WO2006134657A1 - 水溶性フィルム - Google Patents
水溶性フィルム Download PDFInfo
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- WO2006134657A1 WO2006134657A1 PCT/JP2005/011071 JP2005011071W WO2006134657A1 WO 2006134657 A1 WO2006134657 A1 WO 2006134657A1 JP 2005011071 W JP2005011071 W JP 2005011071W WO 2006134657 A1 WO2006134657 A1 WO 2006134657A1
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- Prior art keywords
- water
- film
- weight
- soluble film
- plasticizer
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Classifications
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/18—Manufacture of films or sheets
-
- 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
- B65D85/00—Containers, packaging elements or packages, specially adapted for particular articles or materials
-
- 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
- C08K5/0008—Organic ingredients according to more than one of the "one dot" groups of C08K5/01 - C08K5/59
- C08K5/0016—Plasticisers
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2329/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an alcohol, ether, aldehydo, ketonic, acetal, or ketal radical; Hydrolysed polymers of esters of unsaturated alcohols with saturated carboxylic acids; Derivatives of such polymer
- C08J2329/02—Homopolymers or copolymers of unsaturated alcohols
- C08J2329/04—Polyvinyl alcohol; Partially hydrolysed homopolymers or copolymers of esters of unsaturated alcohols with saturated carboxylic acids
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/30—Sulfur-, selenium- or tellurium-containing compounds
-
- 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
Definitions
- the present invention relates to a water-soluble film mainly composed of polybulal alcohol (hereinafter also referred to as "PVA"), and more specifically, it is less colored during film formation and is in contact with a drug.
- PVA polybulal alcohol
- the present invention relates to a water-soluble film that is less colored over time and excellent in water solubility.
- PVA-based films are used for packaging chemicals such as agricultural chemicals and detergents by virtue of their water solubility.
- a water-soluble unit packaging bag used for powerful applications contains 1 to 10 mol% of carboxyl groups, has a saponification degree of 80 mol% or more, and a 4 wt% aqueous solution viscosity at 20 ° C.
- Patent Document 1 Japanese Patent Laid-Open No. 4-170405
- Patent Document 2 Japanese Patent Laid-Open No. 10-060207
- Patent Document 3 Japanese Patent Laid-Open No. 2001-329130
- Patent Document 4 Japanese Patent Laid-Open No. 9-316270
- An object of the present invention is to provide a water-soluble film containing as a main component a PVA-based rosin which has little coloration during film formation and little coloration with time even when contacted with a drug. is there.
- a PVA-based film containing PVA-based resin (A) has a dissolution time in water at 20 ° C of 60 seconds in terms of a film thickness of 76 m.
- a water-soluble film having a film b-value of 0.5 or less and a film b-value of 1.0 or less after standing at 80 ° C for 72 hours meets the above purpose.
- the present invention has been completed.
- the present invention is as follows.
- PVA-based resin (A) containing at least two plasticizers (B) and sulfite (C), and PVA-based resin (A) plasticizer for 100 parts by weight
- B) A water-soluble film having a content of 5 to 50 parts by weight and a content ratio (CZB: weight ratio) of sulfite (C) to plasticizer (B) of more than 0.02 and not more than 0.35.
- PVA-based resin force Anionic group-modified amount 1 to:
- the average saponification degree of the PVA-based ⁇ (A) is 80.0 to 99.9 mole 0/0, the water-soluble film according V, and whether the deviation of [1] to [5].
- the plasticizer (B) is at least
- a drug package comprising the water-soluble film according to any one of [1] to [13], wherein 5 to 50 g of liquid drug or powder drug is hermetically packaged.
- the water-soluble film of the present invention is an excellent water-soluble film that is excellent in water-solubility, has no coloration during film formation, and has little coloration over time even when in contact with a drug.
- Various uses for example, packaging of chemicals such as agricultural chemicals and detergents (unit packaging), (hydraulic) transfer film, sanitary products such as napkin 'paper diapers, filth disposal products such as ostomy bags, medical supplies such as blood-sucking sheets, It can be used for temporary substrates such as a seedling sheet 'seed tape' embroidery base fabric, and is particularly useful for packaging of drugs (particularly liquid detergents).
