Classifications

• • 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
  • 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
  • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
  • C11D1/66—Non-ionic compounds
  • C11D1/83—Mixtures of non-ionic with anionic compounds
• • 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
  • C11D17/04—Detergent materials or soaps characterised by their shape or physical properties combined with or containing other objects
  • C11D17/041—Compositions releasably affixed on a substrate or incorporated into a dispensing means
  • C11D17/042—Water soluble or water disintegrable containers or substrates containing cleaning compositions or additives for cleaning compositions
• • 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
  • C11D17/04—Detergent materials or soaps characterised by their shape or physical properties combined with or containing other objects
  • C11D17/041—Compositions releasably affixed on a substrate or incorporated into a dispensing means
  • C11D17/042—Water soluble or water disintegrable containers or substrates containing cleaning compositions or additives for cleaning compositions
  • C11D17/043—Liquid or thixotropic (gel) compositions
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B65—CONVEYING; PACKING; STORING; HANDLING THIN OR FILAMENTARY MATERIAL
  • B65D—CONTAINERS FOR STORAGE OR TRANSPORT OF ARTICLES OR MATERIALS, e.g. BAGS, BARRELS, BOTTLES, BOXES, CANS, CARTONS, CRATES, DRUMS, JARS, TANKS, HOPPERS, FORWARDING CONTAINERS; ACCESSORIES, CLOSURES, OR FITTINGS THEREFOR; PACKAGING ELEMENTS; PACKAGES
  • B65D65/00—Wrappers or flexible covers; Packaging materials of special type or form
  • B65D65/38—Packaging materials of special type or form
  • B65D65/46—Applications of disintegrable, dissolvable or edible materials
• • 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
  • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
  • C11D1/02—Anionic compounds
  • C11D1/12—Sulfonic acids or sulfuric acid esters; Salts thereof
  • C11D1/22—Sulfonic acids or sulfuric acid esters; Salts thereof derived from aromatic compounds
• • 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
  • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
  • C11D1/66—Non-ionic compounds
  • C11D1/72—Ethers of polyoxyalkylene glycols
• • 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
• • 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
  • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
  • C11D3/16—Organic compounds
  • C11D3/20—Organic compounds containing oxygen
  • C11D3/2003—Alcohols; Phenols
  • C11D3/2041—Dihydric alcohols

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.
• the phenomenon that the drug in the package volatilizes to the outside over time is due to the barrier performance of the water-soluble film used in the package.
• the PVA contained in the water-soluble film has better barrier properties than general polymers, and is extremely resistant to non-polar substances such as gases such as oxygen and hydrogen, and lipophilic substances such as olefins.
• the barrier properties against substances with relatively small molecular weights and high polarity such as water, lower alcohols and lower fatty acids are not so high.
• the main components of chemicals such as household laundry detergents packaged in packages are surfactants, many of which have relatively low molecular weights and high polarity.
• the barrier performance of a water-soluble film containing PVA is strongly influenced by the affinity between the drug to be packaged and the water-soluble film, and the crystal structure of PVA such as PVA crystals and PVA amorphous in the water-soluble film. be.
• the dimensional change (area change rate) of the water-soluble film containing PVA is strongly influenced by the affinity between the drug to be packaged and the water-soluble film, as well as the residual stress present in the water-soluble film from the film-forming process. estimated to be Therefore, even in a package using a water-soluble film having a specific area change rate as described in Patent Document 1, the barrier performance of the water-soluble film is not sufficient, and the long-term and high-temperature environment is not sufficient. It is presumed that wrinkles may occur in the package when the package is stored in such a condition, and the problem of poor appearance may occur over time.
• the relationship between the barrier performance of the water-soluble film containing PVA, the affinity between the drug to be packaged and the water-soluble film, and the crystal structure of PVA such as PVA crystals and PVA amorphous in the water-soluble film is as follows. is estimated to be First, it is believed that the surfactant, which is the main component of the drug to be packaged and also the component that permeates the water-soluble film, cannot permeate the PVA crystal portion in the water-soluble film. Therefore, the barrier performance of the water-soluble film tends to improve as the amount of PVA crystals in the water-soluble film increases.
