WO2017043512A1 - Film soluble dans l'eau et emballage de produits chimiques - Google Patents

Film soluble dans l'eau et emballage de produits chimiques Download PDF

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Publication number
WO2017043512A1
WO2017043512A1 PCT/JP2016/076261 JP2016076261W WO2017043512A1 WO 2017043512 A1 WO2017043512 A1 WO 2017043512A1 JP 2016076261 W JP2016076261 W JP 2016076261W WO 2017043512 A1 WO2017043512 A1 WO 2017043512A1
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Prior art keywords
water
film
soluble film
pva
weight
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PCT/JP2016/076261
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English (en)
Japanese (ja)
Inventor
貴裕 日裏
勝間　勝彦
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日本合成化学工業株式会社
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Priority to JP2016556039A priority Critical patent/JP6828435B2/ja
Publication of WO2017043512A1 publication Critical patent/WO2017043512A1/fr

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Classifications

    • 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
    • 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
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L29/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an alcohol, ether, aldehydo, ketonic, acetal or ketal radical; Compositions of hydrolysed polymers of esters of unsaturated alcohols with saturated carboxylic acids; Compositions of derivatives of such polymers
    • C08L29/02—Homopolymers or copolymers of unsaturated alcohols
    • C08L29/04—Polyvinyl alcohol; Partially hydrolysed homopolymers or copolymers of esters of unsaturated alcohols with saturated carboxylic acids