- the water-soluble film of the present invention is a PVA-based film comprising a PVA-based resin (A), and has a dissolution time in water at 20 ° C of 60 seconds or less in terms of a film thickness of 76 / zm. Yes, film The b value of the film is 0.5 or less, and the b value of the film after standing at 80 ° C. for 72 hours is 1.0 or less.
- the film of the present invention has solubility in water at 20 ° C, and the dissolution time is 60 seconds or less, preferably 50 seconds or less, more preferably 40 seconds or less in terms of film thickness of 76 m. is there. If the strong dissolution time exceeds 60 seconds, the water solubility targeted by the present invention cannot be obtained. That is, if it does not dissolve after 60 seconds, for example, when washing is performed using a detergent packaged in a film, the detergent does not disperse well in the aquarium, or part of the film is applied to clothing. Inconveniences such as adhesion may occur, and inconveniences such as inability to dissolve in water if the film is stored for a long time.
- the "dissolution time in water at 20 ° C" as used herein refers to cutting a film sample to a size of 40 mm x 40 mm, holding it in a slide mount and fixing it in a 1 liter beaker. Liters), and while stirring with a magnetic stirrer (rotor length 3 cm, rotation speed 200 to 300 rpm), keeping the water temperature at 20 ° C, immersing the film fixed on the slide mount in the power water and continuing stirring.
- the time (seconds) required for the film to dissolve is
- “dissolution” is a force that means that the residue of the film becomes invisible when the film is immersed in water. In this case, insoluble fine particles having a diameter of 1 mm or less are also dispersed. Then, it is included in the meaning of dissolution.
- the dissolution time may be obtained as it is by a solubility test.
- the film thickness is other than 76 m, the following conversion formula is used.
- the film of the present invention has a b value of 0.5 or less, preferably ⁇ 0.1 to 0.5, and a b value of the film after standing at 80 ° C. for 72 hours is 1.0.
- it is preferably 0.5 to 1.0. If the b value of the strong film is outside the above range, the object of the present invention cannot be achieved. If it has b value of this invention, since transparency is high, for example, it will have the effect that the commercial value of a white detergent can be maintained highly.
- the b value in the present invention is a value obtained based on the color specification value Hunter Lab, and is measured according to JIS Z 8730.
- the water-soluble film as described above is not particularly limited, but is preferably the following film.
- the plasticizer (B) with respect to 100 parts by weight of PVA-based resin (A). It is a water-soluble film having a content of 5 to 50 parts by weight and a content ratio (CZB: weight ratio) of sulfite (C) to plasticizer (B) of more than 0.02 and not more than 0.35.
- the PVA-based resin (A) used in the present invention can be produced by a known method without particular limitation. That is, it can be obtained by saponifying a bull ester polymer obtained by polymerizing a vinyl ester compound.
- strong burester compounds include formate, acetate, trifluoroacetic acid, propionate, butyrate, strong purate, laurate, versatic acid, palmitic acid, stearic acid Force used when vinyl or the like is used alone or in combination Vinyl acetate is preferred for practical use.
- the PVA-based resin (A) used in the present invention is preferably a char-group-modified PVA-based resin in terms of solubility.
- a kind of terionic group among the above-mentioned forces such as carboxyl group, sulfonic acid group, and phosphoric acid group, carboxyl group and sulfonic acid group are preferable, and carboxyl group is particularly preferable. ! /
- a carboxyl group-modified PVA resin which is a particularly suitable PVA resin (A)
- PVA resin (A) can be produced by any method, for example, (i) a non-carboxyl group-containing resin.
- a method of saponification after copolymerization of a saturated monomer and a vinyl ester compound (ii) A vinyl ester compound was polymerized by coexisting a carboxyl group-containing alcohol, aldehyde or thiol as a chain transfer agent. Examples of methods that can be used later include the ability to explain these in more detail. The present invention is not limited to these.
