WO2003006239A1 - Film etanche soluble dans l'eau - Google Patents

Film etanche soluble dans l'eau Download PDF

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Publication number
WO2003006239A1
WO2003006239A1 PCT/JP2002/007036 JP0207036W WO03006239A1 WO 2003006239 A1 WO2003006239 A1 WO 2003006239A1 JP 0207036 W JP0207036 W JP 0207036W WO 03006239 A1 WO03006239 A1 WO 03006239A1
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WO
WIPO (PCT)
Prior art keywords
water
soluble
film
polyvinyl alcohol
film according
Prior art date
Application number
PCT/JP2002/007036
Other languages
English (en)
Japanese (ja)
Inventor
Masanori Ookubo
Shuuichi Kitamura
Takahiro Tsuji
Shinya Okuda
Original Assignee
The Nippon Synthetic Chemical Industry Co., Ltd.
Keiwa Kabushiki Kaisha
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 The Nippon Synthetic Chemical Industry Co., Ltd., Keiwa Kabushiki Kaisha filed Critical The Nippon Synthetic Chemical Industry Co., Ltd.
Priority to GB0401397A priority Critical patent/GB2394226B/en
Publication of WO2003006239A1 publication Critical patent/WO2003006239A1/fr

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Classifications

    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61F—FILTERS IMPLANTABLE INTO BLOOD VESSELS; PROSTHESES; DEVICES PROVIDING PATENCY TO, OR PREVENTING COLLAPSING OF, TUBULAR STRUCTURES OF THE BODY, e.g. STENTS; ORTHOPAEDIC, NURSING OR CONTRACEPTIVE DEVICES; FOMENTATION; TREATMENT OR PROTECTION OF EYES OR EARS; BANDAGES, DRESSINGS OR ABSORBENT PADS; FIRST-AID KITS
    • A61F13/00—Bandages or dressings; Absorbent pads
    • A61F13/15—Absorbent pads, e.g. sanitary towels, swabs or tampons for external or internal application to the body; Supporting or fastening means therefor; Tampon applicators
    • A61F13/15203—Properties of the article, e.g. stiffness or absorbency
    • A61F13/15211—Properties of the article, e.g. stiffness or absorbency soluble or disintegratable in liquid
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61F—FILTERS IMPLANTABLE INTO BLOOD VESSELS; PROSTHESES; DEVICES PROVIDING PATENCY TO, OR PREVENTING COLLAPSING OF, TUBULAR STRUCTURES OF THE BODY, e.g. STENTS; ORTHOPAEDIC, NURSING OR CONTRACEPTIVE DEVICES; FOMENTATION; TREATMENT OR PROTECTION OF EYES OR EARS; BANDAGES, DRESSINGS OR ABSORBENT PADS; FIRST-AID KITS
    • A61F13/00—Bandages or dressings; Absorbent pads
    • A61F13/15—Absorbent pads, e.g. sanitary towels, swabs or tampons for external or internal application to the body; Supporting or fastening means therefor; Tampon applicators
    • A61F13/51—Absorbent pads, e.g. sanitary towels, swabs or tampons for external or internal application to the body; Supporting or fastening means therefor; Tampon applicators characterised by the outer layers
    • A61F13/514—Backsheet, i.e. the impermeable cover or layer furthest from the skin
    • A61F13/51401—Backsheet, i.e. the impermeable cover or layer furthest from the skin characterised by the material
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/30—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/36—Layered products comprising a layer of synthetic resin comprising polyesters
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
    • C08J7/04—Coating
    • C08J7/0427—Coating with only one layer of a composition containing a polymer binder
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
    • C08J7/04—Coating
    • C08J7/043—Improving the adhesiveness of the coatings per se, e.g. forming primers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2329/00—Characterised 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
    • C08J2329/02—Homopolymers or copolymers of unsaturated alcohols
    • C08J2329/04—Polyvinyl alcohol; Partially hydrolysed homopolymers or copolymers of esters of unsaturated alcohols with saturated carboxylic acids
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2467/00—Characterised by the use of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Derivatives of such polymers

