特に制限はなく、酸性であっても、中性であっても、アルカリ性であってもよい。薬剤の形態としては、粉末状、塊状、ゲル状、液体状などが挙げられるが、薬剤の拡散性に優れる観点から粉末状または塊状であることが好ましい。包装形態に特に制限はないが、薬剤を単位量ずつ包装(好ましくは密封包装)するユニット包装の形態が好ましい。本発明のPVAフィルムを薬剤包装用フィルムとして使用して薬剤を包装することにより、本発明の包装体が得られる。 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. Examples of the medicine to be packaged include agricultural chemicals and detergents (including bleaching agents), and agricultural chemicals are preferable. There are no particular restrictions on the specific type of pesticide, but it is preferably a jumbo agent because the effects of the present invention are more prominent. In particular, it should be a floating type jumbo agent that floats on the water surface after spraying. preferable. There is no restriction | limiting in particular in the physical property of the chemical | medical agent packaged with the PVA film of this invention, It may be acidic, neutral, or alkaline. Examples of the form of the drug include powder, lump, gel, liquid and the like. From the viewpoint of excellent drug diffusibility, it is preferably powder or lump. Although there is no restriction | limiting in particular in a packaging form, The form of the unit packaging which packages a chemical | medical agent unit by unit quantity (preferably sealed packaging) is preferable. By packaging the drug using the PVA film of the present invention as a film for drug packaging, the package of the present invention is obtained.
 以下、実施例により本発明をより詳細に説明するが、本発明はこれらの実施例により何ら限定されるものではない。なお、以下の実施例および比較例において採用した評価方法を以下に示す。 Hereinafter, the present invention will be described in more detail with reference to examples, but the present invention is not limited to these examples. The evaluation methods employed in the following examples and comparative examples are shown below.
薬剤包装のモデル試験
 以下の実施例または比較例で製造したPVAフィルムを20℃65%RHで24時間調湿した。続いて、3~4mmφのポリエチレンペレット2.5gを、調湿したPVAフィルムで密封包装した。具体的には、ポリエチレンペレットが入る部分の形状が30mm×30mmの正方形になるように、3方をヒートシールして袋を作製した上でこれにポリエチレンペレットを入れ、残りの一方をヒートシールすることにより包装した。次に、18cm×25cmのバットに、15℃の水を深さ2cmまで入れ、バットの中央の水面にポリエチレンペレットを包装した前記の袋を浮かべた。水面に袋を浮かべてからPVAフィルムが溶解して袋の中のポリエチレンペレットが水面に拡散しはじめるまでの時間を破袋時間とし、破袋時間が80秒以下の場合を溶解性が「○」(良好)と判定し、80秒を超える場合を溶解性が「×」(不良)と判定した。また、水面に袋を浮かべてから180秒後の様子を上部からカメラで撮影し、ポリエチレンペレットがバットの面積(450cm)に対して80%以上拡散していた場合を拡散性が「○」(良好)と判定し、60%以上80%未満拡散していた場合を拡散性が「△」(やや良好)と判定し、60%未満拡散していた場合を拡散性が「×」(不良)と判定した。なお、拡散の判定において、バットの中を25等分(1エリアは3.6cm×5cm)し、その等分したエリアの中に1個でもポリエチレンペレットがあれば、そのエリアは拡散していると判段することにより行った。
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 mmφ 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. 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). In addition, 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 “◯”. (Good), when the diffusion was 60% or more and less than 80%, the diffusivity was determined as “△” (slightly good), and when the diffusion was less than 60%, the diffusivity was “x” (bad) ). In the determination of diffusion, 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.
[実施例1]
 重合度1,700、けん化度88モル%のPVA(酢酸ビニルの単独重合体のけん化物)を100質量部、グリセリンを20質量部、ポリオキシエチレンラウリルエーテル硫酸ナトリウムを0.1質量部、および、水面拡展剤としてジオクチルスルホコハク酸ナトリウムを5質量部を含み、PVAの含有率が10質量%である水溶液を作製した。この水溶液を80℃の金属ロール上で乾燥して剥離した後、100℃で1分間熱処理し、厚みが40μmのPVAフィルムを製造した。
 得られたPVAフィルムを用いて、上記した方法により薬剤包装のモデル試験を実施した。得られた結果を表1に示した。
[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 μm.