Definitions

  • the present invention relates to a water-soluble film (hereinafter sometimes referred to as a PVA-based film) comprising a polyvinyl alcohol-based resin (hereinafter, polyvinyl alcohol may be abbreviated as PVA) as a main component. More specifically, it is excellent in solubility in water, particularly in cold water, and in particular, excellent packaging in water even in the state of packaging a liquid detergent or other liquid into a package.
  • PVA polyvinyl alcohol
  • the present invention relates to a water-soluble film capable of forming a body and a medicine package using the same.
  • the PVA film is a film made of a PVA resin having water solubility while being a thermoplastic resin, and a hydrophobic film usually used for packaging films such as a polyethylene terephthalate film and a polyolefin film, Various physical properties and feeling of touch are greatly different.
  • water-soluble unit packaging bag used for such applications, for example, 5 to 30 parts by weight of a plasticizer, 1 to 10 parts by weight of starch, and 0.01 to 2 parts by weight of a surfactant are blended with 100 parts by weight of PVA.
  • Water-soluble film see, for example, Patent Document 1
  • the plasticizer (B) is 20 to 50 parts by weight
  • the filler (C) is 2 to 30 parts by weight
  • the surfactant (D) is 0.1 parts by weight per 100 parts by weight of the anionic group-modified PVA resin (A).
  • a water-soluble film made of a resin composition containing 01 to 2.5 parts by weight is known.
  • the water-soluble films disclosed in Patent Documents 1 and 2 are excellent in solubility in water at ordinary temperatures such as 20 ° C. and 25 ° C., and can be used as a medicine package in which a liquid detergent or the like is packaged.
  • the water-soluble film is not considered at all in terms of solubility in cold water such as 5 ° C., and the cold water solubility is also an important physical property considering the water temperature in winter, etc.
  • the water-soluble film disclosed in the literature is still not satisfactory, and further improvement is desired as a water-soluble film capable of forming a good package.
  • the inventors of the present invention have excellent cold water solubility of the water-soluble film by using a PVA-based resin having a large molecular weight dispersion in the water-soluble film mainly composed of the PVA-based resin.
  • a water-soluble film that is excellent in cold water solubility and can form a good packaging body can be obtained even in the state of packaging a liquid such as a liquid detergent to form a packaging body.
  • the gist of the present invention is a water-soluble film containing a PVA resin (A) and a plasticizer (B), and the dispersion ratio (Mw / Mn) of the PVA resin (A) is 3 or more. It relates to a certain water-soluble film.
  • the present invention also provides a medicine package in which a liquid detergent is packaged with the water-soluble film.
  • the water-soluble film of the present invention uses a PVA-based resin having a large molecular weight dispersion such as a dispersion ratio of 3 or more, thereby being excellent not only in water solubility at room temperature but also in cold water solubility. Even in the state of packaging a liquid such as a detergent, it is possible to obtain a water-soluble film that is excellent in cold water solubility and can form a good packaging, and can be used for various packaging applications. In particular, it is useful for unit packaging applications such as drugs.
  • the weight average molecular weight of the PVA resin (A) is 70,000 or less, high mechanical strength can be obtained in the water-soluble film.
  • the PVA resin (A) contains two or more of a PVA resin (A1) having a weight average molecular weight of 70,000 or more and a PVA resin (A2) having a weight average molecular weight of less than 70,000, the water-soluble film is good. High solubility can be obtained.
  • the content ratio (weight ratio) of the PVA resin (A1) and the PVA resin (A2) is 90/10 to 10/90, good solubility of the water-soluble film can be obtained.
  • the plasticizer (B) contains a polyhydric alcohol (b1) having a melting point of 80 ° C. or higher and a polyhydric alcohol (b2) having a melting point of 50 ° C. or lower, excellent toughness of the water-soluble film can be obtained. It becomes like this.
  • the content of the plasticizer (B) is 20 parts by weight or more with respect to 100 parts by weight of the PVA resin (A)
  • a water-soluble film can be obtained over time when a liquid such as a liquid detergent is packaged to form a package.
  • excellent tension can be obtained.
  • the water content of the water-soluble film is 3 to 15% by weight, good flexibility of the water-soluble film can be obtained and the occurrence of blocking can be suppressed.
  • water solubility at normal temperature refers to water solubility in the temperature range of 25 ⁇ 5 ° C.
  • cold water solubility refers to water solubility in the temperature range of 5 ⁇ 5 ° C.
  • the water-soluble film of the present invention contains a PVA resin (A) and a plasticizer (B).
  • PVA resin (A) used in the present invention will be described.
  • the dispersion ratio (Mw / Mn) of the PVA resin is 3 or more, preferably 3 to 8, more preferably 3.1 to 7, Particularly preferred is 3.2 to 6.5, and particularly preferred is 3.2 to 5.0. If the dispersion ratio (Mw / Mn) is too low, the molecular chain of the high polymerization degree becomes long, and the cold water solubility decreases. If the dispersion ratio is too high, the solubility becomes too fast and there is a possibility that a hole will be formed during water sealing.
  • the weight average molecular weight of the PVA resin (A) is preferably 70,000 or less from the viewpoint of flexibility of the water-soluble film, particularly 40,000 to 65,000, and more preferably 45 , 60,000 is preferable.
  • the weight average molecular weight is too high, flexibility is lowered and cold water solubility tends to be lowered. If the weight average molecular weight is too low, the mechanical properties tend to be low.
  • examples of the PVA-based resin (A) include unmodified PVA and modified PVA-based resins.
  • the PVA-based resin (A) can be produced as follows. That is, (1) when producing a PVA resin, the dispersion ratio (Mw / Mn) is adjusted to be 3 or more, or (2) a PVA resin having a large weight average molecular weight and a weight average molecular weight It can adjust and manufacture by using 2 or more types of small PVA-type resin together.
  • the average saponification degree of the PVA resin (A) used in the present invention is preferably 80 mol% or more, particularly 82 to 99.9 mol%, more preferably 85 to 98.5 mol%, particularly
  • the average saponification degree is preferably too small, and if the average saponification degree is too small, the solubility of the water-soluble film tends to decrease over time depending on the pH of the drug to be packaged. In addition, when the average saponification degree is too large, the solubility in water tends to be greatly reduced due to the heat history during film formation.
  • the average saponification degree is preferably 80 mol% or more, particularly 82 to 99 mol%, It is preferably 85 to 90 mol%.
  • the average saponification degree is preferably 80 mol% or more, particularly 85 to 99.9 mol%, more preferably 90 mol%. It is preferably ⁇ 98 mol%.
  • the weight average molecular weight of the PVA resin (A) is preferably 70,000 or less, particularly 10,000 to 70,000, more preferably 15,000 to 65,000, and particularly 20,000. It is preferably from ⁇ 60,000. If the weight average molecular weight is too small, the mechanical strength of the water-soluble film as a packaging material tends to decrease. On the other hand, if the weight average molecular weight is too large, the aqueous solution viscosity during film formation tends to be high and productivity tends to decrease.