- ethylenically unsaturated dicarboxylic acid maleic acid, fumaric acid, itaconic acid, etc.
- ethylenically unsaturated dicarboxylic acid monoester Tel maleic acid monoalkyl ester, fumaric acid monoalkyl ester, itaconic acid monoalkyl ester, etc.
- ethylenically unsaturated dicarboxylic acid diester maleic acid dialkyl ester, fumaric acid dialkyl ester, itaconic acid dialkyl ester, etc.
- diesters must be converted to carboxyl groups by hydrolysis during copolymerization], or ethylenically unsaturated carboxylic acid anhydrides (hydrous maleic acid, itaconic anhydride, etc.), or Examples include monomers such as ethylenically unsaturated monocarboxylic acids ((meth) acrylic acid,
- n is an integer of 0 to 5
- R, R and R are respectively
- a lower alkyl group (preferably an alkyl group having 1 to 6 carbon atoms such as methyl, ethyl, propyl, butyl, pentyl, hexyl, etc.) having a hydrogen atom or a substituent may be used. Show. ]
- Specific examples include mercaptoacetic acid, 2-mercaptopropionic acid, 3-mercaptopropionic acid, 2-mercaptostearic acid, and the like.
- sulfonic acid group-modified PVA and phosphoric acid group-modified PVA in the case of sulfonic acid group-modified PVA, ethylene sulfonic acid, allyl sulfonic acid, methallyl sulfonic acid, styrene sulfonic acid, 2-
- olefin-2-sulfonic acid such as acrylamido-2-methylpropanesulfonic acid or a salt thereof
- phosphoric acid group-modified PVA it can be copolymerized with ethylenephosphonic acid or the like.
- an unsaturated monomer having a carboxyl group an unsaturated monomer having a sulfonic acid group, phosphorus
- these monomers can be polymerized in the presence of a small amount of other common monomers within the range without impairing water solubility. Examples include the following.
- olefins such as ethylene, propylene, isobutylene, ⁇ -otaten, ⁇ -dodecene, ⁇ -otadecene, etc.
- unsaturated such as acrylic acid, methacrylic acid, crotonic acid, maleic acid, maleic anhydride, itaconic acid, etc.
- Poly (oxy) alkyl ethers such as poly (meth) aryl ether, polyoxyethylene (meth) acrylate, polyoxypropylene (meth) acrylate, and other polyoxyalkylene (meth) acrylates, polyoxyethylene (meth) acrylamide, and polyoxypropylene (meth) acrylamide Lucylene (meth) acrylamide, polyoxyethylene (1- (meth) acrylamide-1,1,1-dimethylpropyl) ester, polyoxyethylene vinyl ether, polyoxypropylene vinyl ether, polyoxyethylene arylamine, polyoxypropylene aryl Ammin, Examples include polyoxyethylene vinylamine, polyoxypropylene vinylamine, and diacrylacetamide.
- N-acrylamidomethyltrimethylammonium chloride N-acrylamidoethyltrimethylammonium chloride, N-acrylamidopropyltrimethylammonium chloride, 2-ataryloxetyltrimethylammonium chloride, 2-methacryloxy shetyl Trimethylammonium chloride, 2-Hydroxy-3-methacryloyloxip Methyl pills Cationic group-containing monomers such as -um chloride and jetyl diallyl ammonium chloride are also included.
- Polyvinyl alcohol-based resins containing an acetoacetyl group can also be used.
- these monomers do not inhibit the object of the present invention, for example, a range of 0.
- It can be copolymerized in an amount of 5 to 10 mol%, more preferably 1 to 7 mol%.
- PVA-based resin (A) not only one type of PVA-based resin (A) but also two or more types can be used in combination.
- the PVA-based resin (A) can be obtained by polymerizing (or copolymerizing) monomers such as the vinyl ester compounds.
