WO2023054721A1 - 水溶性フィルム、製造方法及び包装体 - Google Patents

水溶性フィルム、製造方法及び包装体 Download PDF

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Publication number
WO2023054721A1
WO2023054721A1 PCT/JP2022/036860 JP2022036860W WO2023054721A1 WO 2023054721 A1 WO2023054721 A1 WO 2023054721A1 JP 2022036860 W JP2022036860 W JP 2022036860W WO 2023054721 A1 WO2023054721 A1 WO 2023054721A1
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Prior art keywords
water
soluble film
film
mass
pva
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PCT/JP2022/036860
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English (en)
French (fr)
Japanese (ja)
Inventor
修 風藤
勝啓 高藤
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Kuraray Co Ltd
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Kuraray Co Ltd
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Priority to EP22876583.0A priority Critical patent/EP4219605A4/en
Priority to JP2023532636A priority patent/JP7343732B2/ja
Priority to CN202280007176.2A priority patent/CN116368076B/zh
Priority to US18/036,640 priority patent/US11939442B2/en
Publication of WO2023054721A1 publication Critical patent/WO2023054721A1/ja
Anticipated expiration legal-status Critical
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/18—Manufacture of films or sheets
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/04—Oxygen-containing compounds
    • C08K5/05—Alcohols; Metal alcoholates
    • C08K5/053—Polyhydroxylic alcohols
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F16/00—Homopolymers and 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
    • C08F16/02—Homopolymers and 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 by an alcohol radical
    • C08F16/04—Acyclic compounds
    • C08F16/06—Polyvinyl alcohol ; Vinyl alcohol
    • 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
    • C08J2300/00—Characterised by the use of unspecified polymers
    • C08J2300/14—Water soluble or water swellable polymers, e.g. aqueous gels
    • 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
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D17/00—Detergent materials or soaps characterised by their shape or physical properties

Definitions

  • the present invention relates to a water-soluble film containing polyvinyl alcohol that is suitably used for packaging various drugs, a method for producing the water-soluble film, and a package using the same.
  • Water-soluble films are used in a wide range of applications, such as packaging of liquid detergents, pesticides, and other chemicals, and seed tapes that contain seeds, making use of their excellent solubility in water.
  • Polyvinyl alcohol hereinafter sometimes referred to as PVA
  • PVA Polyvinyl alcohol
  • the water-solubility of the water-soluble film is improved by adding various additives such as a plasticizer to the water-soluble film containing polyvinyl alcohol, or by using modified polyvinyl alcohol into which a carboxyl group is introduced as the raw material of the water-soluble film. known to be enhanced.
  • Patent Document 1 discloses a water-soluble film containing a PVA-based resin and a plasticizer, wherein the area change rate when immersed in a predetermined solution has a specific value.
  • a water-soluble film has been proposed to show According to the water-soluble film, the water-solubility of the water-soluble film is not impaired, and the tension of the water-soluble film over time is not impaired even when a liquid such as a liquid detergent is packaged to form a package. It is said that a water-soluble film capable of forming a flexible package can be obtained.
  • Surfactants are the main components of drugs packaged in water-soluble films, and many of them have relatively low molecular weights and high polarity. Moreover, the PVA contained in the water-soluble film is a hydrophilic polymer, and has a high affinity with these highly polar substances. Therefore, when a package using such a water-soluble film is stored for a long period of time, it is presumed that these substances permeate the water-soluble film, reach the heat-sealed portion, and adversely affect the seal strength.
  • the present invention provides a water-soluble film that maintains good water solubility and is less likely to cause a decrease in sealing strength during long-term storage when a drug such as laundry detergent is packaged, a method for producing the same, and a drug using the water-soluble film.
  • the purpose is to provide a package in which
  • the present inventors have found that the contact angle when a model detergent is dropped on a water-soluble film, the complete dissolution time when immersed in deionized water after immersion in the model detergent, and immersion in the model detergent The inventors have found that the above problems can be solved by setting the swelling degree at the time of heating to a specific range. Based on these findings, the present invention was completed through further studies.
  • the present invention [1] A water-soluble film containing PVA with a polymerization degree of 100 to 3,000 and containing 1 to 50 parts by mass of a polyhydric alcohol-based plasticizer per 100 parts by mass of PVA, wherein the water-soluble film is Monoethanolamine 8.6% by mass, dodecylbenzenesulfonic acid 23.8% by mass, propylene glycol 9.5% by mass, lauryl alcohol ethoxylate-7 ethylene oxide adduct 23.8% by mass, oleic acid 19.1% by mass , Diethylene glycol 9.5% by mass, and a model detergent containing 5.7% by mass of water after immersion for 24 hours in an environment of 23 ° C. and 50% RH, then deionized water was dropped on the film surface.
  • the water-soluble film is Monoethanolamine 8.6% by mass, dodecylbenzenesulfonic acid 23.8% by mass, propylene glycol 9.5% by mass, lauryl alcohol ethoxylate-7 ethylene oxide adduct 23.8%
  • the contact angle after 6 seconds was 20° or more, and the water-soluble film was immersed in the model detergent at 23°C and 50% RH for 24 hours, and then immersed in deionized water at 5°C.
  • the present invention [2] After the water-soluble film was immersed in the model detergent for 24 hours in an environment of 23°C and 50% RH, deionized water was dropped on the film surface, and the contact angle was 35° after 6 seconds of dropping.
  • the draft ratio obtained by dividing the linear velocity of the support on which the membrane-forming undiluted solution is poured by the linear velocity of the membrane-forming undiluted solution on the die lip is 2 to 60, and the draft ratio is 2 to 60 on the support.
  • a method for producing a water-soluble film [8] The method for producing a water-soluble film according to [6] or [7], which includes a step of heat-treating the water-soluble film under conditions of 80 to 300°C; [9] A package in which the water-soluble film according to any one of [1] to [5] contains a drug; [10] The package according to [9] above, wherein the drug is an agricultural chemical, detergent or disinfectant; [11] The package according to [9] or [10], wherein the drug is liquid; Regarding.
  • a water-soluble film that maintains good water solubility and is less likely to cause a decrease in sealing strength during long-term storage when a drug such as laundry detergent is packaged, a method for producing the same, and the water-soluble film.