  • the weight average molecular weight of the unmodified PVA is preferably 70,000 or less, particularly 10,000 to 70,000, more preferably 15 6,000 to 65,000, particularly 20,000 to 60,000.
  • the weight average molecular weight of the modified PVA resin is preferably not more than 70,000, particularly 10,000 to 70,000, Is preferably 15,000 to 65,000, more preferably 20,000 to 60,000.
  • the average saponification degree is measured according to JIS K 6726 3.5. Moreover, a weight average molecular weight and a number average molecular weight are measured by GPC on the following conditions.
  • Equipment Prominence made by Shimadzu Corporation Column: Tosoh TSKgel ⁇ -M13 ⁇ m 7.8 mmI. D. x30cm Guard column: Tosoh TSK guard column ⁇ 6.0 mmI. D.
  • each of the above PVA resins (A) can be used alone or in combination with an unmodified PVA and a modified PVA resin, and further, a saponification degree, a weight average polymerization degree, a modified species. Also, two or more kinds having different modification amounts can be used in combination.
  • two types of PVA resins are used in combination, two types of PVA resins (A1) having a weight average molecular weight of 70,000 or more and PVA resins (A2) having a weight average molecular weight of less than 70,000 must be contained. Is preferred.
  • the PVA-based resin (A1) preferably has a weight average molecular weight of 70,000 or more, more preferably 72,000 to 150,000, particularly preferably 73,000, from the viewpoint of the toughness of the water-soluble film. ⁇ 140,000.
  • the average degree of saponification is preferably from 80 to 99 mol%, particularly preferably from 85 to 98 mol%, more preferably from 87 to 97 mol%, from the viewpoint of solubility.
  • the PVA resin (A2) preferably has a weight average molecular weight of less than 70,000, more preferably 10,000 to 68,000, and particularly preferably 20,000 to 58,000 from the viewpoint of solubility. It is.
  • the average degree of saponification is preferably from 80 to 99 mol%, particularly preferably from 85 to 98 mol%, more preferably from 87 to 97 mol%, from the viewpoint of solubility.
  • the PVA resin (A1) and the PVA resin (A2) are both unmodified PVA from the viewpoint of excellent solubility over time in an acidic solution.
  • a PVA resin having a dispersion ratio (Mw / Mn) of 3 or more and preferably a weight average molecular weight of 70,000 or less is used as the PVA resin (A).
  • the PVA resin means an unmodified PVA or a modified PVA resin.
  • Unmodified PVA can be produced by saponifying a vinyl ester polymer obtained by polymerizing a vinyl ester compound.
  • vinyl ester compounds examples include vinyl formate, vinyl acetate, vinyl trifluoroacetate, vinyl propionate, vinyl butyrate, vinyl caprate, vinyl laurate, vinyl versatate, vinyl palmitate, and vinyl stearate. Although it is mentioned, it is preferable to use vinyl acetate.
  • the vinyl ester compounds may be used alone or in combination of two or more.
  • modified PVA resin examples include nonionic group-modified PVA resin, cationic group-modified PVA resin, and anionic group-modified PVA resin.
  • modified PVA resin used in the present invention it is preferable to use an anionic group-modified PVA resin in terms of solubility.
  • anionic group examples include a carboxyl group, a sulfonic acid group, and a phosphoric acid group. From the viewpoint of chemical resistance and stability over time, a carboxyl group and a sulfonic acid group, particularly a carboxyl group is preferable. .
  • the modified amount of the anionic group-modified PVA resin is preferably 1 to 10 mol%, more preferably 2 to 9 mol%, particularly preferably 2 to 8 mol%, particularly preferably. If the amount of modification is too small, the solubility in water tends to decrease. If the amount is too large, the productivity of the modified PVA-based resin decreases or the biodegradability decreases. There is a tendency, and there is a tendency that blocking is likely to occur, so that practicality is lowered.
  • the modified PVA resin is a method of copolymerizing the vinyl ester compound and an unsaturated monomer copolymerizable with the vinyl ester compound, and then saponifying, or post-modifying unmodified PVA. It can be manufactured by a method or the like.
  • the following unsaturated monomer copolymerizable with the vinyl ester compound may be copolymerized.
  • a modified PVA resin is obtained, a modified group is used as the following monomer. It is necessary to copolymerize the unsaturated monomer having.
  • unsaturated monomers include olefins such as ethylene, propylene, isobutylene, ⁇ -octene, ⁇ -dodecene, ⁇ -octadecene, 3-buten-1-ol, 4-penten-1-ol, 5- Derivatives such as hydroxy group-containing ⁇ -olefins such as hexen-1-ol and acylated products thereof, unsaturated acids such as acrylic acid, methacrylic acid, crotonic acid, maleic acid, maleic anhydride, itaconic acid, undecylenic acid, Examples thereof include salts, monoesters, dialkyl esters, amides such as diacetone acrylamide, acrylamide and methacrylamide, olefin sulfonic acids such as ethylene sulfonic acid, allyl sulfonic acid and methallyl sulfonic acid, and salts thereof. These may be used alone or in combination of two or more.
  • modified PVA resin examples include those having a primary hydroxyl group in the side chain.
  • the number of primary hydroxyl groups is usually 1 to 5, preferably 1 to 2, and particularly preferably 1. It is done.
  • examples thereof include a PVA resin having a 1,2-diol structural unit in the side chain and a PVA resin having a hydroxyalkyl group in the side chain.
  • Such a PVA resin having a 1,2-diol structural unit in the side chain includes, for example, (i) a method of saponifying a copolymer of vinyl acetate and 3,4-diacetoxy-1-butene, and (ii) acetic acid.
  • a copolymerization method in the preparation of the PVA resin (A) for example, a known polymerization method such as a solution polymerization method, an emulsion polymerization method, a suspension polymerization method and the like can be arbitrarily used. It is carried out by a solution polymerization method using a lower alcohol such as isopropyl alcohol as a solvent. In this solution polymerization, the monomer is charged in the case of a modified PVA resin. First, the whole amount of the vinyl ester compound and a part of the unsaturated monomer having a carboxyl group, for example, are charged, and polymerization is performed. Any method may be used, such as a method of starting and adding the remaining unsaturated monomers continuously or in portions during the polymerization period, or a method of batch-feeding the unsaturated monomers having a carboxyl group. it can.
  • a known polymerization catalyst such as an azo catalyst such as azobisisobutyronitrile or a peroxide catalyst such as acetyl peroxide, benzoyl peroxide or lauroyl peroxide is appropriately selected depending on the polymerization method. be able to.
  • the polymerization reaction temperature is selected from the range of 50 ° C. to about the boiling point of the polymerization catalyst.
  • the obtained copolymer is dissolved in alcohol and carried out in the presence of a saponification catalyst.
  • the alcohol include alcohols having 1 to 5 carbon atoms such as methanol, ethanol, butanol and the like.
  • the concentration of the copolymer in the alcohol is selected from the range of 20 to 50% by weight.
  • the saponification catalyst examples include alkali catalysts such as alkali metal hydroxides and alcoholates such as sodium hydroxide, potassium hydroxide, sodium methylate, sodium ethylate, potassium methylate, and the like. It is also possible to use a catalyst.
  • the saponification catalyst is preferably used in an amount of 1 to 100 mmol equivalents relative to the vinyl ester compound. These saponification catalysts can be used alone or in combination of two or more.
  • examples of a method for post-modifying the above-mentioned unmodified PVA include a method of converting the unmodified PVA into acetoacetate ester, acetalization, urethanization, etherification, grafting, phosphoric esterification, and oxyalkylene.