- the polymerization reaction (or copolymerization reaction) is carried out using a known radical polymerization catalyst such as azobisisobutyl-tolyl, peracid acetyl, benzoyl peroxide, or peroxylauroyl.
- a known radical polymerization catalyst such as azobisisobutyl-tolyl, peracid acetyl, benzoyl peroxide, or peroxylauroyl.
- the reaction temperature is selected in the range of about 35 ° C to boiling point (preferably 40 ° C to 80 ° C, particularly preferably 50 to 80 ° C).
- the obtained polymer (or copolymer) is dissolved in alcohol and carried out in the presence of an alkaline catalyst.
- the alcohol include methanol, ethanol, butanol and the like.
- the concentration of the polymer (or copolymer) in the alcohol is selected in the range of 20-50% by weight.
- an alkali catalyst such as an alkali metal hydroxide or alcoholate such as sodium hydroxide, potassium hydroxide, sodium methylate, sodium methylate, potassium methylate or the like can be used.
- an acid catalyst may be used.
- the amount of the Kenyi catalyst used must be 1 to 100 millimolar equivalents relative to the butyl ester compound.
- the carboxyl group of the carboxyl group-containing PVA resin produced by such a method is usually an alkali metal salt type such as sodium salt.
- an alkali metal salt type such as sodium salt.
- the strong sodium salt is changed to a divalent metal salt such as calcium, magnesium or copper. It can also be avoided by substitution.
- the method is not limited to the above method.
- PVA partially or completely conjugated
- a method of post-reacting a carboxyl group-containing compound having a functional group reactive with the hydroxyl group can also be carried out.
- a sulfonic acid-modified PVA resin modified with a sulfonic acid group it can also be produced by a method of Michael addition of a monomer having a sulfonic acid group to PVA.
- the average saponification degree of the PVA-based resin (A) is preferably 80.0 to 99.9 mol%. To ⁇ or 90.0 to 98.5 Monore 0/0, especially from 92.0 to 97.0 Monore 0/0 force ⁇ preferably! /,. If the average saponification degree is less than 80.0 mol%, there may be a problem that the water solubility of the film decreases with time depending on the ⁇ ⁇ of the drug to be packaged. If it exceeds 50%, the water solubility may be greatly lowered due to the heat history during film formation, which is not preferable.
- the viscosity of the 4% by weight aqueous solution of the above PVA-based rosin at 20 ° C is preferably 10 to 35 mPa's, more preferably 15 to 30 mPa's, and particularly preferably 15 to 25 mPa's. . If the viscosity is less than lOmPa's, the mechanical strength of the film as a packaging material may be reduced. On the other hand, if it exceeds 35 mPa's, the aqueous solution viscosity during film formation may be high and productivity may be reduced. Absent.
- the average saponification degree is measured in accordance with JIS K 67263.5, and the 4 wt% aqueous solution viscosity is measured in accordance with JIS K 6726 3.11.
- the modified amount of the above-described ionic group-modified PVA-based resin suitable in the present invention is preferably 1 to: 2 mol%, more preferably 2 to 6 mol%, particularly 3 to 5 mol%. Is preferred. If the amount of modification S is less than 1 mol%, the water solubility may be significantly reduced due to the influence of chemicals such as liquid detergents. On the other hand, if it exceeds 10 mol%, the productivity of PVA bulk powder may decrease. There is a possibility that the biodegradability is lowered, which is preferable.
- plasticizers (B) it is necessary to use at least two kinds of plasticizers (B) in combination.
- one plasticizer is used, problems such as sulfite being deposited on the surface of the film immediately after film formation and film strength are reduced.
- the plasticizer (B) used in the present invention is not particularly limited.
- at least one of the present invention include phenol S, N-methylol pyrrolidone, sonorebitole, mannitol, xylitol, 2,3-butanediol, 1,3-butanediol, reduced maltose starch syrup, reduced lactose, reduced starch syrup (reduced starch saccharified product), etc
- Preferred is one comprising a plasticizer (B2) having a molecular weight of 100 or more and 200 or less and having 3 or more hydroxyl groups in the molecule.