  • FIG. 4 is a diagram for explaining a method for measuring the seal strength when a water-soluble film is immersed in a model detergent under an environment of 23° C. and 50% RH for 24 hours and then heat-sealed at 165° C.
  • FIG. 4 is a diagram for explaining a method for measuring the seal strength when a water-soluble film is immersed in a model detergent under an environment of 23° C. and 50% RH for 24 hours and then heat-sealed at 165° C.
  • model detergents imitating household laundry detergents have the following compositions. Monoethanolamine 8.6% by mass Dodecylbenzenesulfonic acid 23.8% by mass Propylene glycol 9.5% by mass Lauryl alcohol ethoxylate-7 ethylene oxide adduct 23.8 wt% Oleic acid 19.1% by mass Diethylene glycol 9.5% by mass Water 5.7% by mass
  • ⁇ Contact angle of water-soluble film> the water-soluble film is immersed in a model detergent for 24 hours in an environment of 23 ° C. and 50% RH, and then deionized water is dropped on the film surface. It is sometimes called an angle.) is measured by the following methods ⁇ 1> to ⁇ 4>.
  • ⁇ 1> The water-soluble film is kept in a room at 23° C. and 50% RH for 16 hours or more to adjust the humidity.
  • the moisture-conditioned water-soluble film is immersed in a model detergent of 100 times or more the mass of the film in an environment of 23° C. and 50% RH for 24 hours.
  • Apparatus Mobile Surface Analyzer manufactured by KRUSS (Kruss Item#MSA) Syringe Dosing System (Kruss Item # DS3910) Measurement environment: 23°C, 35% RH Measurement procedure: Specimen size: 2 inches x 3 inches Deionized water solution volume: 1 ⁇ L The time that the droplet and the film contact is 0 seconds, Measure up to 10 seconds over time (0.06 second intervals) The Young Laplace method is used for fitting the contact angle of the droplet ⁇ 4> This measurement is repeated three times, and the average value thereof is taken as the contact angle after immersion in the detergent. The reason for selecting the data after 6 seconds of dropping is that the data around 6 seconds after dropping has the least variation, and accurate measurement values can be obtained.
  • the contact angle of the water-soluble film is 20° or more. If the contact angle of the water-soluble film is less than 20°, the seal strength (hereinafter sometimes referred to as seal strength) may be insufficient during long-term storage when chemicals such as laundry detergent are packaged.
  • the lower limit of the contact angle of the water-soluble film is preferably 22° or more, more preferably 23° or more, and even more preferably 24° or more.
  • the upper limit of the contact angle of the water-soluble film is preferably 35° or less, more preferably 33° or less, even more preferably 31° or less, and particularly preferably 29° or less. When the contact angle of the water-soluble film is equal to or less than the above upper limit, the seal strength tends to be sufficient.
  • the contact angle of the water-soluble film is presumed to strongly depend on the affinity between the water-soluble film and the model detergent on the surface of the water-soluble film. Therefore, the composition of the water-soluble film (e.g., the degree of saponification and modification of PVA, the type and content of the plasticizer, additives) and the film-forming conditions (draft ratio, drying conditions, draw ratio, etc.), the contact angle of the water-soluble film can be controlled.
  • the composition of the water-soluble film e.g., the degree of saponification and modification of PVA, the type and content of the plasticizer, additives
  • the film-forming conditions e.g., the degree of saponification and modification of PVA, the type and content of the plasticizer, additives
  • the degree of swelling of the water-soluble film when the water-soluble film is immersed in a model detergent in an environment of 23° C. and 50% RH for 1 hour (hereinafter sometimes referred to as the degree of swelling) is as follows: 1> to ⁇ 4>.
  • ⁇ 1> A test piece measuring 20 cm in width direction and 20 cm in length direction is cut out from a water-soluble film.
  • ⁇ 2> Store the cut test piece in a room at 23° C. and 50% RH for 16 hours or longer to condition the humidity.
  • the mass of the humidity-conditioned test piece is measured as "the mass of the test piece before immersion in the model detergent", and the test piece is placed in a model detergent that is 100 times or more the mass of the test piece in an environment of 23 ° C. and 50% RH. Soak for 1 hour.
  • the mass of the test piece was measured in an environment of 23 ° C. and 50% RH in the "test after immersion in model detergent.
  • the degree of swelling of the water-soluble film is 30-50%. If the degree of swelling of the water-soluble film exceeds 50%, the water-soluble film may absorb the model detergent, resulting in insufficient seal strength.
  • the upper limit of the degree of swelling of the water-soluble film is preferably 45% or less, more preferably 43% or less, even more preferably 41% or less.
  • the degree of swelling of the water-soluble film is less than 30%, it is considered that the amount of PVA crystals in the water-soluble film is large, so that the softening of the water-soluble film during heat sealing becomes insufficient, resulting in insufficient sealing. It is presumed that the strength will be insufficient.
  • the lower limit of the degree of swelling of the water-soluble film is preferably 32% or higher, more preferably 34% or higher, even more preferably 36% or higher.
  • the degree of swelling of the water-soluble film is strongly influenced by the crystal structure of PVA such as PVA crystals and PVA amorphous in the water-soluble film. Therefore, by adjusting the composition of the water-soluble film (for example, the degree of saponification and modification of PVA, the type and content of the plasticizer) and the film-forming conditions (draft ratio, drying conditions, draw ratio, etc.), the water-soluble film can control the degree of swelling.
  • ⁇ Complete dissolution time of water-soluble film> the water-soluble film is immersed in a model detergent for 24 hours under an environment of 23° C. and 50% RH, and then immersed in deionized water at 5° C. for complete dissolution time (hereinafter referred to as complete dissolution time ) is measured by the following ⁇ 1> to ⁇ 6> methods ⁇ 1> Place the water-soluble film in a constant temperature and humidity chamber adjusted to 20 ° C and 65% RH for 16 hours or more to adjust the humidity do.
  • ⁇ 2> After cutting out a rectangular sample with a length of 40 mm and a width of 35 mm from the humidity-conditioned water-soluble film, it was immersed in a model detergent of 100 times or more the mass of the film at 23 ° C. and 50% RH for 24 hours. Soak for hours.
  • ⁇ 3> Put 300 mL of deionized water into a 500 mL beaker, and adjust the water temperature to 5 ⁇ 0.3° C. while stirring with a magnetic stirrer equipped with a 3 cm long bar at a rotation speed of 280 rpm.