Definitions

  • the present invention relates to an environment-friendly water-soluble waterproofing film that exhibits excellent water resistance when used and exhibits excellent water solubility or water dispersibility at the time of disposal, and particularly relates to napkins, diapers, nursing sheets, and simple
  • the present invention relates to a water-soluble waterproof film useful for sanitary articles and medical articles such as toilets and colostomy, and sewage disposal bags.
  • various unit packaging materials such as bactericides, insecticides, dyes, detergents, pesticides, etc., and hygiene and medical supplies such as laundry bags, napkins, diapers, nursing sheets, simple toilets, ostomy, etc.
  • a water-soluble film composed of a polybiol alcohol resin, a polyethylene oxide resin, a cellulose resin, a starch resin, or the like is often used.
  • these water-soluble films need to be easily dissolved and dispersed in water at the time of disposal, and lose their form.
  • water-rich liquids and dirt are stored. In doing so, sufficient water resistance is also required.
  • Examples of using such a film having both water solubility and water resistance include (1) JP-A-4-200470, (2) JP-A-4-208153, and (3) JP-A-4-12081 62.
  • a storage bag for an excretion treatment device using a film in which a water-repellent agent is coated on one side of a film comprising a polyvinyl alcohol having a degree of genification of 79 to 98% and a gelling agent of polyvinyl alcohol, Disposable backsheets and portable urine collection bags have been proposed.
  • Japanese Patent Application Laid-Open No. 6-142127 a water-resistant and microbial-decomposable resin layer is formed on the inner side, and an airtight water-soluble or water-dispersible resin layer (polyvinyl alcohol) is formed outside.
  • a waste disposal bag composed of two layers is proposed.
  • Japanese Patent Application Laid-Open No. 7-266515 discloses a waste treatment in which a vinyl acetate / vinyl chloride / methyl methacrylate copolymer polymer is laminated on one surface of a film made of water-soluble polyvinyl alcohol. Substrates have been proposed.
  • the present invention is an environmentally friendly type that has excellent water resistance when used and has excellent water solubility at the time of disposal, and exhibits water dispersibility. It is intended to provide a water-soluble waterproof film.
  • a water-soluble polyvinyl alcohol-based film has a resin layer formed from a biodegradable resin composition containing an aliphatic polyester resin and a cellulose derivative.
  • the present invention has been completed by finding that a water-soluble waterproof film provided with a “biodegradable resin layer” can solve the above series of problems.
  • the effect of the present invention is remarkably exerted when the aliphatic polyester resin is a polyprolactone and when the cellulose derivative is cellulose acetate. Further, it has been clarified that an excellent adhesion effect can be obtained by further adding a compound having two or more isocyanate groups in the molecule to the biodegradable resin composition.
  • a water-soluble waterproof film can be used in such a manner as to come into contact with water-containing contaminants or water splashes.
  • the water-soluble film does not dissolve even if it is supplied, or if it comes into contact with water during transportation.
  • dissolution starts from the water-soluble polyvinyl alcohol-based film side, and the whole water-soluble film dissolves in water and Z or Dispersion and incineration after disposal do not generate any pollutants such as dioxin, which is favorable in terms of environment and sanitation.
  • the waterproof layer is formed of the biodegradable resin composition, the waterproof layer is decomposed by a bacterium such as soil bacteria, and thus does not pollute the environment.
  • the water-soluble polyvinyl alcohol-based film used in the present invention may be a film formed from a polyvinyl alcohol-based resin, and such a polyvinyl alcohol-based resin is generally obtained by polymerization of vinyl acetate.
  • a saponified product or a derivative thereof obtained by genifying the resulting polyvinyl acetate with a saponification catalyst such as an alkali or an acid in a lower alcohol solvent is used. If necessary, a monomer copolymerizable with biel acetate is used.
  • a modified polypinyl alcohol-based resin such as a saponified copolymer of styrene and vinyl acetate can also be used, but is not particularly limited thereto.
  • the content of the copolymerizable monomer is preferably about 0.5 mol% to about 10 mol%, and more preferably about 1 mol% to about 7 mol%.
  • Examples of such a monomer include olefins such as ethylene, propylene, isobutylene, ⁇ -octene, -dodecene, and ⁇ -octadecene; Unsaturated acids such as acetic acid, methacrylic acid, crotonic acid, maleic acid, maleic anhydride, itaconic acid or salts thereof or mono- or dialkyl esters; nitriles such as acrylonitrile and methacrylonitrile; acrylamide; Amides such as methacrylamide, olefinsulfonic acids such as ethylenesulfonic acid, arylsulfonic acid and methacrylsulfonic acid or salts thereof, alkyl vinyl ethers, dimethylarylvinyl ketone, N-vinylpyrrolidone, vinyl chloride, vinylidene chloride , Polyoxyethylene (meth) aryl ether, polyoxyalkylene (meth) aryl ether