- a plasticizer (B2) having a molecular weight of 100 or more and 200 or less and having 3 or more hydroxyl groups in the molecule.
- the plasticizer (Bl) include glycerin.
- plasticizer (B2) examples include diglycerin and trimethylolpropane.
- Particularly suitable plasticizers (B) include those containing at least glycerol, diglycerol and Z or trimethylolpropane.
- the content ratio of B1 and B2 (B2ZB1; weight ratio) is 15/85 to 85/15. In particular, it is preferably 20 / 80-80 / 20, more preferably 25/75 to 75/25.
- the content ratio is less than 15Z85, the blocking resistance tends to decrease, while when it exceeds 85Z15, the temporal flexibility tends to decrease.
- the content (total amount) of the plasticizer (B) in the film is 5 to 50 parts by weight with respect to 100 parts by weight of the PVA resin (A). It is about 40 wt.%, More preferably 15 to 35 parts by weight. If the amount is less than 5 parts by weight, it is difficult to obtain a plastic effect. If the amount exceeds 50 parts by weight, the film strength decreases and the plasticizer bleeds on the film surface over time.
- the water-soluble film of the present invention typically further contains sulfite (C).
- sulfite (C) When the sulfite (C) is not contained, the film comes into contact with a chemical such as a liquid cleaning agent, causing disadvantages such as increased coloration of the film.
- Examples of the sulfite (C) used in the present invention include alkali metal salts of sulfite (for example, sodium sulfite and potassium sulfite), and preferably sodium sulfite.
- CZB weight ratio
- a resin composition [I] is obtained by adding at least two types of plasticizers (B) and sulfites (C) to the PVA-based resin (A). Although the film is formed, the resin composition [I] can further contain a surfactant (D), a filler (E), starch (F), and the like, if necessary.
- the surfactant (D) is not particularly limited, and examples thereof include polyoxyethylene nonyl phenyl ether, polyoxyethylene octyl nonyl ether, polyoxyethylene dodecyl phenyl ether, polyoxyethylene alkylaryl ether. , Polyoxyethylene sorbitan monolaurate, polyoxyethylene sorbitan monopalmitate, polyoxyethylene sorbitan monostearate, polyoxyethylene sorbitan monooleate, polyoxyalkylene alkyl ether phosphate monoethanolamine salt, polyoxy Examples thereof include polyoxyethylene alkylamino ethers such as ethylene lauryl amino ether and polyoxyethylene stearyl amino ether, which are used alone or in combination of two or more. Of these, polyoxyalkylene alkyl ether phosphate monoethanolamine salt and polyoxyethylene alkylamino ether are preferable in terms of peelability.
- the content of the strong surfactant (D) in the film is not particularly limited, but is 0.01 to 3.0 parts by weight with respect to 100 parts by weight of the PVA-based resin (A). Particularly preferred is 0.03 to 2.5 parts by weight, and more preferred is 0.05 to 2.0 parts by weight. If the content is less than 0.01 part by weight, the peelability between the metal surface of the film forming apparatus such as a drum or belt and the film formed is difficult to manufacture, and if it exceeds 3.0 parts by weight, It is not preferable because it causes bleeding and blocking, resulting in poor handling.
- Examples of the filler (E) include inorganic fillers and organic fillers.
- the inorganic filler preferably has an average particle size of 1 to 10 ⁇ m. If the average particle size is less than 1 ⁇ m, the blocking effect of the film is less than 10 ⁇ m. Exceeding this is preferable because the appearance of the film deteriorates and the commercial value is lowered. Specific examples include, for example, talc, clay, silicon dioxide, kieselguhr, kaolin, mica, asbestos, gypsum, graphite, glass balloon, glass beads, calcium sulfate, barium sulfate, ammonium sulfate, calcium sulfite.