  • a plasticizer (B) is contained in the PVA resin (A) from the viewpoint of imparting flexibility to the water-soluble film in the case of a medicine package. Only one type of plasticizer (B) can be used, or at least two types can be used in combination. In particular, the toughness of the water-soluble film itself when using at least two types as a package is used. This is preferable.
  • plasticizer (B) is a polyhydric alcohol (b1) having a melting point of 80 ° C. or higher (hereinafter sometimes abbreviated as plasticizer (b1)), and the other type has a melting point. It is a polyhydric alcohol (b2) (hereinafter sometimes abbreviated as a plasticizer (b2)) that is 50 ° C. or lower.
  • polyhydric alcohol (b1) having a melting point of 80 ° C. or higher many of sugar alcohols, monosaccharides and polysaccharides can be applied. Among them, for example, salicyl alcohol (83 ° C.), catechol (105 ° C.) ), Resorcinol (110 ° C.), hydroquinone (172 ° C.), bisphenol A (158 ° C.), bisphenol F (162 ° C.), dipentyl glycol (127 ° C.) and the like, phloroglucinol (218 ° C.), etc.
  • Trihydric alcohols such as erythritol (121 ° C), threitol (88 ° C), pentaerythritol (260 ° C), xylitol (92 ° C), arabitol (103 ° C), fucitol (153 ° C), glucose (146 ), Pentahydric alcohols such as fructose (104 ° C.), mannitol (16 ° C), hexahydric alcohols such as sorbitol (95 ° C), inositol (225 ° C), octahydric alcohols such as lactitol (146 ° C), sucrose (186 ° C), trehalose (97 ° C), maltitol (145 ° C), etc.
  • erythritol 121 ° C
  • threitol 88 ° C
  • pentaerythritol 260 ° C
  • xylitol 92
  • the inside of () shows melting
  • those having a melting point of 85 ° C. or higher, particularly 90 ° C. or higher are preferable from the viewpoint of the tensile strength of the water-soluble film.
  • the upper limit of the melting point is preferably 300 ° C., particularly 200 ° C.
  • the number of hydroxyl groups in one molecule is preferably 4 or more from the viewpoint of compatibility with the PVA resin (A), and more preferably 5 to 10 Particularly preferred is 6-8, and specific examples include sorbitol, sucrose, trehalose and the like.
  • the plasticizer (b1) preferably has a molecular weight of 150 or more, more preferably 160 to 500, and particularly preferably 180 to 400, in terms of the tension of the water-soluble film. Specifically, sorbitol, sucrose, etc. are mentioned as a suitable thing, for example.
  • the polyhydric alcohol (b2) having a melting point of 50 ° C. or lower is an aliphatic alcohol, for example, preferably ethylene glycol ( ⁇ 13 ° C.), diethylene glycol ( ⁇ 11 ° C.), triethylene glycol ( ⁇ 7 ° C.).
  • Propylene glycol ( ⁇ 59 ° C.), tetraethylene glycol ( ⁇ 5.6 ° C.), 1,3-propanediol ( ⁇ 27 ° C.), 1,4-butanediol (20 ° C.), 1,6-hexanediol ( 40 ° C), tripropylene glycol, dihydric alcohols such as polyethylene glycol having a molecular weight of 2000 or less, and trihydric or higher alcohols such as glycerin (18 ° C), diglycerin, triethanolamine (21 ° C). These may be used alone or in combination of two or more. The values in parentheses indicate melting points.
  • the lower limit of the melting point is usually ⁇ 80 ° C., preferably ⁇ 10 ° C., particularly preferably 0 ° C.
  • the number of hydroxyl groups in one molecule is 4 or less, particularly 3 or less because flexibility at room temperature (25 ° C.) can be easily controlled.
  • glycerin and the like are preferable.
  • the plasticizer (b2) preferably has a molecular weight of 100 or less, more preferably 50 to 100, and particularly preferably 60 to 95, in terms of easy control of flexibility.
  • glycerol etc. are suitable, for example.
  • a plasticizer (b3) other than the plasticizers (b1) and (b2) may be used in combination.
  • the plasticizer (b3) include trimethylolpropane (58 ° C.), diethylene glycol. Alcohols such as monomethyl ether, cyclohexanol, carbitol, polypropylene glycol, ethers such as dibutyl ether, carboxylic acids such as stearic acid, oleic acid, linoleic acid, linolenic acid, sorbic acid, citric acid, adipic acid, cyclohexanone, etc.
  • Ketones such as monoethanolamine, triethanolamine, ethylenediamine and imidazole compounds, and amino acids such as alanine, glycine, aspartic acid, glutamic acid, histidine, lysine and cysteine. These may be used alone or in combination of two or more.
  • the content of the plasticizer (B) is preferably 20 parts by weight or more with respect to 100 parts by weight of the PVA resin (A), particularly 27 to 70 parts by weight, more preferably 30 to 60 parts by weight. Part by weight, in particular 35 to 50 parts by weight is preferred.
  • the content of the plasticizer (B) is too small, when a liquid such as a liquid detergent is packaged to form a package, the tension of the water-soluble film tends to be deteriorated over time. In addition, when there is too much, it exists in the tendency for mechanical strength to fall.
  • the content ratio (b1 / b2) of the plasticizer (b1) and the plasticizer (b2) is preferably 0.1 to 5, particularly 0.2 to 4.5, Further, it is preferably 0.5 to 4, particularly preferably 0.7 to 3. If the content is too small, the water-soluble film tends to be too soft and blocking tends to occur, and if it is too large, the water-soluble film tends to be too hard and tends to be brittle even in a low humidity environment.
  • the content of the plasticizer (b1) and the plasticizer (b2) is 5 to 40 parts by weight of the plasticizer (b1), more preferably 8 to 100 parts by weight of the PVA resin (A).
  • the amount is preferably 30 parts by weight, particularly 10 to 25 parts by weight, and the plasticizer (b2) is preferably 5 to 40 parts by weight, more preferably 10 to 35 parts by weight, and particularly preferably 15 to 30 parts by weight. If the amount of the plasticizer (b1) is too small, the water-soluble film tends to be too soft and blocking tends to occur. If the amount is too large, the water-soluble film tends to be too hard and tends to be brittle even in a low humidity environment. is there.
  • plasticizer (b2) when there is too little plasticizer (b2), there exists a tendency for a water-soluble film to become hard too much, and there exists a tendency for it to become brittle also in a low-humidity environment, and when too much, a water-soluble film becomes too soft and tends to produce blocking. There is.
  • the total amount of the plasticizer (b1) and the plasticizer (b2) is preferably 70% by weight or more, more preferably 80% by weight or more, and particularly 87% by weight or more with respect to the entire plasticizer (B). In particular, it is preferably 90% by weight or more, more preferably 95% by weight or more. Particularly preferred is the case where the entire plasticizer (B) consists solely of the plasticizer (b1) and the plasticizer (b2). If the total amount of the plasticizers (b1) and (b2) is too small, the mechanical strength tends to decrease.
  • a filler (C), a surfactant (D) and the like can be further contained as necessary.
  • the filler (C) used in the present invention is contained for the purpose of blocking resistance, and specific examples include inorganic fillers and organic fillers. Among them, organic fillers are preferable.
  • the average particle diameter is preferably 0.1 to 20 ⁇ m, more preferably 0.5 to 15 ⁇ m. In addition, the said average particle diameter can be measured with a laser diffraction type particle size distribution measuring apparatus etc., for example.
  • Such an inorganic filler preferably has an average particle size of 1 to 10 ⁇ m. If the average particle size is too small, the effect of dispersibility of the water-soluble film in water tends to be small. When the water-soluble film is formed and processed, it tends to become a pinhole when it is stretched, or the appearance may deteriorate.
  • the inorganic filler include, for example, talc, clay, silicon dioxide, diatomaceous earth, kaolin, mica, asbestos, gypsum, graphite, glass balloon, glass beads, calcium sulfate, barium sulfate, ammonium sulfate, calcium sulfite, and calcium carbonate.
