CN105940050B - Polyvinyl alcohol film - Google Patents
Polyvinyl alcohol film Download PDFInfo
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- CN105940050B CN105940050B CN201580007431.3A CN201580007431A CN105940050B CN 105940050 B CN105940050 B CN 105940050B CN 201580007431 A CN201580007431 A CN 201580007431A CN 105940050 B CN105940050 B CN 105940050B
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- Prior art keywords
- film
- pva
- polyvinyl alcohol
- mass parts
- pva film
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Classifications
-
- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
- A01N25/00—Biocides, pest repellants or attractants, or plant growth regulators, characterised by their forms, or by their non-active ingredients or by their methods of application, e.g. seed treatment or sequential application; Substances for reducing the noxious effect of the active ingredients to organisms other than pests
- A01N25/34—Shaped forms, e.g. sheets, not provided for in any other sub-group of this main group
-
- 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
-
- 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
- B65D65/02—Wrappers or flexible covers
-
- 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
- C08K5/0008—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
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/36—Sulfur-, selenium-, or tellurium-containing compounds
- C08K5/41—Compounds containing sulfur bound to oxygen
- C08K5/42—Sulfonic acids; Derivatives thereof
-
- 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
- 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
Abstract
The diffusivity of quick dissolving and packaging medicament also excellent polyvinyl alcohol film and the package body obtained using it after [subject] offer is put into water.[solution] polyvinyl alcohol film, it includes polyvinyl alcohol, water surface spreading agent and plasticizer, the content of plasticizer is 10 ~ 40 mass parts relative to the polyvinyl alcohol of 100 mass parts;And package body, to be packed with the polyvinyl alcohol film.It is preferred that the content of water surface spreading agent is 0.1 ~ 15 mass parts relative to the polyvinyl alcohol of 100 mass parts, it is preferred that water surface spreading agent is dialkyl sulfosuccinate salt, furthermore it is preferred that at least one of alkyl in dialkyl sulfosuccinate salt is the alkyl that carbon atom number is 6 ~ 12.
Description
Technical field
The present invention relates to by pesticide, detergent when medicaments carry out modular packaging etc. for useful polyvinyl alcohol
Film and the package body obtained using it.
Background technology
There are following methods:To (unit be packed with per unit amount as various medicaments of representative etc. using pesticide, detergent
Formula is packed) in water-solubility membrane, when use, is directly thrown into the packaged configuration in water, by contents melting or is dispersed in water
To use.The advantages of modular packaging, is, can be used in the case where not being in direct contact with dangerous medicament;Due to packet
A certain amount is filled, therefore when in use without metering;Post processing or the post processing for not needing to packing container, bag etc. are simple
Deng.
For example, the big granula (JUMBO) in paddy field after putting into paddy field, coats its water-solubility membrane dissolving, it is enclosed in
Big granula in package body is diffused into paddy field entirety in a manner of water surface etc. to float on, and thus spreads pesticide activity component.At this point, such as
Fruit water-solubility membrane is insufficient without the quickly diffusivity of dissolving or pesticide activity component, then cannot dissipate pesticide activity component
Cloth is in the entirety of paddy field.
As the water-solubility membrane for modular packaging, it is known that polyvinyl alcohol film is (below sometimes by " polyvinyl alcohol " abbreviation
For " PVA "), specifically, for example known use the film (reference obtained with the modified PVA specifically containing sulfonic unit
Patent document 1), the film (with reference to patent document 2) of compound comprising PVA and containing water-soluble sulfonate etc..
Existing technical literature
Patent document
Patent document 1:Japanese Unexamined Patent Publication 7-118407 bulletins
Patent document 2:Japanese Unexamined Patent Publication 9-40834 bulletins.
Invention content
Problems to be solved by the invention
Further change however, known water-solubility membrane exists in terms of dissolubility and the diffusivity of packaging medicament
Good leeway.Therefore, the object of the present invention is to provide quick dissolving after putting into water and the diffusions of packaging medicament
The excellent PVA film of property and the package body obtained using it.