- Calcium carbonate, whisker-like calcium carbonate, charcoal Magnesium acid, dosonite, dolomite, potassium titanate, carbon black, glass fiber, alumina fiber, boron fiber, processed mineral fiber, carbon fiber, carbon hollow sphere, bentonite, montmorillonite, copper powder, sodium sulfate, potassium sulfate, zinc sulfate , Copper sulfate, iron sulfate, magnesium sulfate, aluminum sulfate, potassium aluminum sulfate, ammonium nitrate, sodium nitrate, potassium nitrate, aluminum nitrate, ammonium chloride salt, sodium chloride, potassium chloride, magnesium chloride, chloride Examples include calcium, sodium phosphate, potassium chromate, and calcium citrate.
- the content of the strong inorganic filler in the film is not particularly limited, but it is preferably 0.1 to 50 parts by weight, particularly preferably 0.5 to 100 parts by weight of the PVA-based resin.
- ⁇ LO weight part.
- the content is less than 0.1 parts by weight, the blocking inhibitory effect is small.
- the content exceeds 50 parts by weight, the tensile elongation of the film is preferably lowered.
- the organic filler preferably has an average particle size of 0.5 to 10 ⁇ m, more preferably 0.5 to 7 111, and particularly preferably 0.5 to 0.5 ⁇ m. -5 m, more preferably ⁇ 0.5 to 3 ⁇ m. If the average particle diameter is less than 0.5 ⁇ m, the cost is increased, and if it exceeds 10 ⁇ m, the dispersibility is lowered, which is not preferable.
- strong organic fillers include, for example, starch, melamine-based resin, polymethyl (meth) acrylate resin, polystyrene-based resin, and biodegradable starch such as polylactic acid and rice starch. Fats and the like can also be mentioned, and polymethyl (meth) acrylate resin, polystyrene resin, and biodegradable resin are particularly preferably used.
- the content of the strong organic filler is not particularly limited, but is preferably 5 to 25 parts by weight, particularly 5 to 15 parts per 100 parts by weight of the PVA resin (A).
- the weight part is preferred. If the content is less than 5 parts by weight, the mechanical strength as a packaging material is insufficient, and if it exceeds 25 parts by weight, the flexibility of the film cannot be obtained.
- the starch (F) is contained for the purpose of preventing blocking and adjusting the mechanical strength.
- the average particle size is 10 m or more.
- esterified starch includes acetate ester starch, succinate ester starch, nitrate ester starch, phosphate ester starch, urine phosphate ester starch, xanthate ester starch.
- etherified starch such as acetoacetated starch, allylic starch, methyl etherified starch, strong ruxymethyl etherified starch, hydroxyethyl etherified starch, hydroxypropyl etherified starch, etc.
- cationized starch Is a reaction product of starch and 2-jetylaminoethyl chloride, starch and 2,3-epoxy
- crosslinked starch such as a reaction product of pyrtrimethylammonium chloride
- examples of the crosslinked starch include formaldehyde crosslinked starch, epichlorohydrin crosslinked starch, phosphate crosslinked starch, acrolein crosslinked starch, etc.
- Raw starch is preferred.
- the content of the strong starch (F) in the film is not particularly limited, but it is preferably 0.1 to 40 parts by weight with respect to 100 parts by weight of the PVA-based resin (A).
- the amount is preferably 1 to 30 parts by weight. If the content is less than 0.1 part by weight, the blocking inhibitory effect is low and the mechanical strength improving effect is also small. If it exceeds 40 parts by weight, the appearance and tensile elongation of the film are significantly lowered, which is not preferable.
- a resin composition comprising a plasticizer (B) and a sulfite (C) in PVA-based resin (A) [I]
- the resin composition [ I] may be made into a PVA film by forming a film (film) with surfactant (D), filler (E) and Z or starch (F) as necessary.
- a method such as a casting method can be employed without any particular limitation.
- a solid content concentration of 10 to 40% by weight is obtained by adding water to the above-described greaves yarn and composition [I] (powder).
- To 39 parts by weight, more preferably 12 to 38% by weight) of the aqueous dispersion or water-solubility of the resin composition [I], or water is added to the PV A-based resin (A) (powder).