  • ⁇ 4> After removing the film sample from the model detergent and quickly wiping off the model detergent adhering to the surface with filter paper, two 50 mm ⁇ 50 mm plastic plates with rectangular windows (holes) of 35 mm length ⁇ 23 mm width were opened. The sample is sandwiched and fixed between the two so that the longitudinal direction of the sample is parallel to the longitudinal direction of the window and the sample is positioned substantially at the center in the width direction of the window. ⁇ 5> The sample fixed to the plastic plate in the above ⁇ 4> is immersed in deionized water in a beaker while taking care not to contact the bar of the magnetic stirrer. ⁇ 6> Measure the time from immersion in deionized water until the sample immersed in deionized water completely disappears.
  • the sample disappears completely means that the undissolved portion of the water-soluble film that can be visually recognized disappears.
  • the complete dissolution time of the water-soluble film is within 100 seconds. If the complete dissolution time exceeds 100 seconds, it may be difficult to use for packaging various chemicals such as liquid detergents and agricultural chemicals.
  • the upper limit of the complete dissolution time is preferably within 90 seconds, more preferably within 75 seconds, and even more preferably within 60 seconds.
  • the lower limit of the complete dissolution time of the water-soluble film is not particularly limited. The strength of the water-soluble film tends to decrease.
  • the lower limit of the complete dissolution time is preferably 5 seconds or longer, more preferably 10 seconds or longer, even more preferably 15 seconds or longer, and particularly preferably 20 seconds or longer.
  • the complete dissolution time of the water-soluble film is strongly influenced by the affinity of PVA for water and the crystal structure of PVA such as PVA crystals and PVA amorphous in the water-soluble film. Therefore, by adjusting the composition of the water-soluble film (for example, the degree of saponification and modification of PVA, the type and content of the plasticizer) and the film-forming conditions (draft ratio, drying conditions, draw ratio, etc.), the water-soluble film complete dissolution time can be controlled.
  • FIG. 1 is a drawing for explaining a method for measuring 165° C. seal strength.
  • FIG. 1(a) is a view of the water-soluble film viewed from its thickness direction
  • FIG. 1(b) is a view showing the water-soluble It is the figure which looked at the film from the side direction.
  • 10 or more test pieces of 100 mm width ⁇ 15 mm length are cut out from a water-soluble film.
  • ⁇ 2> Store the cut test piece in a room at 23° C. and 50% RH for 16 hours or longer to condition the humidity.
  • the humidity-conditioned test piece is immersed in a model detergent of 100 times or more the mass of the test piece for 1 hour in an environment of 23°C and 50% RH while preventing the test pieces from overlapping each other.
  • ⁇ 4> After removing the test piece from the model detergent and wiping off the model detergent adhering to the surface of the water-soluble film with filter paper, as shown in FIG.
  • one of the short sides with a length of 15 mm is heat-sealed with a width of 5 mm at a set heat sealing pressure of 1.2 MPa using a thermal tilting device HG-100-2 manufactured by Toyo Seiki Seisakusho Co., Ltd. do.
  • Atmosphere 23°C
  • 50% RH Chuck interval 50mm
  • Tensile speed 300mm/min ⁇ 6> Perform this measurement on at least five sets of heat-sealed test pieces, and take the average value of the obtained maximum test forces as the 165° C. seal strength [N/15 mm].
  • the 165°C seal strength of the water-soluble film is preferably 2.0 to 10.0 N/15 mm.
  • the 165° C. seal strength is more preferably 2.5 N/15 mm or more, more preferably 3.0 N/15 mm or more.
  • the 165° C. seal strength is 10.0 N/15 mm or less, the strength of the water-soluble film is prevented from being lowered, and the water-soluble film other than the heat-sealed portion is less likely to be torn.
  • the 165° C. seal strength is more preferably 9.5 N/15 mm or less, even more preferably 8.5 N/15 mm or less.
  • the upper limit of the thickness of the water-soluble film of the present invention is preferably 80 ⁇ m or less, more preferably 70 ⁇ m or less, even more preferably 60 ⁇ m or less, and particularly preferably 50 ⁇ m or less.
  • the lower limit of the thickness of the water-soluble film is preferably 5 ⁇ m or more, more preferably 10 ⁇ m or more, still more preferably 15 ⁇ m or more, and particularly preferably 20 ⁇ m or more.
  • the thickness of the water-soluble film can be obtained by measuring the thickness at 10 arbitrary points (for example, 10 arbitrary points on a straight line drawn in the length direction of the water-soluble film) and calculating the average value thereof. .
  • the water-soluble film of the present invention contains PVA.
  • PVA those produced by saponifying a vinyl ester polymer obtained by polymerizing a vinyl ester monomer can be used.
  • vinyl ester monomers include vinyl formate, vinyl acetate, vinyl propionate, vinyl valerate, vinyl laurate, vinyl stearate, vinyl benzoate, vinyl pivalate, and vinyl versatate. Of these, vinyl acetate is preferred.
  • the vinyl ester polymer is preferably obtained by using only one or two or more vinyl ester monomers as a monomer, and is preferably obtained by using only one vinyl ester monomer as a monomer. More preferably, it may be a copolymer of one or more vinyl ester monomers and other monomers copolymerizable therewith.
  • vinyl ester monomers include, for example, ethylene; olefins having 3 to 30 carbon atoms such as propylene, 1-butene and isobutene; acrylic acid or salts thereof; Acrylics such as ethyl, n-propyl acrylate, i-propyl acrylate, n-butyl acrylate, i-butyl acrylate, t-butyl acrylate, 2-ethylhexyl acrylate, dodecyl acrylate, octadecyl acrylate, etc.
  • methacrylic acid or its salt methacrylic acid 2 - methacrylic acid esters such as ethylhexyl, dodecyl methacrylate, octadecyl methacrylate; Acrylamide derivatives such as propyldimethylamine or its salts, N-methylolacrylamide or its derivatives; salts, methacrylamide derivatives such as N-methylolmethacrylamide or derivatives thereof; N-vinylamides such as N-vinylformamide, N-vinylacetamide, N-vinylpyrrolidone; methyl vinyl ether, ethyl vinyl ether, n-propyl vinyl ether, i
  • monomers that can be copolymerized with these vinyl ester monomers monomers that generate bulky functional groups on polymer side chains after polymerization and saponification are not preferable because they tend to reduce the seal strength of the resulting water-soluble film.