  • N-acrylamidomethyltrimethylammonium chloride N-acrylamidoethyltrimethylammonium chloride, N-acrylamidopropyltrimethylammonium chloride, 2-acryloxylethyltrimethylammonium chloride, 2-methacryloxyshethyl Trimethylammonium chloride, 2-hydroxy-3-methacryloyloxypropyl trimethylammonium chloride, aryltrimethylammonium chloride, methylaryltrimethylammonium chloride, 3-butenetrimethylammonium chloride, Cationic group-containing monomers such as dimethyldiallylammonium chloride and methyldiarylammonium chloride are also included.
  • a polyvinyl alcohol-based resin containing an acetoacetyl group can also be used.
  • any known polymerization method can be applied without any particular limitation, but usually, Solution polymerization is performed using an alcohol such as methanol, ethanol, or isopropanol as a solvent.
  • emulsion polymerization, suspension polymerization and the like can also be used.
  • the polymerization reaction is carried out using a known radical polymerization catalyst such as azobisisobutyronitrile, acetyl peroxide, benzoyl peroxide, lauroyl peroxide, etc., and the reaction temperature is about 35 ° C. to a boiling point, preferably. Is selected from the range of about 50 ° C to about 80 ° C.
  • a known radical polymerization catalyst such as azobisisobutyronitrile, acetyl peroxide, benzoyl peroxide, lauroyl peroxide, etc.
  • the saponification of the obtained polymer is carried out in the presence of an alcohol catalyst by dissolving the polymer in alcohol.
  • the alcohol used in this case include methanol, ethanol, and vinyl alcohol.
  • the concentration of the polymer in the alcohol may be appropriately adjusted in the range of about 20% by weight to about 50% by weight.
  • the saponification catalyst it is possible to use an alkali metal hydroxide such as sodium hydroxide, potassium hydroxide, sodium methylate, sodium ethylate, potassium methylate or the like, or an alcohol catalyst such as alcoholate. it can.
  • the amount of these catalysts used may be about 1 millimolar equivalent to about 100 millimolar equivalents to the polymer. Incidentally, in some cases, it is also possible to genate with an acid catalyst.
  • the average degree of genification of the polyvinyl alcohol-based resin thus obtained is not particularly limited, but is preferably about 65 mol% to about 99 mol%. That is, if the average degree of saponification is less than 65 mol%, the water solubility or dispersibility in water will be reduced, and the film strength will be inferior. This is because the water dispersibility decreases.
  • the average degree of genification is about 75 mol% to about 95 mol%, preferably about 80 mol% to about 90 mol%.
  • the average degree of genification is about 75 mol% to about 95 mol%, preferably about 83 mol% to about 92 mol%.
  • the average saponification degree is measured according to JIS K 67263.5. Is to react the residual acetic acid groups in the polyvinyl alcohol resin with a known amount of sodium hydroxide, and calculate the ratio of the polyvinyl alcohol resin to be genified from the consumption of sodium hydroxide to obtain the average degree of saponification. decide.
  • the viscosity of the aqueous solution at 4% by weight of the polyvinyl alcohol resin can be applied in the range of about 5 millipascal seconds (mPa ⁇ s) (20 ° C) to about 40 mPa ⁇ s (20 ° C). Within this range, a viscosity of about lOmPas (20 ° C) to about 35 mPas (20 ° C) is preferable, and a viscosity of about 15 mPa's (20 ° C) to about 30 mPas (20 ° C). Particularly preferred.
  • the viscosity was measured in accordance with] ISK 6726 3.11.2. Specifically, a 4% by weight aqueous solution of a polyvinyl alcohol resin was prepared and placed in a falling ball viscometer together with steel balls. It measures the time for a ball to naturally fall from the upper marking line to the lower marking line of the falling ball viscometer, and applies these measured values to the following equation to calculate the viscosity.
  • ⁇ ⁇ ⁇ t ⁇ ⁇ : aqueous solution viscosity, ⁇ : coefficient of steel ball, t: falling time]
  • the polyvinyl alcohol-based resin not only one kind of the polyvinyl alcohol-based resin but also two or more kinds of polyvinyl alcohol-based resins can be used in combination. It is.
  • the aqueous solution of the polyvinyl alcohol-based resin is smoothed (at a temperature of about 80 ° C. to about 130 ° C.) using a roll, a drum, an endless belt, or the like.
  • the water-soluble polyvinyl alcohol of the present invention may be cast by a method such as casting on a transparent metal surface, or a method in which a composition obtained by appropriately adding water or a plasticizer and a filler to the resin is melt-molded by means such as an extrusion method.
  • the former casting method can be particularly suitably used.
  • an aqueous solution having a concentration of about 10% by weight to about 50% by weight is applicable, and a concentration of about 13% by weight to about 45% by weight is preferable.