- a plasticizer (B) is added to a PVA-based aqueous resin solution adjusted to a solid content concentration of 10 to 40% by weight (preferably 11 to 38 parts by weight, more preferably 13 to 35% by weight).
- a powerful aqueous dispersion or aqueous solution is passed through a slit such as a T-die, and an endless belt or drum roll having a surface temperature of 50 to 100 ° C, preferably 55 to 95 ° C (preferably in terms of productivity).
- the PVA film of the present invention can be obtained by casting on a metal surface, drying, and further heat-treating if necessary.
- the solid content concentration of the above-mentioned rosin composition [I] is less than 10% by weight or more than 40% by weight, the film forming property is deteriorated, which is not preferable. If the temperature of the metal surface is less than 50 ° C, the drying efficiency is lowered, and if it exceeds 100 ° C, foaming may occur!
- an aqueous dispersion or aqueous solution of the resin composition [I] is cast on a plastic substrate or a metal substrate such as a polyethylene terephthalate film or a polyethylene film, and is dried and then PVA is used. System films can also be obtained.
- the force explained for the casting method is not limited to this in the present invention.
- the dissolution time in water at 20 ° C needs to be 60 seconds or less. Saponification degree of PVA resin, 4% aqueous solution viscosity, degree of polymerization, modified PVA, modified species and amount, drying temperature and time during film formation, film thickness, etc. This is achieved by adjusting.
- the thickness of the PVA film obtained by force cannot be generally specified depending on the application, but it is 5 to: LOO / zm, especially 10 to 80 / ⁇ ⁇ . If the thickness is less than 5 m, the mechanical strength of the film is lowered. On the other hand, if it exceeds 100 m, the dissolution rate in cold water is significantly slowed, and the efficiency during film formation is also unfavorable.
- the surface of the PVA film may be plain, but an embossed pattern or a satin pattern may be provided on one side or both sides of the film.
- the water-soluble film of the present invention includes other water-soluble polymers (unmodified PVA-based resin, modified PVA-based resin other than an anionic group, poly (ethylene)) within the range not impairing the object of the present invention.
- water-soluble polymers unmodified PVA-based resin, modified PVA-based resin other than an anionic group, poly (ethylene)
- perfumes antifungal agents, colorants, extenders, antifoaming agents, ultraviolet absorbers, and the like.
- the water-soluble film of the present invention is useful for various packaging applications, but is particularly useful for unit packaging applications for drugs and the like.
- the powerful drug is not particularly limited, such as a detergent or agricultural chemical, but a drug used by dissolving or dispersing in water is good, and may be alkaline, neutral, or acidic.
- the shape of the drug may be any shape such as granules, tablets, powders, powders, and liquids.
- the water-soluble film of the present invention comprises a liquid detergent having a pH of 6 to 12, preferably 7 to: L 1 and a water content of less than 10% by weight, preferably 0.1 to 7% by weight.
- a liquid detergent having a pH of 6 to 12, preferably 7 to: L 1 and a water content of less than 10% by weight, preferably 0.1 to 7% by weight.
- liquid detergent examples include liquid detergents mainly composed of higher fatty acids, pentaethylene glycol and dipropylene glycol monomethyl ether.
- a drug package in which a liquid drug or a powder drug is hermetically wrapped with the water-soluble film of the present invention, and the drug usually has an amount of 5 to 50 g. Included.
- the water-soluble film of the present invention is extremely water-soluble, there is no adhesion of the water-soluble polymer to the laundry when it is put into a washing machine and washed, and the b value is low and the transparency is high. In addition, it has the effect that the commercial value of the white detergent can be maintained high.
- the coloration of the film was evaluated by measuring the b value in accordance with JIS Z 8730 using a spectrophotometer “UV3100” manufactured by Shimadzu Corporation.
- the film sample was cut into a size of 40 mm X 40 mm and fixed by being sandwiched between slide mounts.
- the film was immersed in the water, and the time (second) until the film was dissolved was measured.
- dissolution means that a strong film cannot be visually recognized.