  • olefins having a small number of carbon atoms such as ethylene and propylene
  • carboxylic acid monomers such as acrylic acid and methacrylic acid
  • sulfonic acid monomers are preferable.
  • carboxylic acid-based monomers and sulfonic acid-based monomers are more preferable because the contact angle, degree of swelling, and complete dissolution time of the resulting water-soluble film are easily balanced.
  • the PVA contained in the water-soluble film of the present invention is preferably carboxylic acid-modified PVA obtained by saponifying a carboxylic acid-vinyl acetate copolymer obtained by copolymerizing vinyl acetate and a carboxylic acid-based monomer.
  • the upper limit of the degree of modification of the carboxylic acid-modified PVA is preferably 10 mol % or less, more preferably 8 mol % or less, and even more preferably 6 mol % or less.
  • the lower limit of the degree of modification of the carboxylic acid-modified PVA is preferably 0.5 mol % or more, more preferably 1 mol % or more, and even more preferably 2 mol % or more.
  • the PVA contained in the water-soluble film of the present invention is also preferably a sulfonic acid-modified PVA obtained by saponifying a sulfonic acid-vinyl acetate copolymer obtained by copolymerizing vinyl acetate and a sulfonic acid-based monomer.
  • the upper limit of the degree of modification of the sulfonic acid-modified PVA is preferably 8 mol % or less, more preferably 6 mol % or less, and even more preferably 4 mol % or less.
  • the lower limit of the degree of modification of the sulfonic acid-modified PVA is preferably 0.3 mol % or more, more preferably 0.7 mol % or more, and even more preferably 1 mol % or more.
  • the upper limit of the ratio of structural units derived from other monomers in the vinyl ester polymer is based on the number of moles of all structural units constituting the vinyl ester polymer, from the viewpoint of the water solubility of the water-soluble film and the suppression of perforation. is preferably 15 mol % or less, more preferably 5 mol % or less.
  • the degree of polymerization of PVA contained in the water-soluble film is 100-3000. If the degree of polymerization of PVA is less than 100, the strength of the water-soluble film may be insufficient.
  • the degree of polymerization of PVA is preferably 200 or higher, more preferably 300 or higher, even more preferably 500 or higher. On the other hand, when the degree of polymerization of PVA exceeds 3000, it may become difficult to ensure the productivity of the PVA and the water-soluble film and the water-solubility of the water-soluble film.
  • the degree of polymerization of PVA is preferably 2500 or less, more preferably 2000 or less, even more preferably 1500 or less.
  • the degree of saponification of PVA contained in the water-soluble film is preferably 80-99.5 mol%.
  • the degree of saponification of PVA is defined as the total number of moles of structural units (typically vinyl ester monomer units) that can be converted to vinyl alcohol units by saponification and vinyl alcohol units in PVA. It refers to the ratio (mol %) occupied by the number of moles.
  • the degree of saponification of PVA can be measured according to the description of JIS K6726-1994.
  • the upper limit of the degree of saponification of unmodified PVA and ethylene-modified PVA is preferably 99.5 mol% or less, more preferably 97 mol% or less, and preferably 95 mol% or less. More preferably, it is particularly preferably 93 mol % or less.
  • the lower limit of the degree of saponification of unmodified PVA and hydrophobic ethylene-modified PVA is preferably 80 mol% or more, more preferably 83 mol% or more, further preferably 85 mol% or more, 87 mol % or more is particularly preferred.
  • the unmodified PVA is PVA obtained by saponifying a vinyl acetate homopolymer obtained by homopolymerizing vinyl acetate.
  • Ethylene-modified PVA is PVA obtained by saponifying an ethylene-vinyl acetate copolymer obtained by copolymerizing vinyl acetate and ethylene.
  • the upper limit of the degree of saponification of carboxylic acid-modified PVA and sulfonic acid-modified PVA is preferably 99 mol% or less, more preferably 97 mol% or less, and particularly preferably 96 mol% or less.
  • the lower limit of the degree of saponification of carboxylic acid-modified PVA and sulfonic acid-modified PVA is preferably 85 mol% or more, more preferably 90 mol% or more, and even more preferably 93 mol% or more.
  • one type of PVA may be used alone as the PVA, or two or more types of PVA having different degrees of polymerization, saponification, or modification may be blended and used.
  • the upper limit of the PVA content in the water-soluble film is not particularly limited, but the lower limit of the PVA content is preferably 50% by mass or more, more preferably 80% by mass or more. % by mass or more is more preferable.
  • the water-soluble film contains 1 to 50 parts by mass of a polyhydric alcohol plasticizer based on 100 parts by mass of PVA. If the content of the polyhydric alcohol plasticizer exceeds 50 parts by mass, the resulting water-soluble film tends to have an excessively large contact angle and degree of swelling.
  • the upper limit of the content of the polyhydric alcohol plasticizer is preferably 40 parts by mass or less, more preferably 30 parts by mass or less.
  • the content of the polyhydric alcohol-based plasticizer is less than 1 part by mass, the resulting water-soluble film tends to have an excessively small contact angle and an excessively large degree of swelling.
  • the 165° C. seal strength of the resulting water-soluble film tends to be too low.
  • the lower limit of the content of the polyhydric alcohol plasticizer is preferably 3 parts by mass or more, more preferably 5 parts by mass or more.
  • examples of the polyhydric alcohol plasticizer contained in the water-soluble film include ethylene glycol, glycerin, diglycerin, propylene glycol, diethylene glycol, triethylene glycol, tetraethylene glycol, trimethylolpropane, sorbitol, and the like. be able to.
  • These polyhydric alcohol plasticizers may be used alone or in combination of two or more.
  • ethylene glycol or glycerin is preferable, and glycerin is more preferable, because the contact angle of the water-soluble film can be particularly easily adjusted.
  • the resulting water-soluble film can contain the polyhydric alcohol-based plasticizer.
  • the content ratio of the polyhydric alcohol plasticizer in the water-soluble film is substantially equal to the content ratio of the polyhydric alcohol plasticizer in the film-forming stock solution of the water-soluble film.