  • a concentration of about 15% to about 40% by weight is more preferred. Good. If the concentration is less than 10% by weight, poor drying or dripping will occur, leading to a decrease in productivity. Conversely, if the concentration exceeds 50% by weight, productivity will decrease due to high viscosity, which is undesirable. By bringing a phenomenon.
  • a plasticizer glycolin, diglycerin, diethylene glycol, triethylene glycol, polyethylene glycol, polypropylene glycol, etc.
  • a release agent sorbitan ester ether, etc.
  • a repelling inhibitor polyoxyethylene alkylphenyl ether, etc.
  • antioxidants phenols, amines, etc.
  • stabilizers phosphates, etc.
  • coloring agents fragrances
  • the water-soluble polyvinyl alcohol-based film of the present invention contains other water-soluble polymers (sodium polyacrylate, poly (ethylene oxide), polyvinylpyrrolidone, dextrin, chitosan, chitin, and the like, as long as the object of the present invention is not impaired. It is also possible to add methylcellulose, hydroxyethylcellulose, starch and the like), a protective agent, a coloring agent and the like.
  • water-soluble polymers sodium polyacrylate, poly (ethylene oxide), polyvinylpyrrolidone, dextrin, chitosan, chitin, and the like.
  • any one containing an aliphatic polyester resin and a cellulose derivative can be used.
  • Representative examples of the aliphatic polyester resin include a polyester represented by the following general formula (1) or (2) or a copolymer of general formulas (1) and (2). )) Are preferred.
  • p and q are average polymerization degrees of the ester blocks contained in the polyester, and are usually about 50 to about 900, preferably an integer of about 100 to about 800. Is not limited to this value.
  • n, m, and 1 in the formula are methylene numbers, and a numerical value of about 1 to about 20 is applicable, but about 2 to about 10 is preferable, and about 4 to about 8 is most preferable.
  • aliphatic or aromatic polyesters having different methylene numbers may be copolymerized in a block or random form as long as the effects of the present invention are not impaired.
  • polyester represented by the general formula (1) examples include polycaprolactone and polypropiolactone.
  • polyester represented by the general formula (2) examples include polyethylene adipamide and polyethylene azetone. Rate, polyethylene sebacate, polyethylene slate, polyethylene decamethylate and the like.
  • polyprolactone is particularly preferred in terms of dispersibility. These may be used in combination of two or more.
  • cellulose derivative examples include cellulose acetates such as cellulose acetate, cellulose diacetate and cellulose triacetate, other cellulose esters such as methyl cellulose, cellulose acetate butyrate, cellulose acetate propionate, cellulose acetate phthalate, cellulose nitrate, and ethyl cellulose.
  • cellulose ethers such as benzylcellulose, cyanoethylcellulose, hydroxyethylcellulose, hydroxypropylcellulose, hydroxypropylmethylcellulose and carboxymethylcellulose. Of these, cellulose acetate is particularly preferable.
  • the content ratio of the aliphatic polyester resin to the cellulose derivative is not particularly limited, but generally, a ratio of about 80: about 20 to about 98: about 2 (weight ratio) is applicable, and within this range, A ratio of about 83: about 17 to about 95: about 5 (weight ratio) is preferred, and a ratio of about 85: about 15 to about 93: about 7 (weight ratio) is particularly preferred.
  • the biodegradable resin composition used in the present invention is obtained.
  • the compound further contains a compound having two or more isocyanate groups in the molecule.
  • the content of the compound having two or more isocyanate groups in the molecule is about 0.5 to about 20 parts by weight, preferably about 1 to about 15 parts by weight, based on 100 parts by weight of the biodegradable resin composition. More preferably, about 2 to about 10 parts by weight.
  • the content of the isocyanate compound is less than 0.5 part by weight, the effect of adhesion between the biodegradable resin composition layer and the water-soluble polyvinyl alcohol-based film is small, and conversely, when the content exceeds 20 parts by weight. Not only is it not expected that the adhesion effect is further improved, but it also causes undesirable phenomena, such as a decrease in the biodegradability of the biodegradable resin composition.
  • the compound having two or more isocyanate groups in the molecule is not particularly limited as long as the stability of the resin composition is not hindered.
  • diisocyanate can be used.
  • Trimeric and multimeric polyisocyanate compounds can also be used.
  • diisocyanates include (a) aliphatic diisocyanates such as tetramethylene diisocyanate and 1,6-methylhexamethylene diisocyanate; (b) range isocyanates; -Phenylene diisocyanate, 4, 4'-Diphenyl methane diisocyanate, 2, 2'-Diphenylene diisocyanate, 3, 3'-Dimethyl-4,4'-Biphenylene diisocyanate Aromatic diisocyanates such as 3,3'-dic-open mouth-4,4'-biphenyl, 1,5-naphthalenediisocyanate, 1,5-tetrahydroxide, (c ) 1,3-S And the like can be used alone or in combination
  • a filler (filament) can be further added to the biodegradable resin composition.
  • the amount of the filler may be about 3 parts by weight to about 40 parts by weight with respect to 100 parts by weight of the biodegradable resin composition.