• the surfactant can diffuse the PVA amorphous part in the water-soluble film, but the diffusion speed depends on the molecular mobility of the PVA polymer in the PVA amorphous (easiness to open gaps between PVA polymer molecules). ), and the affinity between the surfactant and the PVA polymer molecule. Therefore, the lower the density of the PVA amorphous portion, the weaker the interaction between the PVA polymer molecules, and the higher the affinity between the surfactant and the PVA polymer molecules, the lower the barrier performance tends to be.
• the present invention provides a water-soluble film that maintains good water solubility and does not easily cause the problem of appearance defects over time during high-temperature, long-term storage even when packaging chemicals such as laundry detergents, and a method for producing the same. And it aims at providing the package which packaged the medicine using the said water-soluble film.
• the present invention [1] A water-soluble film containing PVA with a degree of polymerization of 100 to 3,000 and containing 1 to 50 parts by mass of a polyhydric alcohol plasticizer per 100 parts by mass of PVA, wherein the water-soluble film comprises: 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 , 9.5% by mass of diethylene glycol, and a package containing a model detergent containing 5.7% by mass of water, the weight reduction rate of the package when the package is stored at 23 ° C.
• RH is 1.0 to 6.0 g/(m 2 ⁇ day) per surface area of the water-soluble film in contact with the model detergent of the package, and the water-soluble film is placed in the model detergent at 23 ° C. and 50% RH. After being immersed in the environment for 24 hours, a tensile test was performed at 23 ° C. and 50% RH. A water-soluble film having a complete dissolution time of 100 seconds or less when immersed in deionized water at 5°C after being immersed in an environment of 50% RH for 24 hours; Regarding.
• the present invention [2] The water-soluble film according to [1] above, wherein the PVA is carboxylic acid-modified or sulfonic acid-modified PVA and has a saponification degree of 90 mol% or more; [3] The water-soluble film according to [1] or [2], which has a thickness of 5 to 80 ⁇ m; [4] A method for producing a water-soluble film according to any one of [1] to [3] above, wherein 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.
• the draft ratio obtained by dividing the linear velocity of the support on which the membrane-forming undiluted solution is drooled by the linear velocity of the membrane-forming undiluted solution on the die lip is 2 to 60, and the film after drying is A method for producing a water-soluble film, wherein the draw ratio obtained by dividing the winding speed by the linear speed of the support is 0.95 to 1.8;
• a water-soluble film that maintains good water-solubility and does not easily cause a problem of poor appearance over time during long-term storage at high temperatures even when a drug such as laundry detergent is packaged, and its production.
• a method and a package body in which a drug is packaged using the water-soluble film are provided.
• 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
• ⁇ Weight reduction rate of the model detergent package> when the water-soluble film is used as a package containing a model detergent (hereinafter sometimes referred to as a model detergent package), the packaging when the package is stored at 23° C. and 50% RH Body weight loss rate is measured by the following methods ⁇ 1> to ⁇ 8>.
• ⁇ 1> Cut out two test pieces of 7 cm ⁇ 7 cm from the water-soluble film.
• ⁇ 2> Two sheets of the cut film are superimposed and heat-sealed on three sides with a sealing width of 1 cm to prepare a pouch with one side open.
• ⁇ 3> Store the pouch in a room at 23° C. and 50% RH for 16 hours or more to adjust the humidity.
• ⁇ 4> Measure the weight of the empty pouch.
• ⁇ 5> Put about 10g of model detergent in a humidified pouch, heat-seal the remaining side with a seal width of 1cm while making sure that no air is left inside, and the area of the unsealed part is 5cm x 5cm. , create a pouch containing the model detergent.
• ⁇ 6> Measure the mass of the prepared pouch.
• ⁇ 7> Store the pouch in a room at 23°C and 50% RH, and periodically measure the mass of the pouch.
• ⁇ 8> In a graph in which the horizontal axis is the storage time and the vertical axis is the pouch weight, storage is continued until the pouch weight decreases at a constant rate.