  • the organic filler preferably has an average particle size of 0.5 to 20 ⁇ m, more preferably 0.5 to 10 ⁇ m, particularly preferably 0.5 to 7 ⁇ m, still more preferably 0.5 to 5 ⁇ m. is there. If the average particle size is too small, the cost tends to be high, and if it is too large, a pinhole tends to be formed when the water-soluble film is stretched.
  • organic filler examples include starch, melamine resin, polymethyl (meth) acrylate resin, polystyrene resin, and biodegradable resins such as polylactic acid.
  • biodegradable resins such as polymethyl (meth) acrylate resins, polystyrene resins and starch are preferably used. These may be used alone or in combination of two or more.
  • starch examples include raw starch (corn starch, potato starch, sweet potato starch, wheat starch, kissava starch, sago starch, tapioca starch, sorghum starch, rice starch, bean starch, kudzu starch, bracken starch, lotus starch, Castor starch, etc.), physically modified starch ( ⁇ -starch, fractionated amylose, wet heat-treated starch, etc.), enzyme-modified starch (hydrolyzed dextrin, enzyme-degraded dextrin, amylose, etc.), chemically modified starch (acid-treated starch, hypochlorous acid) Chloric acid oxidized starch, dialdehyde starch, etc.), chemically modified starch derivatives (esterified starch, etherified starch, cationized starch, crosslinked starch, etc.) and the like. These may be used alone or in combination of two or more. Of these, raw starch, especially corn starch and rice starch are
  • the content of the filler (C) is preferably 1 to 30 parts by weight, more preferably 2 to 25 parts by weight, particularly 2.5 to 20 parts by weight, based on 100 parts by weight of the PVA resin (A). Part.
  • the content is too small, the blocking resistance tends to decrease, and when the content is too large, a pinhole tends to be formed when the water-soluble film is stretched.
  • the surfactant (D) used in the present invention is contained for the purpose of improving the peelability from the cast surface during the production of a water-soluble film, and is a nonionic surfactant, a cationic surfactant, an anionic surfactant. Agents and the like.
  • polyoxyethylene nonyl phenyl ether polyoxyethylene octyl nonyl ether, polyoxyethylene dodecyl phenyl ether, polyoxyethylene alkyl allyl ether, polyoxyethylene sorbitan monolaurate, polyoxyethylene sorbitan monopalmitate, polyoxyethylene sorbitan Nonionic interfaces such as monostearate, polyoxyethylene sorbitan monooleate, polyoxyalkylene alkyl ether phosphate monoethanolamine salt, polyoxyethylene lauryl amino ether, polyoxyethylene alkylamino ether such as polyoxyethylene stearyl amino ether An activator is mentioned and it is used 1 type or in combination of 2 or more types. Of these, polyoxyalkylene alkyl ether phosphate monoethanolamine salt and polyoxyethylene lauryl amino ether are preferable in terms of production stability.
  • the content of the surfactant (D) is preferably 0.01 to 3 parts by weight, more preferably 0.1 to 2.5 parts by weight, based on 100 parts by weight of the PVA resin (A). In particular, the amount is preferably 0.5 to 2 parts by weight.
  • the content is too small, the peelability between the cast surface of the film forming apparatus and the formed water-soluble film tends to decrease, and the productivity tends to decrease.
  • the content is too large, the water-soluble film is used as a package. There is a tendency to cause inconveniences such as a decrease in adhesive strength during heat sealing.
  • water-soluble polymers for example, sodium polyacrylate, polyethylene oxide, polyvinylpyrrolidone, dextrin, chitosan, chitin, methylcellulose, hydroxyethylcellulose, etc.
  • Fragrances rust inhibitors, colorants, extenders, antifoaming agents, ultraviolet absorbers, fluorescent brighteners, liquid paraffins, bitterness components (for example, denatonium benzoate, etc.) and the like can also be contained.
  • these may be used alone or in combination of two or more.
  • an antioxidant from the viewpoint of suppressing yellowing.
  • antioxidants include sulfites such as sodium sulfite, potassium sulfite, calcium sulfite and ammonium sulfite, tartaric acid, ascorbic acid, sodium thiosulfate, catechol, Rongalite, etc.
  • the blending amount is preferably 0.1 to 10 parts by weight, more preferably 0.2 to 5 parts by weight, and particularly preferably 0.3 to 3 parts by weight with respect to 100 parts by weight of the PVA resin (A).
  • a PVA resin composition comprising a PVA resin (A) and a plasticizer (B), and further containing a filler (C) and a surfactant (D) as necessary.
  • the PVA-based resin composition is obtained or dissolved or dispersed with water to prepare a film-forming raw material, and formed into a water-soluble film (PVA-based film).
  • a method such as a casting method can be employed, and the casting method is preferable in terms of film thickness accuracy.
  • the casting method is performed, for example, as follows.
  • the dissolution method normal temperature dissolution, high temperature dissolution, pressure dissolution, etc. are usually employed. Among them, high temperature dissolution and pressure dissolution are preferred because there are few undissolved materials and excellent productivity.
  • the dissolution temperature is usually 80 to 100 ° C., preferably 90 to 100 ° C. when dissolving at high temperature, and usually 80 to 130 ° C., preferably 90 to 120 ° C. when dissolving under pressure.
  • the dissolution time is usually 1 to 20 hours, preferably 2 to 15 hours, and more preferably 3 to 10 hours. If the dissolution time is too short, undissolved products tend to remain, and if the dissolution time is too long, productivity tends to decrease.
  • examples of the stirring blade include paddle, full zone, max blend, twister, anchor, ribbon, and propeller.
  • defoaming treatment is performed on the obtained PVA resin aqueous solution.
  • examples of the defoaming method include stationary defoaming, vacuum defoaming, and biaxial extrusion defoaming. It is done. Of these, stationary defoaming and biaxial extrusion defoaming are preferable.
  • the temperature for stationary defoaming is usually 50 to 100 ° C., preferably 70 to 95 ° C., and the defoaming time is usually 2 to 30 hours, preferably 5 to 20 hours.
  • water is added to the PVA resin (A) (powder) to form a PVA resin aqueous solution, and further, a plasticizer (B) and other blends are added to disperse the PVA resin composition in water.
  • a liquid or aqueous solution is obtained.
  • water is added to the PVA resin composition containing the PVA resin (A) and further the plasticizer (B) and various blends to obtain an aqueous dispersion or aqueous solution of the PVA resin composition.
  • the solid concentration of the aqueous dispersion or aqueous solution of the PVA resin composition is preferably 10 to 50% by weight, particularly 15 to 40% by weight, and more preferably 20 to 35% by weight.
  • the concentration is too low, the productivity of the water-soluble film tends to decrease. If the concentration is too high, the viscosity becomes too high, and it takes time to defoam the dope. Tend to. Furthermore, if the temperature of the metal surface of the endless belt or drum roll is too low, drying tends to take time, and if it is too high, foaming tends to occur during film formation.
  • the aqueous dispersion or aqueous solution is passed through a slit such as a T-die, cast onto a cast surface such as a metal surface of an endless belt or drum roll, or a plastic substrate surface such as a polyethylene terephthalate film, dried, and dried as necessary.
  • the PVA film (water-soluble film) of the present invention can be obtained by further heat treatment. For example, it can be performed under the following film forming conditions.
  • the temperature of the discharge part in the aqueous dispersion or aqueous solution of the PVA-based resin composition is preferably 60 to 98 ° C, particularly 70 to 95 ° C. If the temperature is too low, the drying time tends to be long and the productivity tends to decrease. If the temperature is too high, foaming or the like tends to occur.