  • Such a filler examples include silica, synthetic mica, titanium oxide, phlogopite pigment, muscovite pigment, talc, clay, kaolin, aluminum hydroxide, calcium carbonate, barium sulfate, satin white, pulp, cellulose and the like.
  • the present invention is not limited to these.
  • a particle having a particle size of about 0.10 m to about 15 m is applicable, and even within these ranges, about 0.15 111 to about 13/111, particularly, A particle size of about 0.20 ⁇ m to about lOm is preferred, but not limited thereto. This is because, when the particle size is less than 0.10 im, the effect of water dispersibility is poor, and conversely, when the particle size exceeds 15 m, the water resistance is lowered, which causes undesirable phenomena.
  • a plasticizer can be further added to the biodegradable resin composition.
  • an amount of about 1 part by weight to about 40 parts by weight can be applied to 100 parts by weight of the biodegradable resin composition, but in particular, from the viewpoint of improving water dispersibility. If so, it is desirable to incorporate an amount of about 3 parts to about 35 parts, especially about 5 parts to about 30 parts by weight. This means that If the amount of the plasticizer is less than 1 part by weight, the effect of improving water dispersibility is difficult to obtain, while if it exceeds 40 parts by weight, undesirable phenomena such as a decrease in water resistance are caused.
  • any plasticizer can be used as long as it exhibits a plasticizing effect.
  • examples thereof include phthalic acid diesters, tetrohydrofluoric acid esters, aliphatic dibasic acids, trimellitic acid esters, and the like.
  • Epoxy hexide Plasticizers such as oral fluoric ester type, epoxidized ester type, adipic ester type, and phosphate type.
  • a water-soluble waterproof film can be obtained by providing such a biodegradable resin layer on at least one surface of the water-soluble polyvinyl alcohol-based film.
  • the method used is not particularly limited, and includes, for example, the following methods.
  • a water-soluble polyvinyl alcohol-based film is produced by the above method (solution casting method, extrusion method), while a biodegradable resin composition is melted by a usual method, for example, casting, T-die or inflation.
  • a biodegradable resin composition film is prepared by an extrusion method or a force-rendering method.
  • a water-soluble waterproof film is produced by hot-press laminating the two or three kinds of films. If necessary, an adhesive may be used.
  • a water-soluble polyvinyl alcohol-based film is prepared in advance, and the biodegradable resin composition is melt-extruded on at least one surface of the water-soluble film by an extruder, and the molten resin film is melted into a water-soluble polypinyl. Extrusion lamination method for bonding to alcohol-based films.
  • the lamination is performed once by the extruder, so that the process can be simplified.
  • esters such as methyl acetate, ethyl acetate, methyl acetate acetate, and ethyl acetate acetate, acetone, Ketones such as methyl ethyl ketone and methyl isobutyl ketone; and aromatic compounds such as toluene and xylene.
  • Such a method is advantageous in that the water-soluble polyvinyl alcohol-based film can be manufactured in one step without damaging the film.
  • a water-soluble polyvinyl alcohol-based film is prepared in advance, a solvent-based anchoring agent is coated on at least one surface of the water-soluble film, and a biodegradable resin composition is mainly formed on the anchor agent layer.
  • a solvent-based agent containing a resin such as a polyester resin, a polyurethane resin, a polyester polyurethane resin, or an acryl-based resin as a main component can be used, and the solvent is the same as that used in the above (3). Similar ones are used.
  • the thickness of the water-soluble polyvinyl alcohol-based film cannot be specified unconditionally because it is appropriately selected depending on the intended use and the like, but is generally about 5 xm to about 80 zm. Is preferably adjusted to a film thickness of about 10 m to about 70 °, more preferably about 10 m to about 30 m. Similarly, the thickness of the biodegradable resin layer cannot be unconditionally specified because it is appropriately selected depending on the intended use, etc., but generally, the thickness is from about 0.1 m to about 30 m. Preferably, it is adjusted to a thickness of from about 0. 0 to about 25, more preferably from about 1 zm to about 20 m, with a thickness of about 1 xm to about 7 m being especially preferred.
  • the thickness of the water-soluble polyvinyl alcohol-based film is less than 5 urn, the film strength and processability will be poor, and if it exceeds 80 m, the water solubility will decrease in addition to the productivity. It depends. Similarly, if the thickness of the biodegradable resin layer is less than 0.1, water resistance and film strength are reduced, and if it exceeds about 30 m, undesirable phenomena such as poor water dispersibility appear. .
  • its thickness can be selected from a range that does not impair the adhesiveness and the protection against water, and is usually about 0.01 to about 10 m, preferably about 0.1 m. ii m to a thickness of about 5 m.