  • the type and amount of polyhydric alcohol plasticizer contained in the undiluted solution for the water-soluble film affects the crystal structure of PVA in the water-soluble film. If the amount of the polyhydric alcohol-based plasticizer, which has a high affinity with PVA, is moderately increased, the motility of the PVA molecules increases when drying the PVA membrane obtained by casting the undiluted membrane-forming solution described later on the support. , the crystallization rate of PVA increases during the production of the water-soluble film, and PVA crystals are easily generated in the resulting water-soluble film.
  • the amount of the polyhydric alcohol-based plasticizer is increased too much, the interaction between the PVA polyhydric alcohol-based plasticizer is strengthened and the interaction between PVA molecules is reduced, resulting in PVA in the resulting water-soluble film. Crystals are less likely to form.
  • the degree of swelling of the water-soluble film is presumed to depend on the amount of PVA crystals in the water-soluble film.
  • the surface of the water-soluble film, which interfaces with hydrophobic air, also tends to be hydrophobic, and this tendency increases as the crystallization rate of PVA during production of the water-soluble film slows down. Therefore, the contact angle and swelling degree of the water-soluble film can be adjusted by adjusting the type and amount of the polyhydric alcohol plasticizer.
  • the water-soluble film of the present invention may contain a water-soluble polymer other than starch and/or PVA. good.
  • 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 that have been etherified, esterified, oxidized, etc.; and more preferably modified starches.
  • the upper limit of the starch content in the water-soluble film is preferably 15 parts by mass or less, more preferably 10 parts by mass or less, relative to 100 parts by mass of PVA.
  • the starch content is equal to or less than the above upper limit, it becomes easier to prevent deterioration of the process passability during the production of the water-soluble film.
  • water-soluble polymers other than PVA examples include dextrin, gelatin, glue, casein, shellac, gum arabic, polyacrylic acid amide, sodium polyacrylate, polyvinyl methyl ether, copolymers of methyl vinyl ether and maleic anhydride, Copolymers of vinyl acetate and itaconic acid, polyvinylpyrrolidone, cellulose, acetyl cellulose, acetylbutyl cellulose, carboxymethyl cellulose, methyl cellulose, ethyl cellulose, hydroxyethyl cellulose, sodium alginate and the like.
  • the upper limit of the content of the water-soluble polymer other than PVA in the water-soluble film is preferably 15 parts by mass or less, more preferably 10 parts by mass or less, relative to 100 parts by mass of PVA.
  • the content of the water-soluble polymer is equal to or less than the above upper limit, it becomes easier to prevent deterioration of the water solubility of the water-soluble film.
  • the water-soluble film preferably contains a surfactant from the viewpoint of improving the handleability and peelability from the film forming apparatus when manufacturing the water-soluble film.
  • the type of surfactant is not particularly limited, and examples thereof include anionic surfactants and nonionic surfactants.
  • anionic surfactants include carboxylic acid types such as potassium laurate; sulfuric acid ester types such as octyl sulfate; and sulfonic acid types such as dodecylbenzene sulfonate.
  • nonionic surfactants include alkyl ether types such as polyoxyethylene lauryl ether and polyoxyethylene oleyl ether; alkylphenyl ether types such as polyoxyethylene octylphenyl ether; and alkyl ester types such as polyoxyethylene laurate.
  • Alkylamine type such as polyoxyethylene laurylamino ether
  • Alkylamide type such as polyoxyethylene lauric acid amide
  • Polypropylene glycol ether type such as polyoxyethylene polyoxypropylene ether
  • allylphenyl ether type such as polyoxyalkylene allylphenyl ether;
  • One type of surfactant may be used alone, or two or more types may be used in combination.
  • nonionic surfactants are preferred, alkanolamide surfactants are more preferred, and aliphatic carboxylic acids (
  • a dialkanolamide eg, diethanolamide, etc.
  • a saturated or unsaturated aliphatic carboxylic acid having 8 to 30 carbon atoms is more preferable.
  • the upper limit of the surfactant content in the water-soluble film is preferably 10 parts by mass or less, more preferably 1 part by mass or less, and 0.5 parts by mass or less per 100 parts by mass of PVA. is more preferable, and 0.3 parts by mass or less is particularly preferable.
  • the content of the surfactant is equal to or less than the above upper limit, it is easy to prevent the surfactant from bleeding out on the surface of the water-soluble film and the deterioration of the appearance of the water-soluble film due to aggregation of the surfactant. Become.
  • the lower limit of the surfactant content is preferably 0.01 parts by mass or more, more preferably 0.02 parts by mass or more, and 0.05 parts by mass or more with respect to 100 parts by mass of PVA. is more preferable.
  • the content of the surfactant is at least the above lower limit, it becomes easy to improve the releasability from the film forming apparatus when producing the water-soluble film. Moreover, it becomes easy to prevent blocking from occurring between water-soluble films.
  • the water-soluble film of the present invention may contain a filler. Incorporation of a filler can improve the mechanical strength and handleability of the water-soluble film, and the model detergent cannot permeate the filler, so the path length required for permeation in the film increases, resulting in a barrier. improvement in sexuality can be expected.
  • fillers include carbon black, metal powder, silica, alumina, calcium carbonate, titanium dioxide, talc, mica, and clay minerals such as bentonite.
  • the upper limit of the filler content in the water-soluble film is preferably 40 parts by mass or less, more preferably 20 parts by mass or less, and further preferably 10 parts by mass or less with respect to 100 parts by mass of PVA. preferable.
  • the lower limit of the filler content in the water-soluble film is preferably 0.1 parts by mass or more, more preferably 0.5 parts by mass or more, and 1 part by mass or more with respect to 100 parts by mass of PVA. It is even more preferable to have
  • the water-soluble film of the present invention contains a plasticizer, starch, a water-soluble polymer other than PVA, a surfactant, water, an antioxidant, an ultraviolet absorber, a lubricant, a cross-linking agent, a colorant, an antiseptic, and an antifungal agent. Ingredients such as agents and other polymer compounds may be contained within the range that does not impair the effects of the present invention.
  • the ratio of the total weight of PVA, plasticizer, starch, water-soluble polymer other than PVA, and surfactant to the total weight of the water-soluble film of the present invention is within the range of 60 to 100% by weight. is preferred, more preferably in the range of 80 to 100% by mass, and even more preferably in the range of 90 to 100% by mass.