  • the film formation rate is preferably 3 to 80 m / min, particularly 5 to 60 m / min, and more preferably 8 to 50 m / min.
  • a hot roll a floating, a far-infrared process, etc. are mentioned other than that.
  • productivity it is preferable in terms of productivity to carry out with a hot roll.
  • the heat treatment temperature is preferably 50 to 150 ° C., particularly preferably 70 to 130 ° C.
  • the heat treatment time is preferably 1 to 60 seconds, particularly 3 to 50 seconds, Is preferably 5 to 40 seconds.
  • an aqueous dispersion or aqueous solution of the PVA resin composition is cast on a plastic substrate or a metal substrate such as a polyethylene terephthalate film or a polyethylene film, and dried to obtain a PVA film (water-soluble film). ) Can also be obtained.
  • the thickness of the PVA film is appropriately selected depending on the application and the like, but is preferably 10 to 120 ⁇ m, more preferably 15 to 110 ⁇ m, and particularly preferably 20 to 100 ⁇ m. If the thickness is too thin, the mechanical strength of the PVA-based film tends to decrease. If the thickness is too thick, the dissolution rate in water tends to be slow, and the film forming efficiency tends to decrease.
  • the width of the PVA film is appropriately selected depending on the application and the like, but is preferably 300 to 5000 mm, more preferably 500 to 4000 mm, and particularly preferably 800 to 3000 mm. If the width is too narrow, the production efficiency tends to decrease, and if it is too wide, it tends to be difficult to control slackness or film thickness.
  • the length of the PVA-based film is appropriately selected depending on the application and the like, but is preferably 500 to 20000 m, more preferably 800 to 15000 m, and particularly preferably 1000 to 10,000 m. If this length is too short, there is a tendency that it takes time to switch the PVA film, and if it is too long, there is a tendency that the appearance defect and weight due to winding tightening become too heavy.
  • the surface of the PVA-based film may be plain (smooth), but from the viewpoint of blocking resistance, slipperiness during processing, reduced adhesion between products, and appearance, one or both sides of the PVA-based film. It is also preferable to provide uneven processing such as an embossed pattern, a fine uneven pattern, and a special engraving pattern.
  • the processing temperature is usually 60 to 150 ° C, preferably 80 to 140 ° C.
  • the processing pressure is usually 2 to 8 MPa, preferably 3 to 7 MPa.
  • the processing time is usually 0.01 to 5 seconds, preferably 0.1 to 3 seconds, although it depends on the processing pressure and the film forming speed.
  • the water content of the obtained PVA-based film is preferably 3 to 15% by weight, particularly 5 to 14% by weight in terms of mechanical strength and heat sealability. Further, it is preferably 6 to 13% by weight. If the water content is too low, the PVA film tends to be too hard, and if it is too high, blocking tends to occur. Adjustment to such a moisture content can be achieved by appropriately setting drying conditions and humidity control conditions. In addition, the said moisture content is measured based on JISK67263.4, and let the value of the obtained volatile matter be a moisture content.
  • the film formation is preferably performed in an environment of 10 to 35 ° C., particularly 15 to 30 ° C., for example.
  • the humidity is usually 70% RH or less.
  • the obtained PVA-type film can be made into a film roll by winding up to a core pipe (S1).
  • the obtained film roll can be supplied as a product as it is, it is preferably wound around a core tube (S2) having a length corresponding to the PVA film width of a desired size and supplied as a film roll.
  • the core tube (S1) around which the PVA film is wound is cylindrical, and the material thereof can be appropriately selected from metals, plastics, etc., but is preferably metal in terms of fastness and strength.
  • the inner diameter of the core tube (S1) is preferably 3 to 30 cm, more preferably 10 to 20 cm.
  • the thickness of the core tube (S1) is preferably 1 to 30 mm, more preferably 2 to 25 mm.
  • the length of the core tube (S1) needs to be longer than the width of the PVA film, and preferably protrudes from 1 to 50 cm from the end of the film roll.
  • the core tube (S2) has a cylindrical shape, and the material thereof can be appropriately selected from paper, metal, plastic and the like, but is preferably paper in terms of weight reduction and handling.
  • the inner diameter of the core tube (S2) is preferably 3 to 30 cm, more preferably 10 to 20 cm.
  • the thickness of the core tube (S2) is preferably 1 to 30 mm, more preferably 3 to 25 mm.
  • the length of the core tube (S2) may be any length that is equal to or longer than the PVA film width of the product, and preferably is equal to or longer than 50 cm.
  • the PVA film When winding on the core tube (S2), the PVA film is slit to a desired width.
  • a slit is slit using a shear blade or a leather blade, but it is preferable to slit with a shear blade in terms of the smoothness of the slit cross section.
  • the obtained film roll is packaged with a packaging film of a water vapor barrier resin, but such a film is not particularly limited, but the moisture permeability is 10 g / m 2 ⁇ 24 hr (according to JIS Z 0208). Measurement)
  • a packaging film of a water vapor barrier resin but such a film is not particularly limited, but the moisture permeability is 10 g / m 2 ⁇ 24 hr (according to JIS Z 0208). Measurement)
  • the following can be used. Specific examples include, for example, single-layer films such as high-density polyethylene, low-density polyethylene, polypropylene, polyester, polyvinylidene chloride-coated polypropylene, and glass-deposited polyester, or laminated films thereof, or split cloth, paper, and non-woven fabric.
  • a laminated film etc. are mentioned. Examples of the laminated film include a laminated film of glass-deposited polyester and polyethylene, a laminated film of polyvinylidene chloride-co
  • Such a film is preferably subjected to an antistatic treatment from the viewpoint of preventing the introduction of foreign substances, and the antistatic agent may be kneaded into the film or coated on the surface.
  • an antistatic agent of about 0.01 to 5% by weight relative to the resin is used, and in the case of surface coating, an antistatic agent of about 0.01 to 1 g / m 2 is used.
  • the antistatic agent for example, alkyldiethanolamine, polyoxyethylene alkylamine, higher fatty acid alkanolamide, sorbitan fatty acid ester and the like are used.
  • a packaging film made of an aluminum material after the film roll is packaged with a packaging film of a water vapor barrier resin and as such a film, an aluminum foil, an aluminum foil and a moisture-resistant plastic film can be used.
  • Laminated film for example, laminated film of aluminum foil and polyethylene film
  • laminated film of aluminum vapor deposited film and moisture resistant plastic film eg laminated film of aluminum vapor deposited polyester film and polyethylene film
  • laminated film of alumina vapor deposited film and moisture resistant plastic film for example, a laminated film of an alumina-deposited polyester film and a polyethylene film.
  • laminated film of aluminum vapor-deposited film and polyolefin film are useful, especially laminated film composed of stretched polypropylene film / polyethylene film / aluminum foil / polyethylene film, stretched polypropylene film / low density polyethylene film / aluminum foil A laminated film or the like is useful.
  • core tube through holes are formed at both ends of the film roll directly from the film roll or after being wrapped with a packaging film in order to prevent scratches at the end and adhesion of foreign matters such as dust.
  • a protective pad can be attached.