The solution to the problem
The present inventor has been repeated to achieve the above object and necessary further investigation, as a result, it has been found that, if comprising
In the PVA film of the plasticizer of specific quantity further input is then formed containing waters surface spreading agents such as dialkyl sulfosuccinate salt
The diffusivity of quick dissolving and packaging medicament also excellent PVA film after into water, based on the discovery further repeatedly into
Row research, so as to complete the present invention.
That is, the present invention relates to:
[1] PVA film, it includes PVA, water surface spreading agent and plasticizer, and the content of plasticizer is relative to 100 mass parts
PVA is 10 ~ 40 mass parts;
[2] according to the PVA film described in [1], wherein, the content of water surface spreading agent relative to the PVA of 100 mass parts for 0.1 ~
15 mass parts;
[3] PVA film according to [1] or [2], wherein, water surface spreading agent is dialkyl sulfosuccinate salt;
[4] PVA film according to [3], wherein, at least one of alkyl in dialkyl sulfosuccinate salt is carbon
Atomicity is 6 ~ 12 alkyl;
[5] PVA film according to [3] or [4], wherein, at least one in the alkyl in dialkyl sulfosuccinate salt
Person is the alkyl of straight-chain;
[6] PVA film according to any one of [1] ~ [5] is Drug packing film;
[7] PVA film according to [6], wherein, medicament is pesticide or detergent;
[8] package body is formed to pack medicament with the PVA film described in [6] or [7].
Invention effect
According to the present invention, provide the diffusivity of quick dissolving and packaging medicament after putting into water excellent PVA
Film and the package body obtained using it.
Specific embodiment
The PVA film of the present invention includes PVA, water surface spreading agent and plasticizer.Also, in the PVA film of the present invention, plasticizer
Content is 10 ~ 40 mass parts relative to the PVA of 100 mass parts.Also contain the water surface spreading agent when including plasticizer with above-mentioned content,
The excellent PVA film of the diffusivity of quick dissolving and packaging medicament after putting into water is consequently formed.
[PVA]
As above-mentioned PVA, PVA, the polyvinylesters as obtained from saponified polyvinyl base ester can be used to be
By vinyl acetate, vinyl formate, vinyl propionate, vinyl butyrate, pivalic acid vinyl acetate, tertiary ethylene carbonate, bay
One or more of vinyl esters such as vinyl acetate, stearic acid vinyl ester, vinyl benzoate, methylvinyl acetate into
Row polymerization obtains.It is excellent from viewpoints such as the ease of manufacturing, acquisition easiness, cost of PVA among above-mentioned vinyl esters
Select vinyl acetate.
Above-mentioned polyvinylesters can be that one or more kinds of vinyl esters is used only as obtained from monomer to gather
Vinyl esters, but as long as within the scope of the effect of the invention or one or more kinds of vinyl esters with
It can be with the copolymer of other monomers of its copolymerization.
As the other monomers that can be copolymerized with above-mentioned vinyl esters, it can be cited for example that ethylene, propylene, 1- butylene, different
The carbon atom numbers such as butylene are 2 ~ 30 alpha-olefin;(methyl) acrylic acid or its salt;(methyl) methyl acrylate, (methyl) acrylic acid
Ethyl ester, (methyl) n-propyl, (methyl) isopropyl acrylate, (methyl) n-butyl acrylate, (methyl) acrylic acid are different
Butyl ester, (methyl) tert-butyl acrylate, (methyl) 2-EHA, (methyl) dodecylacrylate, (methyl)
Octadecyl acrylate etc. (methyl) acrylate;(methyl) acrylamide;N- methyl (methyl) acrylamide, N- ethyls
(methyl) acrylamide, N, N- dimethyl (methyl) acrylamide, diacetone (methyl) acrylamide, (methyl) acrylamido
Propane sulfonic acid or its salt, (methyl) acrylamido diemethylamine or its salt, N- methylols (methyl) acrylamide or its derivative
Object etc. (methyl) acrylamide derivative;The N- second such as N- vinyl formamides, N- vinyl acetamides, n-vinyl pyrrolidone
Eneamide;Methyl vinyl ether, ethyl vinyl ether, n-propyl vinyl ether, isopropyl-ethylene base ether, n-butyl vinyl base
The vinyl ethers such as ether, isobutyl vinyl ether, tert-Butyl vinyl ether, dodecyl vinyl, stearyl vinyl ethers;
The cyano such as (methyl) acrylonitrile are for ethylene;The vinyl halides such as vinyl chloride, vinylidene chloride, vinyl fluoride, vinylidene fluoride;Acetic acid alkene
The allyl compounds such as propyl ester, allyl chloride;Maleic acid or its salt, ester or acid anhydrides;Itaconic acid or its salt, ester or acid anhydrides;Ethylene
The vinyl silyl groups compound such as base trimethoxy silane;Unsaturated sulfonic acid etc..Above-mentioned polyvinylesters, which can have, to be originated from
The structural unit of one or more of other monomers.