  • the method for producing a water-soluble film is not particularly limited. discharge into a solvent), a dry-wet film-forming method, a gel film-forming method (a method of obtaining a water-soluble film by cooling and gelling the undiluted film-forming solution and then removing the solvent by extraction), or a combination thereof.
  • a film can be formed by any method such as a method of using an extruder to obtain a film-forming stock solution and extruding it from a T-die or the like to form a film, such as a melt extrusion film-forming method or an inflation molding method. can.
  • the cast film-forming method or the melt extrusion film-forming method is preferable because a homogeneous water-soluble film can be obtained with high productivity.
  • the cast film-forming method or the melt-extrusion film-forming method for the water-soluble film will be described below.
  • the undiluted film-forming solution is heated to remove the solvent, thereby solidifying into a film.
  • the solidified film is peeled off from the support, dried with a drying roll or a drying oven if necessary, heat-treated if necessary, and wound up to form a roll-shaped long water-soluble film. you can get the film.
  • the upper limit of the volatile fraction (concentration of volatile components such as solvents removed by volatilization or evaporation during film formation) of the film-forming stock solution is preferably 90% by mass or less, and 80% by mass or less. is more preferred.
  • the volatile matter concentration of the membrane-forming stock solution is equal to or less than the above upper limit, the viscosity of the membrane-forming stock solution becomes low, and it becomes easy to prevent the thickness uniformity of the obtained water-soluble film from being impaired.
  • the lower limit of the volatile content of the film-forming stock solution is preferably 50% by mass or more, more preferably 55% by mass or more. When the volatile content of the membrane-forming stock solution is at least the above lower limit, the viscosity of the membrane-forming stock solution increases, making it easier to prevent difficulty in producing a water-soluble film.
  • the method of preparing the membrane-forming stock solution includes a method of dissolving PVA and additives such as plasticizers and surfactants in a dissolution tank or the like, or a method of using a single-screw or twin-screw extruder to prepare water-containing PVA.
  • a method of melt-kneading a method of melt-kneading together with a plasticizer, a surfactant, and the like.
  • the method of dissolving in a dissolving tank or the like or the method of using a twin-screw extruder is preferable.
  • the prepared membrane-forming stock solution is sent to a T-die or the like through a pipe or the like, and discharged in the form of a membrane onto the support through the die lip.
  • a film-forming stock solution containing PVA is poured from a die through a die lip onto a support in the form of a film and dried, in which the film-forming stock solution is
  • the draft ratio which is obtained by dividing the linear velocity of the support on which the liquid is drooled by the linear velocity of the membrane-forming stock solution on the die lip, is preferably 2 to 60.
  • the upper limit of the draft ratio is more preferably 50 or less, even more preferably 40 or less, and particularly preferably 30 or less.
  • the draft ratio When the draft ratio is equal to or less than the above upper limit, it becomes easy to prevent the resulting water-soluble film from having an excessively large contact angle, an excessively small degree of swelling, and a decrease in the 165°C seal strength. In addition, when the draft ratio is equal to or less than the above upper limit, it becomes easier to prevent the thickness of the water-soluble film to be obtained from becoming non-uniform, or the complete dissolution time to be lengthened due to a decrease in water solubility.
  • the lower limit of the draft ratio is more preferably 5 or more, still more preferably 8 or more, and particularly preferably 10 or more.
  • the linear velocity of the membrane-forming solution in the die lip can be obtained by dividing the volumetric flow rate of the membrane-forming solution by the area of the die lip opening (the width of the die lip x the opening of the lip).
  • the rate of decrease of the volatile content of the undiluted film-forming solution on the support is 0.5 to 7% by mass/second.
  • the upper limit of the volatile content reduction rate of the membrane-forming stock solution is preferably less than 6% by mass/second, more preferably less than 5% by mass/second. If the rate of decrease of the volatile matter in the film-forming stock solution is below the above upper limit, the contact angle of the obtained water-soluble film becomes too small, the degree of swelling becomes too large, and the 165°C seal strength decreases. becomes easier to prevent.
  • the lower limit of the reduction rate of the volatile matter in the film-forming stock solution is more preferably 1% by mass/second or more, and further preferably 2% by mass/second or more.
  • the rate of decrease of the volatile matter in the film-forming stock solution is at least the above lower limit, the contact angle of the obtained water-soluble film becomes too large, the degree of swelling becomes too small, and the 165°C seal strength decreases. becomes easier to prevent.
  • the rate of decrease of the volatile content of the membrane-forming stock solution on the support can be calculated by the following formula.
  • Decrease rate of volatile content of film-forming stock solution on support (volatile content of film-forming solution - volatile content in film immediately after peeling from support) / contact time between film and support
  • the volatile content can be calculated from the change in mass before and after drying the film in an electric heat dryer at 105° C. for 16 hours, in the same manner as the volatile content in the film forming stock solution.
  • the surface temperature of the support onto which the undiluted membrane-forming solution is poured is preferably 50 to 110°C.
  • the upper limit of the surface temperature of the support is more preferably 100° C. or lower, more preferably 95° C. or lower.
  • the surface temperature of the support is equal to or lower than the above upper limit, it becomes easier to prevent the contact angle of the resulting water-soluble film from becoming too small, the degree of swelling from becoming too large, and the 165°C seal strength from decreasing.
  • the lower limit of the surface temperature of the support is more preferably 60° C.
  • the surface temperature of the support is equal to or higher than the above lower limit, the PVA film is dried slowly, thereby making it easier to prevent excessive crystallization of PVA.
  • the contact angle of the resulting water-soluble film from becoming too large, the degree of swelling from becoming too small, and the 165° C. seal strength from decreasing.
  • it becomes easy to prevent the water solubility of the resulting water-soluble film from being lowered and the complete dissolution time to be prolonged.
  • the drying rate may be adjusted by uniformly blowing hot air onto the entire non-contact surface side of the PVA membrane.
  • the upper limit of the hot air temperature is preferably 105° C. or lower, more preferably 100° C. or lower.
  • the lower limit of the hot air temperature is preferably 75°C or higher, more preferably 85°C or higher.
  • the temperature of the hot air is equal to or higher than the above lower limit, it becomes easy to prevent the contact angle of the resulting water-soluble film from becoming too large, the degree of swelling from becoming too small, and the 165° C. seal strength from decreasing. Moreover, it becomes easy to prevent the water solubility of the resulting water-soluble film from being lowered and the complete dissolution time to be prolonged.