  • the biodegradable resin layer when the biodegradable resin layer is thin, defects such as pinholes may occur during production or use of the product, or the effects of fine irregularities of the water-soluble polypinyl alcohol-based film may be caused. Due to concerns, in order to prevent such pinholes and sufficiently exhibit water resistance, two or more (two) biodegradable resin layers are laminated on at least one surface of a water-soluble polyvinyl alcohol-based film. Is preferred.
  • the thickness of each layer constituting the resin layer should be 5 m or less, preferably 0.1 I II! ⁇ 5 m thickness. In other words, if the thickness of each layer exceeds 5 zm, the above-mentioned series of phenomena is unlikely to occur, but the production cost will rise sharply and become uneconomical.
  • the composition of the biodegradable resin composition forming each layer may be the same or different from each other.
  • the water-soluble waterproofing film of the present invention thus obtained can be used for various applications, but in particular, disposable disposable diapers, nursing sheets, sanitary napkins, simple toilets, sanitary articles such as ostomy, medical supplies, and waste disposal bags, etc. It is especially useful as a backsheet for disposable diapers and a waste disposal bag. '
  • the water-soluble waterproof film of the present invention is disposed so that the biodegradable resin layer side is directed inward, that is, toward the human body, and is disposed of.
  • the biodegradable resin layer side is placed inside, that is, at a position where it comes into contact with waste.
  • Example 1 In addition, the notation “part” in the examples means a weight basis unless otherwise specified.
  • Example 1 In addition, the notation “part” in the examples means a weight basis unless otherwise specified.
  • a 15% ethyl acetate solution of a biodegradable resin composition containing 91: 9 (weight ratio) of force-prolactone and cellulose acetate was applied with a bar coater so that the film thickness after drying was 7 m. This was followed by forming a biodegradable resin layer to produce a water-soluble waterproof film.
  • the obtained water-soluble waterproof film was sampled to a size of 35mniX 25mm, and the test piece was placed in a beaker filled with water and fixed so as to be parallel to the water surface, and then at 50 ° C and 60 ° C. , The state of the film after a lapse of time under weak stirring was observed.
  • the evaluation criteria are as follows.
  • the following waterproof sheet was biodegraded using a household garbage disposer (“BGD-150” manufactured by Hitachi, Ltd.), and the degree of decomposition calculated from the weight ratio required to reach 80%. The number of days was measured.
  • a water-soluble waterproof film was produced by performing the same procedure as in Example 1 except that the specifications were changed to those of the polyvinyl alcohol-based film and the biodegradable resin layer as shown in Table 1.
  • Example 9 The same evaluation as in Example 1 was performed for the obtained water-soluble waterproof film.
  • a synthetic mica (“Somasif ME-100”, manufactured by Corp Chemical Co., Ltd.) was produced on a single side of a polybiol alcohol-based film as shown in Table 1 in a 15% ethyl acetate solution of the biodegradable resin composition as shown in Table 1.
  • a dispersion obtained by adding an amount of 20 parts to 100 parts of the degradable resin composition is applied with a bar coater so that the film thickness after drying is 7 m, and biodegradation is performed.
  • a water-soluble waterproof film was produced by forming a water-soluble resin layer. The same evaluation as in Example 1 was performed for the obtained water-soluble waterproof film.
  • diisonol phthalate was added to a biodegradable resin composition as shown in Table 1 in an amount of 20 parts with respect to 100 parts of the biodegradable resin composition.
  • the obtained 15% ethyl acetate solution was applied with a bar coater so that the film thickness after drying became 7, a biodegradable resin layer was formed, and a water-soluble waterproof film was produced.
  • Example 12 The same evaluation as in Example 1 was performed for the obtained water-soluble waterproof film.
  • diisonol phthalate was added to a biodegradable resin composition as shown in Table 1 in an amount of 20 parts with respect to 100 parts of the biodegradable resin composition.
  • a dispersion obtained by further adding a synthetic mica (“Somasif ME_100”, manufactured by Corp Chemical) in an amount of 20 parts to 100 parts of the biodegradable resin composition to the obtained 15% ethyl acetate solution was used.
  • a water-soluble waterproof film was prepared by applying a coating at Barco overnight to form a biodegradable tree layer so that the film thickness after drying was 711.
  • Example 13 The same evaluation as in Example 1 was performed for the obtained water-soluble waterproof film. Examples 13 to 5
  • an isocyanate compound [in Examples 13 and 15, 2,6-tolylene diisocyanate (“Takenate A-3” manufactured by Mitsui Takeda Chemical Co., Ltd.))