• the weight loss rate of the water-soluble film model detergent package is 1.0 to 6.0 g/(m 2 ⁇ day). If the weight loss rate exceeds 6.0 g/(m 2 ⁇ day), problems such as changes in drug composition over time and reduction in the amount of drug to be packaged tend to occur.
• the upper limit of the weight loss rate is preferably 5.0 g/(m 2 ⁇ day) or less, more preferably 4.0 g/(m 2 ⁇ day) or less, and 3.5 g/(m 2 ⁇ day). ) or less, and particularly preferably 3.0 g/(m 2 ⁇ day) or less.
• the weight loss rate is less than 1.0 g/(m 2 ⁇ day), the water solubility of the film may be insufficient.
• the lower limit of the weight loss rate is preferably 1.2 g/(m 2 ⁇ day) or more, more preferably 1.4 g/(m 2 ⁇ day) or more, and 1.6 g/(m 2 ⁇ day). ) or more, and particularly preferably 1.8 g/(m 2 ⁇ day) or more.
• the weight loss rate of the water-soluble film model detergent package is strongly influenced by the affinity between the model detergent to be packaged and the water-soluble film, and the crystal structure of PVA such as PVA crystals and PVA amorphous in the water-soluble film. estimated to be 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, additives) and the film forming conditions (draft ratio, drying conditions, draw ratio, etc.), The weight loss rate of the water soluble film model detergent package can be controlled.
• ⁇ Elastic modulus of water-soluble film when stretched 100%> a water-soluble film was immersed in a model detergent in an environment of 23°C and 50% RH for 24 hours, and then subjected to a tensile test at 23°C and 50% RH. (hereinafter sometimes referred to as elastic modulus at 100% stretching) is measured by the following methods ⁇ 1> to ⁇ 4>.
• ⁇ 1> Cut out a test piece measuring 1.5 cm in the width direction and 15 cm in the length direction from the 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 elastic modulus of the water-soluble film when stretched 100% is 9-35 MPa. If the elastic modulus at 100% stretching exceeds 35 MPa, the water solubility may be insufficient.
• the upper limit of the elastic modulus at 100% stretching is preferably 33 MPa or less, more preferably 30 MPa or less, and even more preferably 28 MPa or less.
• the elastic modulus at 100% elongation is less than 9 MPa, the package containing the medicine may have poor appearance such as wrinkles due to the decrease in the amount of the medicine.
• the lower limit of the elastic modulus at 100% stretching is preferably 11 MPa or more, more preferably 18 MPa or more, and even more preferably 23 MPa or more.
• the elastic modulus of the water-soluble film when stretched 100% 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, additives) and the film forming conditions (draft ratio, drying conditions, draw ratio, etc.), The elastic modulus of the water-soluble film at 100% stretching can be controlled.
• ⁇ Complete dissolution time 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 immersed in deionized water at 5°C for complete dissolution (hereinafter referred to as complete dissolution time). ) is measured by the following methods ⁇ 1> to ⁇ 6>. ⁇ 1> The water-soluble film is placed in a thermo-hygrostat adjusted to 20° C. and 65% RH for 16 hours or longer to condition the humidity.
• ⁇ 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, the water-solubility of the water-soluble film becomes insufficient, and it may be difficult to use the water-soluble film 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. On the other hand, there is no particular lower limit for the complete dissolution time. There is a tendency that the strength 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.
• 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 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 is equal to or more than the above lower limit, it is easy to prevent the water-soluble film from being perforated when used as a model detergent package, and to prevent the weight loss rate of the water-soluble film from becoming too high.
• 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
• vinyl ester monomers include olefins with a small number of carbon atoms such as ethylene and propylene, carboxylic acid monomers such as acrylic acid and methacrylic acid, and sulfonic acid monomers. Monomers are preferred.
• 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 100-3,000. If the degree of polymerization of PVA is less than 100, the strength of the water-soluble film may be insufficient.
• the lower limit of the degree of polymerization of PVA is preferably 200 or more, more preferably 300 or more, and even more preferably 500 or more.