  • the upper limit of the hot air velocity is preferably 10 m/sec or less, more preferably 7 m/sec or less.
  • the lower limit of the hot air velocity is preferably 1 m/sec or more, more preferably 3 m/sec or more.
  • the PVA membrane formed by casting the undiluted membrane solution onto the support in the form of a film is dried on the support to a volatile content of preferably 5 to 50% by mass, and then peeled off. dried further.
  • a drying method There is no particular limitation on the drying method, and examples include a method of contacting with a drying oven or a drying roll.
  • the number of drying rolls is preferably 3 or more, more preferably 4 or more, and even more preferably 5 or more.
  • the number of drying rolls is preferably 30 or less.
  • the upper limit of the temperature of the drying furnace and drying rolls is preferably 110°C or less, more preferably 100°C or less, more preferably 90°C or less, and even more preferably 85°C or less.
  • the lower limit of the temperature of the drying oven and drying rolls is preferably 40° C. or higher, more preferably 45° C. or higher, and even more preferably 50° C. or higher.
  • the upper limit of the draw ratio obtained by dividing the winding speed of the film after drying by the linear velocity of the support on which the undiluted film-forming solution is drooled is 1.80 or less. It is preferably 1.75 or less, more preferably 1.70 or less.
  • the draw ratio is equal to or less than the above upper limit, it becomes easy to prevent the resulting water-soluble film from having an excessively large contact angle, an excessively small degree of swelling, and a decrease in the 165°C seal strength.
  • the lower limit of the draw ratio is preferably 0.95 or higher, more preferably 1.00 or higher, and even more preferably 1.05 or higher. When the draw ratio is at least the above lower limit, it becomes easier to prevent the contact angle of the obtained water-soluble film from becoming too small, the degree of swelling from becoming too large, and the 165° C. seal strength from decreasing.
  • the method for producing a water-soluble film of the present invention preferably includes a step of heat-treating the water-soluble film under conditions of 80 to 300°C. By performing heat treatment, the contact angle, degree of swelling, and complete dissolution time of the water-soluble film can be adjusted.
  • the upper limit of the heat treatment temperature is more preferably 280° C. or lower, still more preferably 260° C. or lower, and particularly preferably 240° C. or lower.
  • the heat treatment temperature is equal to or lower than the above upper limit, it becomes easy to prevent the contact angle of the water-soluble film from becoming too large, the swelling degree from becoming too small, and the 165° C. seal strength from decreasing.
  • the lower limit of the heat treatment temperature is more preferably 90° C.
  • the heat treatment temperature is equal to or higher than the above lower limit, it becomes easy to prevent the contact angle of the water-soluble film from becoming too small, the degree of swelling from becoming too large, and the 165° C. seal strength from decreasing.
  • the water-soluble film thus produced is further subjected to humidity conditioning treatment, embossing, cutting of both ends (edges) of the film, etc., as required, and then rolled onto a cylindrical core. be wound up.
  • the upper limit of the volatile content of the water-soluble film finally obtained by a series of treatments is preferably 5% by mass or less, more preferably 4% by mass or less.
  • the lower limit of the volatile content of the water-soluble film is preferably 1% by mass or more, more preferably 2% by mass or more.
  • the water-soluble film of the present invention can be suitably used for various water-soluble film applications.
  • Such water-soluble films include, for example, pharmaceutical packaging films, hydraulic transfer base films, embroidery base films, release films for forming artificial marble, seed packaging films, waste bag films, and the like. be done.
  • the water-soluble film of the present invention is preferably used as a drug packaging film because the effects of the present invention are exhibited more remarkably.
  • the types of drugs include agricultural chemicals, detergents (including bleaching agents), disinfectants, and the like. There are no particular restrictions on the physical properties of the drug, and it may be acidic, neutral, or alkaline.
  • the drug may also include a boron-containing compound.
  • the drug may be in the form of powder, mass, gel or liquid.
  • the form of packaging is not particularly limited, but the form of unit packaging (preferably sealed packaging) in which the drug is packaged per unit amount is preferred.
  • the package of the present invention can be obtained by packaging a drug using the film of the present invention as a drug packaging film.
  • Transport test A transport test was conducted on a package in which a model detergent was packaged with a water-soluble film according to the methods ⁇ 1> to ⁇ 7> below. ⁇ 1> Cut out two test pieces of 7 cm ⁇ 7 cm from the water-soluble film. ⁇ 2> Two cut test pieces are stored in a room at 23° C. and 50% RH for 16 hours or more to condition the humidity. ⁇ 3> In an environment of 23°C and 50% RH, two humidity-conditioned test pieces are immersed in a model detergent for 16 hours. ⁇ 4> After wiping off the model detergent adhering to the surface with filter paper, stack two test pieces taken out of the model detergent and heat-seal the three sides with a seal width of 1 cm to create a pouch with one side open. .
  • ⁇ 5> Pour 20 cm 3 of model detergent into the pouch, adjust the seal width so that the film is stretched without wrinkles on the pouch surface, and heat-seal the remaining one side to form the model detergent package.
  • 100 of the above packages are prepared, packed in a 45 L polyethylene bag, and placed in a cardboard box (320 x 335 x 325 cm). Fill the gap between the polyethylene bag and the cardboard box with cushioning material. Then, the cardboard box containing the package is loaded on a truck, and a transport test is conducted by making 10 round trips between Okayama Prefecture and Tokyo.
  • ⁇ 7> Visually observe the packages after transportation to determine the number of broken packages.
  • Example 1 100 parts by mass of carboxylic acid-modified PVA (degree of saponification 96 mol%, degree of polymerization 1200) obtained by saponifying 4 mol% monomethyl maleate (MMM)-modified polyvinyl acetate, polyhydric alcohol plasticizer 25 parts by mass of glycerin as an agent, 0.2 parts by mass of lauric acid diethanolamide as a surfactant, and water were charged into a twin-screw extruder to prepare a film-forming stock solution having a volatile content of 60% by mass.