  • hexamethylene diisocyanate (“Coronate HL", manufactured by Nippon Polyurethane Industry Co., Ltd.) was added in an amount of 5 parts based on 100 parts of the biodegradable resin composition to obtain 15%.
  • the ethyl acetate solution was applied over Barco overnight so that the film thickness after drying became 7 m to form a biodegradable resin layer, thereby producing a water-soluble waterproof film.
  • Example 2 The same evaluation as in Example 1 was performed for the obtained water-soluble waterproof film.
  • a water-soluble waterproof film having no missing parts and excellent adhesion was obtained.
  • a 15% ethyl acetate solution of the biodegradable resin composition as shown in Table 1 was applied to a barco film so that the film thickness after drying was 2 m. And then apply the same solution to the surface of the biodegradable resin composition layer previously coated with Barco so that the thickness after drying is 2 m. Then, a water-soluble waterproof film was produced.
  • Example 2 The same evaluation as in Example 1 was performed for the obtained water-soluble waterproof film. No pinholes were generated, and a good water-soluble waterproof film was obtained.
  • a synthetic mica (“Somasif ME-100” manufactured by Corp Chemical) is biodegraded in a 15% ethyl acetate solution of the biodegradable resin composition as shown in Table 1.
  • a dispersion prepared by adding 20 parts to 100 parts of the conductive resin composition is coated with a bar coater so that the film thickness after drying becomes 2 m, and the same dispersion is applied first.
  • the coated biodegradable resin layer was coated with Barco overnight so that the film thickness after drying was 2 zm, to produce a water-soluble waterproof film.
  • Example 2 The same evaluation as in Example 1 was performed for the obtained water-soluble waterproof film. No pinholes were generated, and a good water-soluble waterproof film was obtained.
  • an isocyanate compound was added to a biodegradable resin composition as shown in Table 1 [In Example 18, 2,6-tolylene diisocyanate (manufactured by Mitsui Takeda Chemical Co., Ltd .; Takenate A-3 ”), and in Example 19, hexamethylene diisocyanate (Nippon Polyurethane Industry Co., Ltd.,“ Coronate HL ”) was added in an amount of 5 parts per 100 parts of the biodegradable resin composition.
  • a 15% ethyl acetate solution obtained by blending was applied over Barco overnight so that the film thickness after drying was 2 zm, and the same solution was applied first to the biodegradable resin composition.
  • a water-soluble waterproof film was prepared by coating the surface of the material layer with Barco overnight so that the film thickness after drying was 2 am.
  • Example 2 The same evaluation as in Example 1 was performed for the obtained water-soluble waterproof film. In addition, as a result of evaluating the adhesion by a cross-cut peeling test, no missing portion was observed, and a water-soluble waterproof film having excellent adhesion was obtained.
  • a water-soluble waterproofing film was prepared in the same manner as in Example 1 except that a biodegradable resin layer consisting of only poly-prolactone was used without using cellulose acetate, and the same evaluation as in Example 1 was performed.
  • a biodegradable resin layer consisting of only poly-prolactone was used without using cellulose acetate, and the same evaluation as in Example 1 was performed.
  • Table 2 shows the evaluation results of the examples and the comparative examples.
  • Table — 1 Polyvinyl alcohol / alcohol film Biodegradable resin layer
  • Example 1 25 96 25 91:97 7
  • Example 2 20 88 20 00 91:95
  • Example 3 20 88 25 80:20 7
  • Example 4 20 88 25 98: 2 7
  • Example 5 20 88 25 75:25 7
  • Example 6 20 88 25 90:10 3
  • Example 7 20 88 15 90:10 1
  • Example 8 25 96 30 85:15 20
  • Example 10 20 88 25 7
  • Example 11 25 96 25 90:10 7
  • Example 12 25 96 25 90:10 7
  • Example 13 20 88 25 91: 9 7
  • Example 14 20 88 25 91: 9 7
  • Example 15 20 88 20 91: 9 7
  • Example 16 20 88 25 91: 9 2 + 2
  • Example 17 20 88 20 85: 15 2 + 2
  • Example 18 20 88 25 91: 9 2 + 2
  • Example 19 20 88 25 91: 9 2 + 2 Comparative Example 1 25 96 25 100
  • the water-soluble waterproofing film of the present invention comprises a resin layer formed from a biodegradable resin composition containing an aliphatic polyester resin and a cellulose derivative on at least one surface of a water-soluble polyvinyl alcohol-based film (biodegradable resin layer).
  • biodegradable resin layer formed from a biodegradable resin composition containing an aliphatic polyester resin and a cellulose derivative on at least one surface of a water-soluble polyvinyl alcohol-based film (biodegradable resin layer).
  • the water-soluble waterproofing film of the present invention can be said to be an environmentally friendly water-soluble waterproofing film. It is useful for processing bags, etc., and is particularly expected to be applied to backsheets for disposable diapers and waste disposal bags. Furthermore, for applications where water resistance is particularly required, By including an isocyanate compound in the biodegradable resin layer, it can also be used as a water-soluble waterproof film with improved adhesion to a water-soluble polyvinyl alcohol-based film.