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.
[実施例2]
 ジオクチルスルホコハク酸ナトリウムの使用量を1質量部に変更したこと以外は実施例1と同様にして、厚みが40μmのPVAフィルムを製造した。
 得られたPVAフィルムを用いて、上記した方法により薬剤包装のモデル試験を実施した。得られた結果を表1に示した。
[Example 2]
A PVA film having a thickness of 40 μm 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.
[実施例3]
 ジオクチルスルホコハク酸ナトリウムの使用量を10質量部に変更したこと以外は実施例1と同様にして、厚みが40μmのPVAフィルムを製造した。
 得られたPVAフィルムを用いて、上記した方法により薬剤包装のモデル試験を実施した。得られた結果を表1に示した。
[Example 3]
A PVA film having a thickness of 40 μm 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.
[実施例4]
 水面拡展剤として、ジオクチルスルホコハク酸ナトリウム5質量部に代えて、ジ(2-エチルヘキシル)スルホコハク酸ナトリウム5質量部を用いたこと以外は実施例1と同様にして、厚みが40μmのPVAフィルムを製造した。
 得られたPVAフィルムを用いて、上記した方法により薬剤包装のモデル試験を実施した。得られた結果を表1に示した。
[Example 4]
A PVA film having a thickness of 40 μm 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.
[実施例5]
 グリセリンの使用量を35質量部に変更したこと以外は実施例3と同様にして、厚みが40μmのPVAフィルムを製造した。
 得られたPVAフィルムを用いて、上記した方法により薬剤包装のモデル試験を実施した。得られた結果を表1に示した。
[Example 5]
A PVA film having a thickness of 40 μm 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.
[実施例6]
 重合度1,700、けん化度88モル%のPVA(酢酸ビニルの単独重合体のけん化物)100質量部に代えて、重合度1,700、けん化度88モル%、2-アクリルアミド-2-メチルプロパンスルホン酸ナトリウム単位の含有率2モル%のPVA(酢酸ビニルと2-アクリルアミド-2-メチルプロパンスルホン酸ナトリウムとの共重合体のけん化物)100質量部を用いたこと以外は実施例1と同様にして、厚みが40μmのPVAフィルムを製造した。
 得られたPVAフィルムを用いて、上記した方法により薬剤包装のモデル試験を実施した。得られた結果を表1に示した。
[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 μm 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.
[実施例7]
 グリセリン20質量部に変えて、グリセリン10質量部およびジグリセリン10質量部を用いたこと以外は実施例6と同様にして、厚みが40μmのPVAフィルムを製造した。
 得られたPVAフィルムを用いて、上記した方法により薬剤包装のモデル試験を実施した。得られた結果を表1に示した。
[Example 7]
A PVA film having a thickness of 40 μm 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.
[実施例8]
 グリセリン20質量部に変えて、グリセリン10質量部、ジグリセリン10質量部および数平均分子量400のポリエチレングリコール5質量部を用いたこと以外は実施例6と同様にして、厚みが40μmのPVAフィルムを製造した。
 得られたPVAフィルムを用いて、上記した方法により薬剤包装のモデル試験を実施した。得られた結果を表1に示した。
[Example 8]
A PVA film having a thickness of 40 μm 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.
[比較例1]
 ジオクチルスルホコハク酸ナトリウムを用いなかったこと以外は実施例1と同様にして、厚みが40μmのPVAフィルムを製造した。
 得られたPVAフィルムを用いて、上記した方法により薬剤包装のモデル試験を実施した。得られた結果を表1に示した。
[Comparative Example 1]
A PVA film having a thickness of 40 μm 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.