  • As the shape of the protective pad a disc-shaped sheet or film is practical according to the film roll.
  • a cushioning function such as foam, woven fabric, and nonwoven fabric.
  • a desiccant can be enclosed separately, or it can be laminated or mixed in the protective pad.
  • the protective pad material is advantageously plastic, and specific examples thereof include polystyrene, polyethylene, polypropylene, polyester, polyvinyl chloride, and the like.
  • the protective pad containing the desiccant examples include, for example, calcium chloride, silica gel, molecular sieves, saccharides, particularly saccharides with high osmotic pressure, desiccants or water absorbents such as water absorbent resins, natural celluloses, synthetic celluloses, A moisture absorbent layer dispersed, impregnated, coated and dried in a moldable material such as glass cloth or non-woven fabric, and these desiccant or water absorbing agent can be used for the above moldable material, polyester film, polyethylene film, polypropylene film, Teflon ( And those sandwiched between thermoplastic resin films such as (registered trademark) film.
  • sheet-like desiccants examples include “Idie Sheet” manufactured by IDY, “Arrow Sheet” and “Zeo Sheet” manufactured by Shinagawa Kasei Co., Ltd., and “High Sheet Dry” manufactured by High Sheet Industrial Co., Ltd. .
  • the film roll wrapped by such means is supported by providing brackets (support plates) at both end projections of the core tube or by placing the both end projections on a gantry, and without being grounded, so-called air Storage and transportation are preferably performed in a floating state.
  • a bracket is used when the film width is relatively small, and a gantry is used when the film width is relatively large.
  • the bracket is made of a veneer plate or a plastic plate, and the size of the bracket is sufficient if the four sides of the bracket are larger than the diameter of the film roll.
  • a pair of brackets are arranged upright and fitted to the core tube protrusions at both ends of the film roll so as to face each other, and are provided on the film roll.
  • a hollow hole slightly larger than the diameter of the core tube may be provided in the central portion of the bracket, or a U-shape may be hollowed from the upper portion of the bracket to the central portion so that the core tube can be easily inserted.
  • the film roll supported by the bracket is stored and transported in a carton such as a cardboard box, but when using a rectangular bracket, the four corners should be cut off to facilitate the work during storage. preferable.
  • the side of the bracket (thickness portion) is the same as the tape width so that the tape does not move or loosen. It is also practical to provide a tape misalignment prevention groove.
  • the temperature should be 10-30 ° C. and humidity 40-75% RH. .
  • the water-soluble film of the present invention thus obtained is useful for various packaging applications and the like, and is particularly useful for unit packaging applications for drugs and the like.
  • the drug is not particularly limited and may be alkaline, neutral, or acidic, and the drug may have any shape such as granules, tablets, powders, powders, liquids, etc. Drugs that are used dissolved or dispersed are preferred and are particularly useful for packaging liquid detergents.
  • the liquid detergent preferably has a pH value of 6 to 12 when dissolved or dispersed in water, particularly preferably 7 to 11.
  • the water content of the liquid detergent is preferably 15% by weight or less, particularly preferably 0.1 to 10% by weight, and more preferably 0.1 to 7% by weight. It is not insolubilized and has excellent water solubility.
  • the pH value is measured according to JIS K 3362 8.3.
  • the water content is measured according to JIS K 3362 7.21.3.
  • the liquid detergent package which is an example of the pharmaceutical package of the present invention, is one in which a liquid detergent is included in a package made of a water-soluble film.
  • the size of the liquid detergent package is usually 10 to 50 mm in length, preferably 20 to 40 mm.
  • the thickness of the package of the water-soluble film is usually 10 to 120 ⁇ m, preferably 15 to 110 ⁇ m, more preferably 20 to 100 ⁇ m.
  • the amount of the liquid detergent to be included is usually 5 to 50 mL, preferably 10 to 40 mL.
  • the surface of the liquid detergent package is smooth. Furthermore, in terms of blocking resistance, slipperiness during processing, reduced adhesion between products (packaging bodies), and appearance, an embossed pattern, fine uneven pattern, special engraving on the outer surface of the packaging body (water-soluble film) It may have been subjected to uneven processing such as a handle. Further, the liquid detergent package of the present invention retains the shape containing the liquid detergent during storage. At the time of use (during washing), the package (water-soluble film) comes into contact with water, so that the liquid detergent contained in the package is dissolved and flows out of the package.
  • a known method can be employed. For example, (1) a method for heat sealing, (2) a method for water sealing, (3) a method for sealing with glue, and the like (2) a method for water sealing is versatile and advantageous.
  • Unmodified PVA (A1) weight average molecular weight 80,000, dispersion ratio 2.58, 4% aqueous solution viscosity at 20 ° C. 22 mPa ⁇ s, average saponification degree 88 mol%
  • Unmodified PVA (A2) weight average molecular weight 27,000, dispersion ratio 2.25, 4% aqueous solution viscosity at 20 ° C. 5 mPa ⁇ s, average saponification degree 88 mol%
  • Example 1 As PVA resin (A), 65 parts of unmodified PVA (A1) and 35 parts of unmodified PVA (A2) (weight average molecular weight 58,000 as PVA resin (A), dispersion ratio 3.3), As plasticizer (B), 10 parts of sorbitol (b1) and 30 parts of glycerin (b2), 8 parts of starch (average particle size 20 ⁇ m) as filler (C), and polyoxyalkylene as surfactant (D) 2 parts of alkyl ether phosphate monoethanolamine salt and water were mixed and dissolved to obtain a PVA aqueous solution (solid content concentration 25%) in which starch was dispersed. The obtained PVA aqueous solution was degassed at 80 ° C.
  • the PVA aqueous solution was cast on a polyethylene terephthalate film, passed through a 3 m drying chamber (105 ° C.) at a speed of 0.350 m / min and dried, and a PVA film (water-soluble film) having a thickness of 94 ⁇ m was obtained. Obtained.
  • the PVA film (water-soluble film) obtained above was evaluated for cold water solubility as follows. The complete dissolution time in 5 ° C. water was 89 seconds.
  • dissolution complete dissolution
  • Example 2 Comparative Example 1>
  • Example 1 it carried out similarly except having changed as shown in Table 1, and obtained the PVA-type film (water-soluble film). About the obtained PVA-type film (water-soluble film), evaluation similar to Example 1 was performed.
  • a package was prepared by the following procedure using a package manufacturing machine manufactured by Engel. That is, a PVA film (bottom film) is fixed on a mold (package to be molded: length 45 mm, width 42 mm, height 30 mm) at the bottom of the manufacturing machine, and the PVA system is also placed at the top of the apparatus. The film (top film) was fixed. The bottom film was heated for 10 seconds with a dryer generating hot air at 90 ° C., and the bottom film was vacuum-formed into a mold.
  • liquid detergent (5.4% glycerin, 22.6% propylene glycol, 10.4% moisture contained in P &G's"Arière Power Gel Ball” (content ratio of polyhydric alcohol in liquid detergent) : 28%)
  • P &G's"Arière Power Gel Ball content ratio of polyhydric alcohol in liquid detergent
  • the water-soluble film of the present invention is a water-soluble film excellent in solubility in water, particularly in cold water, and is a water-soluble film that can form a good package, and can be used for various packaging applications. In particular, it is useful for unit packaging applications such as drugs.