• the polymerization degree of PVA exceeds 3,000, 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 upper limit of the polymerization degree of PVA is preferably 2,500 or less, more preferably 2,000 or less, and even more preferably 1,500 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 higher the degree of saponification the less acetic acid groups that disturb the crystal structure of PVA in the water-soluble film.
• the upper limit of the saponification degree of unmodified PVA and ethylene-modified PVA is 99.5 mol% or less because it becomes easy to achieve both the weight loss rate of the model detergent package of the water-soluble film and the water solubility of the water-soluble film.
• the lower limit of the degree of saponification of unmodified PVA and ethylene-modified PVA is preferably 80 mol% or more, more preferably 83 mol% or more, further preferably 85 mol% or more, and 87 mol%. It is particularly preferable that it is above.
• the degree of saponification of the unmodified PVA and the ethylene-modified PVA is at least the above lower limit, it becomes easier to control the weight loss rate of the water-soluble film model detergent package and the elastic modulus of the water-soluble film when stretched 100%.
• 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 even more 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.
• the degree of saponification of the carboxylic acid-modified PVA and the sulfonic acid-modified PVA is at least the above lower limit, it is easy to control the weight loss rate of the model detergent package of the water-soluble film and the elastic modulus of the water-soluble film when stretched 100%. Become.
• 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-based plasticizer is less than 1 part by mass, the water solubility of the water-soluble film tends to decrease and the complete dissolution time tends to be too long.
• the content of the polyhydric alcohol plasticizer is preferably 3 parts by mass or more, more preferably 5 parts by mass or more.
• the content of the polyhydric alcohol-based plasticizer exceeds 50 parts by mass, the weight loss rate of the model detergent package of the water-soluble film becomes too large, or the elastic modulus of the water-soluble film when stretched 100% becomes too high. It may become too low.
• the content of the polyhydric alcohol plasticizer is preferably 40 parts by mass or less, more preferably 30 parts by mass or less.
• 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, from the viewpoint of preventing bleeding out to the water-soluble film surface.
• 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 content of the polyhydric alcohol-based plasticizer in the water-soluble film is substantially equal to the content of the polyhydric alcohol-based plasticizer in the film forming stock solution of the water-soluble film. Adjusting the content of the polyhydric alcohol-based plasticizer in the film is substantially equivalent to adjusting the amount of the polyhydric alcohol-based plasticizer added to the film forming stock solution for the water-soluble film.
• the motility of the PVA molecules when drying the PVA film obtained by casting the undiluted film-forming solution described later on the support. is likely to increase, PVA crystals are likely to be generated in the water-soluble film.
• the weight loss rate of the water-soluble film model detergent package is estimated to depend on the amount of PVA crystals contained in the water-soluble film.
• the amount of the polyhydric alcohol-based plasticizer added to the undiluted solution for forming the water-soluble film is too small, the mobility of the PVA molecules decreases when drying the PVA film obtained by casting the undiluted film-forming solution on the support. By doing so, PVA crystals are less likely to form in the water-soluble film.
• the amount of the polyhydric alcohol plasticizer in the raw solution for forming the water-soluble film is too large, the interaction between the PVA and the polyhydric alcohol plasticizer is strengthened, and the raw solution for forming the film is cast onto the support. When the PVA film is dried, the interaction between PVA molecules is reduced, and PVA crystals are less likely to form in the water-soluble film.
• 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, and alkanolamide surfactants are particularly preferred, since they can further reduce film surface abnormalities that occur during the production of water-soluble films.
• Dialkanolamides eg, diethanolamide, etc.
• of eg, saturated or unsaturated aliphatic carboxylic acids having 8 to 30 carbon atoms, etc.
• 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 content of the surfactant 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. It is even more preferable to have When 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.
• a filler By containing a filler, the mechanical strength and handleability of the water-soluble film can be improved, and since the model detergent cannot permeate the filler, the path length required for permeation in the film increases (hereinafter , sometimes referred to as a baffle plate effect.) can be expected to improve barrier properties.
• fillers examples include carbon black, metal powder, silica, alumina, calcium carbonate, titanium dioxide, talc, mica, and clay minerals such as bentonite, among which a greater baffle effect can be expected.