[比較例2]
 ジオクチルスルホコハク酸ナトリウム5質量部に代えて、アリルスルホン酸ナトリウム10質量部を用いたこと以外は実施例1と同様にして、厚みが40μmのPVAフィルムを製造した。
 得られたPVAフィルムを用いて、上記した方法により薬剤包装のモデル試験を実施した。得られた結果を表1に示した。
[Comparative Example 2]
A PVA film having a thickness of 40 μm 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.
[比較例3]
 グリセリンの使用量を5質量部に変更したこと以外は実施例1と同様にして、厚みが40μmのPVAフィルムを製造した。
 得られたPVAフィルムを用いて、上記した方法により薬剤包装のモデル試験を実施した。得られた結果を表1に示した。
[Comparative Example 3]
A PVA film having a thickness of 40 μm 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.
[比較例4]
 ジオクチルスルホコハク酸ナトリウムを用いなかったこと以外は比較例3と同様にして、厚みが40μmのPVAフィルムを製造した。
 得られたPVAフィルムを用いて、上記した方法により薬剤包装のモデル試験を実施した。得られた結果を表1に示した。
[Comparative Example 4]
A PVA film having a thickness of 40 μm was produced in the same manner as in Comparative Example 3 except that dioctyl sodium 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.
Figure JPOXMLDOC01-appb-T000001
Figure JPOXMLDOC01-appb-T000001
 以上の結果から明らかなように、本発明の規定を満たす実施例1~8のPVAフィルムは、水溶性および拡散性に優れていた。 As is clear from the above results, the PVA films of Examples 1 to 8 that satisfy the provisions of the present invention were excellent in water solubility and diffusibility.

Claims (8)

  1.  ポリビニルアルコール、水面拡展剤および可塑剤を含み、可塑剤の含有量がポリビニルアルコール100質量部に対して10~40質量部であるポリビニルアルコールフィルム。 A polyvinyl alcohol film containing polyvinyl alcohol, 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 polyvinyl alcohol.
  2.  水面拡展剤の含有量がポリビニルアルコール100質量部に対して0.1~15質量部である、請求項1に記載のポリビニルアルコールフィルム。 The polyvinyl alcohol film according to claim 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 polyvinyl alcohol.
  3.  水面拡展剤がジアルキルスルホコハク酸塩である、請求項1または2に記載のポリビニルアルコールフィルム。 The polyvinyl alcohol film according to claim 1 or 2, wherein the water surface spreading agent is a dialkylsulfosuccinate.
  4.  ジアルキルスルホコハク酸塩におけるアルキル基の少なくとも一方が炭素数6~12のアルキル基である、請求項3に記載のポリビニルアルコールフィルム。 The polyvinyl alcohol film according to claim 3, wherein at least one of the alkyl groups in the dialkylsulfosuccinate is an alkyl group having 6 to 12 carbon atoms.
  5.  ジアルキルスルホコハク酸塩におけるアルキル基の少なくとも一方が直鎖状のアルキル基である、請求項3または4に記載のポリビニルアルコールフィルム。 The polyvinyl alcohol film according to claim 3 or 4, wherein at least one of the alkyl groups in the dialkyl sulfosuccinate is a linear alkyl group.
  6.  薬剤包装用フィルムである、請求項1~5のいずれか1項に記載のポリビニルアルコールフィルム。 The polyvinyl alcohol film according to any one of claims 1 to 5, which is a drug packaging film.
  7.  薬剤が農薬または洗剤である、請求項6に記載のポリビニルアルコールフィルム。 The polyvinyl alcohol film according to claim 6, wherein the drug is an agrochemical or a detergent.
  8.  薬剤を請求項6または7に記載のポリビニルアルコールフィルムで包装してなる包装体。 A package formed by packaging the drug with the polyvinyl alcohol film according to claim 6 or 7.
PCT/JP2015/052003 2014-02-06 2015-01-26 Polyvinyl alcohol film WO2015118978A1 (en)

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CN105940050B (en) 2018-07-10

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