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Abstract

Un film étanche soluble dans l'eau présente une excellente résistance à l'eau et une excellente solubilité ou dispersibilité dans l'eau. Ce film est constitué d'un alcool polyvinylique soluble dans l'eau et d'une couche de résine (biodégradable) formée sur au moins une surface de celui-ci à partir d'une composition de résine biodégradable comprenant une résine polyester aliphatique et un dérivé de cellulose.
PCT/JP2002/007036 2001-07-12 2002-07-11 Film etanche soluble dans l'eau WO2003006239A1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
GB0401397A GB2394226B (en) 2001-07-12 2002-07-11 Water-soluble waterproof film

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JP2001-211947 2001-07-12
JP2001211947 2001-07-12

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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US7026175B2 (en) 2004-03-29 2006-04-11 Applied Materials, Inc. High throughput measurement of via defects in interconnects
CN103937269A (zh) * 2014-03-24 2014-07-23 山东理工大学 一种聚肽与聚己内酯改进聚乙烯醇膜耐水性的方法

Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20080091157A1 (en) * 2006-10-17 2008-04-17 Morris Yang Sanitary napkin including a stabilizing layer with dry stiffness index and wet stiffness loss
US7488310B2 (en) * 2006-10-17 2009-02-10 Mcneil-Ppc, Inc. Sanitary napkin including a moisture sensitive stabilizing layer

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1994000293A1 (fr) * 1992-06-26 1994-01-06 The Procter & Gamble Company Compositions de films multicouches impermeables aux liquides, biodegradables
JPH06126897A (ja) * 1991-12-27 1994-05-10 Kyoraku Co Ltd 包装用多層構造体
JPH06142127A (ja) * 1992-11-13 1994-05-24 Aisero Kagaku Kk 汚物処理袋

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH06126897A (ja) * 1991-12-27 1994-05-10 Kyoraku Co Ltd 包装用多層構造体
WO1994000293A1 (fr) * 1992-06-26 1994-01-06 The Procter & Gamble Company Compositions de films multicouches impermeables aux liquides, biodegradables
JPH06142127A (ja) * 1992-11-13 1994-05-24 Aisero Kagaku Kk 汚物処理袋

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US7026175B2 (en) 2004-03-29 2006-04-11 Applied Materials, Inc. High throughput measurement of via defects in interconnects
CN103937269A (zh) * 2014-03-24 2014-07-23 山东理工大学 一种聚肽与聚己内酯改进聚乙烯醇膜耐水性的方法

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GB2394226B (en) 2005-03-23
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