• Clay minerals such as talc, mica, and bentonite, which have a large aspect ratio, are preferred.
• 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 even more preferably 10 parts by mass or less relative to 100 parts by mass of PVA. .
• 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. 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 from becoming uneven and the water-solubility from deteriorating.
• the lower limit of the draft ratio is more preferably 5 or more, even 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 upper limit of the draw ratio obtained by dividing the winding speed of the film after drying by the linear speed of the support of the undiluted film-forming solution is preferably 1.8 or less. It is more preferably 75 or less, and even more preferably 1.70 or less.
• the draw ratio is equal to or less than the above upper limit, it becomes easier to prevent the water solubility of the water-soluble film from being lowered due to excessive generation of PVA crystals.
• 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 is easy to prevent the weight loss rate of the model detergent package of the water-soluble film from becoming too large, or the elastic modulus of the water-soluble film at 100% stretching from becoming too low. Become.
• the weight loss rate of the model detergent package of the water-soluble film, the elastic modulus at 100% stretching of the water-soluble film, and the complete dissolution time can be controlled.
• the reason why it is possible is presumed as follows. That is, the PVA membrane formed by casting the undiluted membrane-forming solution on the support is in a state where tension is constantly applied in the flow direction (MD direction) of the PVA membrane during the drying process. It can be said that the PVA membrane during drying is substantially stretched in the MD direction, coupled with the volume shrinkage associated with volatilization of the solvent contained in the membrane undiluted solution.
• the weight loss rate of the water-soluble film model detergent package is estimated to depend on the amount of PVA crystals contained in the water-soluble film. It is presumed that by adjusting the ratio, it is possible to control the weight loss rate of the water-soluble film model detergent package and the like.
• the upper limit of the surface temperature of the support onto which the membrane-forming stock solution is poured is preferably 110°C or lower, preferably 100°C or lower, and more preferably 95°C or lower.
• the weight loss rate of the model detergent package of the water-soluble film becomes too high, or the elastic modulus of the water-soluble film when stretched 100% becomes too low. becomes easier to prevent.
• the lower limit of the surface temperature of the support is preferably 50° C. or higher, more preferably 60° C. or higher, and even more preferably 65° C. or higher.
• the PVA film formed by casting the film-forming undiluted solution onto the support is slowly dried, resulting in excessive PVA crystal formation. , it becomes easier to prevent the water solubility of the water-soluble film from decreasing. In addition, when the PVA film is dried, it becomes easier to prevent occurrence of film surface abnormalities such as foaming.
• 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 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 temperature of the drying oven and the drying roll is equal to or lower than the above upper limit, the weight loss rate of the model detergent package of the water-soluble film becomes too large, or the elastic modulus of the water-soluble film when stretched 100% becomes too low. easier to prevent.
• 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. When the temperature of the drying oven and the drying roll is equal to or higher than the above lower limit, it becomes easier to prevent the water solubility of the water-soluble film from being impaired.
• 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.
• 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 temperature of the heat treatment is equal to or lower than the above upper limit, the weight loss rate of the water-soluble film model detergent package is prevented from increasing, and the elastic modulus at 100% stretching is prevented from decreasing. It becomes easier to prevent wrinkles from getting worse.
• the lower limit of the heat treatment temperature is more preferably 90° C. or higher, still more preferably 100° C. or higher, and particularly preferably 105° C. or higher.
• the heat treatment temperature is equal to or higher than the above lower limit, it becomes easier to prevent the water solubility of the water-soluble film from being impaired.
• 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.
• Weight loss rate of model detergent package The weight loss rate of the model detergent package when stored at 23°C and 50% RH was determined by the method described above.
• model detergent packages Thirty of the above model detergent packages are prepared, placed in a hot air dryer set at 50°C, and stored for two weeks. ⁇ 5> Two weeks later, the model detergent package was taken out and allowed to stand in a room at 23°C and 50% RH for 4 hours.