- insoluble particles having a diameter of 1 mm or less are dispersed and included in the meaning of dissolution.
- the obtained PVA film is cut to a size of 12 cm ⁇ 10 cm, and then sealed in two directions using a heat sealer to produce a bag (6 cm ⁇ 10 cm size).
- a heat sealer to produce a bag (6 cm ⁇ 10 cm size).
- a PVA film was obtained in the same manner as in Example 1 except that the types and amounts of plasticizer and sodium sulfite were changed as shown in Table 1. The obtained film was evaluated in the same manner as in Example 1.
- a PVA film was obtained in the same manner as in Example 1 except that sodium sulfite was added. The obtained film was evaluated in the same manner as in Example 1.
- a PVA film was obtained in the same manner as in Example 1 except that the amount of sodium sulfite added was 0.7 parts and the total amount of sodium sulfite Z plasticizer was 0.02.
- the obtained film was evaluated in the same manner as in Example 1.
- the initial b value was 0.17.
- the b value after durability was as high as 1.11.
- a PVA film was obtained in the same manner as in Example 1 except that 20 parts of glycerin and 3.0 parts of sodium sulfite were used as plasticizers.
- the obtained film was evaluated in the same manner as in Example 1. did.
- the initial b value was 0.26, which was a low force.
- Sodium sulfite was deposited on the film surface.
- the contents of the plasticizer and sulfite indicate parts by weight with respect to 100 parts by weight of PVA resin.
- the "initial value” of the b value indicates the value immediately after film formation, and the “durability” indicates the above "actual drug packaging test”.
- G 1 y Glycerin
- TMP ⁇ Limethylolpropane
- D ⁇ — G 1 y Diglycerin
- the water-soluble film of the present invention is an excellent water-soluble film that is excellent in water-solubility, has no coloration during film formation, and has little coloration over time even when in contact with a drug.
- Various applications for example, packaging of chemicals such as agricultural chemicals and detergents (unit packaging), (hydraulic pressure) transfer film, sanitary products such as napkin 'paper diapers, filth disposal products such as ostomy bags, medical supplies such as blood-absorbing sheets, It can be used for temporary substrates such as a seedling sheet 'seed tape' embroidery base fabric, and is particularly useful for packaging of drugs (particularly liquid detergents).
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Manufacturing & Machinery (AREA)
- Materials Engineering (AREA)
- Mechanical Engineering (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Manufacture Of Macromolecular Shaped Articles (AREA)
Abstract
Description
Claims
Priority Applications (4)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US11/922,072 US7754318B2 (en) | 2005-06-16 | 2005-06-16 | Water-soluble film |
CN200580050163XA CN101203551B (zh) | 2005-06-16 | 2005-06-16 | 水溶性膜 |
PCT/JP2005/011071 WO2006134657A1 (ja) | 2005-06-16 | 2005-06-16 | 水溶性フィルム |
GB0723771A GB2442626A (en) | 2005-06-16 | 2005-06-16 | Water-soluble film |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
PCT/JP2005/011071 WO2006134657A1 (ja) | 2005-06-16 | 2005-06-16 | 水溶性フィルム |
Publications (1)
Publication Number | Publication Date |
---|---|
WO2006134657A1 true WO2006134657A1 (ja) | 2006-12-21 |
Family
ID=37532029
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/JP2005/011071 WO2006134657A1 (ja) | 2005-06-16 | 2005-06-16 | 水溶性フィルム |
Country Status (4)
Country | Link |
---|---|
US (1) | US7754318B2 (ja) |
CN (1) | CN101203551B (ja) |
GB (1) | GB2442626A (ja) |
WO (1) | WO2006134657A1 (ja) |
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CN101203551B (zh) | 2011-09-28 |
US7754318B2 (en) | 2010-07-13 |
GB2442626A (en) | 2008-04-09 |
GB0723771D0 (en) | 2008-01-16 |
US20090291282A1 (en) | 2009-11-26 |
CN101203551A (zh) | 2008-06-18 |
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