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  • Chemical & Material Sciences (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Manufacturing & Machinery (AREA)
  • Mechanical Engineering (AREA)
  • Materials Engineering (AREA)
  • Manufacture Of Macromolecular Shaped Articles (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Medical Preparation Storing Or Oral Administration Devices (AREA)
  • Biological Depolymerization Polymers (AREA)
  • Wrappers (AREA)

Abstract

L'invention concerne un film soluble dans l'eau qui comporte une résine de poly(alcool de vinyle) (A) et un plastifiant (B), le rapport de dispersion (Mw/Mn) de la résine de poly(alcool de vinyle) (A) étant d'au moins 3. Par conséquent, l'invention concerne un film soluble dans l'eau pouvant former un excellent emballage qui présente non seulement une excellente solubilité dans l'eau à des températures ordinaires, mais également une excellente solubilité dans l'eau froide, et, en particulier, une excellente solubilité dans l'eau froide, même lorsqu'il sert d'emballage pour un liquide tel qu'un détergent liquide. Il est également possible d'obtenir un excellent emballage de produits chimiques par emballage de divers produits chimiques au moyen du film soluble dans l'eau.
PCT/JP2016/076261 2015-09-11 2016-09-07 Film soluble dans l'eau et emballage de produits chimiques WO2017043512A1 (fr)

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR20200013694A (ko) * 2017-05-26 2020-02-07 인피니트 머티리얼 솔루션즈, 엘엘씨 수용성 중합체 조성물

Citations (5)

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JP2013518173A (ja) * 2010-01-29 2013-05-20 モノソル リミテッド ライアビリティ カンパニー Ｐｖｏｈポリマーのブレンド材を有する改良された水溶性フィルムおよびそれで作られたパケット
WO2014089386A1 (fr) * 2012-12-06 2014-06-12 The Procter & Gamble Company Sac soluble comprenant un colorant teintant
WO2014089270A1 (fr) * 2012-12-06 2014-06-12 The Procter & Gamble Company Utilisation d'une composition pour réduire le suintement et la migration à travers un film soluble dans l'eau
WO2015098978A1 (fr) * 2013-12-25 2015-07-02 株式会社クラレ Alcool polyvinylique modifié et film hydrosoluble le contenant
WO2015098979A1 (fr) * 2013-12-25 2015-07-02 株式会社クラレ Alcool polyvinylique modifié et film hydrosoluble contenant celui-ci

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2013518173A (ja) * 2010-01-29 2013-05-20 モノソル リミテッド ライアビリティ カンパニー Ｐｖｏｈポリマーのブレンド材を有する改良された水溶性フィルムおよびそれで作られたパケット
WO2014089386A1 (fr) * 2012-12-06 2014-06-12 The Procter & Gamble Company Sac soluble comprenant un colorant teintant
WO2014089270A1 (fr) * 2012-12-06 2014-06-12 The Procter & Gamble Company Utilisation d'une composition pour réduire le suintement et la migration à travers un film soluble dans l'eau
WO2015098978A1 (fr) * 2013-12-25 2015-07-02 株式会社クラレ Alcool polyvinylique modifié et film hydrosoluble le contenant
WO2015098979A1 (fr) * 2013-12-25 2015-07-02 株式会社クラレ Alcool polyvinylique modifié et film hydrosoluble contenant celui-ci

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR20200013694A (ko) * 2017-05-26 2020-02-07 인피니트 머티리얼 솔루션즈, 엘엘씨 수용성 중합체 조성물
JP2020521870A (ja) * 2017-05-26 2020-07-27 インフィニット・マテリアル・ソリューションズ，エルエルシー 水溶性ポリマー組成物
JP7358340B2 (ja) 2017-05-26 2023-10-10 インフィニット・マテリアル・ソリューションズ，エルエルシー 水溶性ポリマー組成物
KR102626745B1 (ko) 2017-05-26 2024-01-17 인피니트 머티리얼 솔루션즈, 엘엘씨 수용성 중합체 조성물

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