• 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 with the support. It was dried by spraying at a speed of 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 The amount of glycerin, which is a polyhydric alcohol plasticizer, was 35 parts by mass with respect to 100 parts by mass of PVA, the draft ratio between the T die and the support was 31, the surface temperature of the support was 80 ° C., and the The procedure was the same as in Example 1 except that the temperature of the hot air blown over the entire non-contact surface was changed to 90°C, the surface temperature of the heat treatment roll was changed to 180°C, and the draw ratio from the support to the winding was changed to 1.8. to obtain a water-soluble film. Using the obtained water-soluble film, the weight loss rate of the model detergent package, the elastic modulus at 100% stretching, and the complete dissolution time were measured. Furthermore, after storage at 50°C for 2 weeks, the appearance of the model detergent package was evaluated. Table 1 shows the results.
• Example 3 MMM 4 mol% modified carboxylic acid-modified PVA (degree of saponification 96 mol%, degree of polymerization 1200) was changed to unmodified PVA (degree of saponification 88 mol%, degree of polymerization 1000), and in Example 4, MMM 4 mol% Modified carboxylic acid-modified PVA (degree of saponification 96 mol%, degree of polymerization 1200) to MMM4 mol% modified carboxylic acid-modified PVA (degree of saponification 88 mol%, degree of polymerization 1200).
• Carboxylic acid-modified PVA degree of saponification 96 mol%, degree of polymerization 1200
• sulfonic acid-modified PVA degree of saponification 99 mol%, degree of polymerization 1200
• AMPS 2-acrylamido-2-methylpropylsulfonic acid
• Example 6 To 100 parts by mass of PVA, 2 parts by mass of bentonite (manufactured by Kunimine Industries Co., Ltd., "Kunipia-F") as a filler is added to a twin-screw extruder, and the volatile content of the membrane-forming stock solution is adjusted to 60% by mass.
• a water-soluble film was obtained in the same manner as in Example 3, except that Using the obtained water-soluble film, the weight loss rate of the model detergent package, the elastic modulus at 100% stretching, and the complete dissolution time were measured. Furthermore, after storage at 50°C for 2 weeks, the appearance of the model detergent package was evaluated. Table 1 shows the results.
• Example 7 MMM 4 mol% modified carboxylic acid-modified PVA (degree of saponification 96 mol%, degree of polymerization 1200) to unmodified PVA (degree of saponification 88 mol%, degree of polymerization 1000), the amount of glycerin as a polyhydric alcohol plasticizer
• a water-soluble film was obtained in the same manner as in Example 2, except that the content was changed to 25 parts by mass based on 100 parts by mass of unmodified PVA.
• the weight loss rate of the model detergent package, the elastic modulus at 100% stretching, and the complete dissolution time were measured.
• the appearance of the model detergent package was evaluated. Table 1 shows the results.
• Example 8> 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. Using the obtained water-soluble film, the weight loss rate of the model detergent package, the elastic modulus at 100% stretching, and the complete dissolution time were measured. Furthermore, after storage at 50°C for 2 weeks, the appearance of the model detergent package was evaluated. Table 1 shows the results.
• Comparative Examples 1 and 2 In Comparative Example 1, the draft ratio between the T die and the support was set to 1.2, the draw ratio from the support to the winding was set to 0.8, and in Comparative Example 2, the draft ratio between the T die and the support was set to 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 65 and 2.1. Using the obtained water-soluble film, the weight loss rate of the model detergent package, the elastic modulus at 100% stretching, and the complete dissolution time were measured. Furthermore, after storage at 50°C for 2 weeks, the appearance of the model detergent package was evaluated. Table 1 shows the results.
• Example 4 The procedure was the same as in Example 1 except that the draft ratio between the T die and the support was changed to 1.2, the surface temperature of the heat treatment roll was changed to 40 ° C., and the draw ratio from the support to the winding was changed to 0.8. to obtain a water-soluble film. Using the obtained water-soluble film, the weight loss rate of the model detergent package, the elastic modulus at 100% stretching, and the complete dissolution time were measured. Furthermore, after storage at 50°C for 2 weeks, the appearance of the model detergent package was evaluated. Table 1 shows the results.

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• 2022
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