  • MMM monomethyl maleate
  • This film-forming stock solution is discharged from a T-die through a die lip at a draft ratio of 11 onto a metal roll (support) having a surface temperature of 90° C., drooling, and blowing hot air at 100° C. at 5 m/sec over the entire non-contact surface of the support. It was dried by spraying at a speed of Under these conditions, the rate of reduction of the volatile matter of the membrane-forming stock solution on the support was 2.3% by mass/sec. It was then peeled from the support and dried from the second drying roll to the final drying roll such that one side and the other side of the PVA film alternately contacted each drying roll. The surface temperatures from the second drying roll to the final drying roll were all 80°C.
  • Example 2 carboxylic acid-modified PVA modified with 4 mol% MMM (degree of saponification 96 mol%, degree of polymerization 1200) was converted to sulfonic acid-modified PVA modified with 2 mol% 2-acrylamido-2-methylpropylsulfonic acid (AMPS) (saponification degree of polymerization 99 mol%, degree of polymerization 1200), in Example 3, carboxylic acid-modified PVA modified with 4 mol% MMM (degree of saponification 96 mol%, degree of polymerization 1200) was converted to unmodified PVA (degree of saponification 88 mol%, degree of polymerization 1200 ), in Comparative Example 1, MMM4 mol% modified carboxylic acid-modified PVA (degree of saponification 96 mol%, degree of polymerization 1200) was changed to unmodified PVA (degree of saponification 99 mol%, degree of polymerization 1200).
  • AMPS 2-acrylamido-2-methylpropy
  • a water-soluble film was obtained in the same manner as in Example 1. Using the obtained water-soluble film, the contact angle, swelling degree, complete dissolution time, and 165° C. seal strength of the water-soluble film were measured. Furthermore, a transportation test was conducted on a package containing a model detergent with this water-soluble film. Table 1 shows the results.
  • Example 4 The draft ratio between the T-die and the support was set to 31, the surface temperature of the support was set to 80°C, the temperature of the hot air blown over the entire non-contact surface with the support was set to 90°C, and the surface temperature of the heat treatment roll was set to 180°C.
  • a water-soluble film was obtained in the same manner as in Example 3, except that the draw ratio from the support to the winding was changed to 1.8. Under these conditions, the rate of reduction of the volatile matter of the membrane-forming stock solution on the support was 5.9% by mass/sec. Using the obtained water-soluble film, the contact angle, swelling degree, complete dissolution time, and 165° C. seal strength of the water-soluble film were measured. Furthermore, a transportation test was conducted on a package containing a model detergent with this water-soluble film. Table 1 shows the results.
  • Example 5 The draft ratio between the T die and the support is set to 3, the surface temperature of the support is set to 105°C, the temperature of the hot air blown over the entire non-contact surface with the support is set to 105°C, and the surface temperature of the heat treatment roll is set to 180°C.
  • a water-soluble film was obtained in the same manner as in Example 3, except that the composition was changed. Under these conditions, the rate of reduction of the volatile matter of the membrane-forming stock solution on the support was 6.7% by mass/sec. Using the obtained water-soluble film, the contact angle, swelling degree, complete dissolution time, and 165° C. seal strength of the water-soluble film were measured. Furthermore, a transportation test was conducted on a package containing a model detergent with this water-soluble film. Table 1 shows the results.
  • Example 6 A water-soluble film was obtained in the same manner as in Example 1, except that the amount of glycerin, which is a polyhydric alcohol plasticizer, was changed to 42 parts by mass with respect to 100 parts by mass of PVA. Under these conditions, the rate of reduction of the volatile matter of the membrane-forming stock solution on the support was 2.4% by mass/second. Using the obtained water-soluble film, the contact angle, swelling degree, complete dissolution time, and 165° C. seal strength of the water-soluble film were measured. Furthermore, a transportation test was conducted on a package containing a model detergent with this water-soluble film. Table 1 shows the results.
  • Example 2 A water-soluble film was obtained in the same manner as in Example 3, except that the draft ratio between the T-die and the support was changed to 1.2, and the draw ratio from the support to the winding was changed to 0.8. Using the obtained water-soluble film, the contact angle, swelling degree, complete dissolution time, and 165° C. seal strength of the water-soluble film were measured. Furthermore, a transportation test was conducted on a package containing a model detergent with this water-soluble film. Table 1 shows the results.
  • Example 3 A water-soluble film was obtained in the same manner as in Example 3, except that the amount of glycerin, which is a polyhydric alcohol plasticizer, was changed to 1 part by mass with respect to 100 parts by mass of PVA. Under these conditions, the rate of reduction of the volatile matter of the membrane-forming stock solution on the support was 2.2 mass %/sec. Using the obtained water-soluble film, the contact angle, swelling degree, complete dissolution time, and 165° C. seal strength of the water-soluble film were measured. Furthermore, a transportation test was conducted on a package containing a model detergent with this water-soluble film. Table 1 shows the results.
  • Example 4 In the same manner as in Example 1, except that the surface temperature of the support was changed to 70 ° C., the temperature of the hot air blown over the entire non-contact surface with the support was changed to 80 ° C., and the surface temperature of the heat treatment roll was changed to 90 ° C. A sexual film was obtained. Under these conditions, the rate of reduction of the volatile matter of the membrane-forming stock solution on the support was 0.4% by mass/sec. Using the obtained water-soluble film, the contact angle, swelling degree, complete dissolution time, and 165° C. seal strength of the water-soluble film were measured. Furthermore, a transportation test was conducted on a package containing a model detergent with this water-soluble film. Table 1 shows the results.
  • Example 5 The procedure was the same as in Example 1 except that the draft ratio between the T-die and the support was changed to 3, the surface temperature of the support was changed to 105°C, and the temperature of the hot air blown over the entire non-contact surface with the support was changed to 105°C. to obtain a water-soluble film. Under these conditions, the rate of decrease of the volatile matter of the membrane-forming stock solution on the support was 7.2 mass %/sec. Using the obtained water-soluble film, the contact angle, swelling degree, complete dissolution time, and 165° C. seal strength of the water-soluble film were measured. Furthermore, a transportation test was conducted on a package containing a model detergent with this water-soluble film. Table 1 shows the results.
  • Example 3 The water-soluble film obtained in Example 3 was heat-sealed without being immersed in the model detergent in the method for measuring the 165°C seal strength, and the 165°C seal strength was measured. Table 1 shows the results. Without immersion in the model detergent, the 165°C seal strength was higher than Example 3 immersed in the model detergent.

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