The structural unit from other monomers ratio shared in above-mentioned polyvinylesters is to be based on being formed poly- second
The molal quantity meter of the entire infrastructure unit of alkenyl esters is preferably 25 moles of % hereinafter, more preferable 15 moles of % are hereinafter, further preferably
For 5 moles of below %.
As long as above-mentioned PVA connects within the scope of the effect of the invention or by one or more kinds of
The monomer modified obtained PVA of branch copolymerization.As this can graft copolymerization monomer, it can be cited for example that unsaturated carboxylic acid or its spread out
Biology;Unsaturated sulfonic acid or derivatives thereof;Carbon atom number is 2 ~ 30 alpha-olefin etc..In PVA be originated from can graft copolymerization list
The ratio of the structural unit (structural unit in graft modification part) of body is with mole based on the entire infrastructure unit for being formed PVA
Number meter is preferably 5 moles of below %.
For above-mentioned PVA, a part of in hydroxyl can be crosslinked, and can not also be crosslinked.In addition, for above-mentioned
PVA, a part of in hydroxyl can react with aldehyde compounds such as acetaldehyde, butyraldehyde etc. and form ethylidene ether structure, can not also be with
The reaction of these compounds is without forming ethylidene ether structure.
The degree of polymerization of above-mentioned PVA is not particularly limited, but preferably more than 300, more preferably more than 500, further excellent
More than 800, particularly preferably more than 1000 are selected as, furthermore it is preferred that for 10000 hereinafter, more preferably 8000 hereinafter, further excellent
5000 are selected as hereinafter, particularly preferably less than 2000.By the way that the degree of polymerization is made to be more than 300, film strength improves, and operability is excellent
It is different.On the other hand, by making the degree of polymerization for 10000 hereinafter, the manufactures of the PVA industrially become easy.It should be explained that this
The degree of polymerization of PVA in specification refers to that the record according to JIS K6726-1994 measures obtained average degree of polymerization.
The saponification degree of above-mentioned PVA is not particularly limited, but the intensity from obtained PVA film, toughness and bag making
Viewpoint is set out, preferably 80 moles of more than %, more preferably 82 moles of more than %, further preferably 84 moles of more than %, in addition,
Preferably 99.9 moles of % hereinafter, more preferably 99 moles of % hereinafter, further preferably 98 moles of below %.By the soap for making PVA
Change degree is 80 moles of more than %, and sufficient toughness can be assigned to film, and morphological stability improves, in addition, by alkaline matter or acid
Property substance be packaged in film carry out keeping when, the water-soluble decline of film can be more efficiently prevented from.On the other hand, by making soap
Change degree is 99.9 moles of % hereinafter, the industry of PVA and the manufacture of stabilization become easy.It should be explained that the PVA in this specification
Saponification degree refer to:Relative to possessed by PVA by saponification and can be converted into the structural unit of vinyl alcohol units (it is typical and
Say as vinyl ester units) with the total mole numbers of vinyl alcohol units, the ratio shared by the molal quantity of the vinyl alcohol units (is rubbed
You are %).Saponification degree can be measured according to the record of JIS K6726-1994.
[water surface spreading agent]
The type of water surface spreading agent is not particularly limited, but from the viewpoints such as effect for significantly more playing the present invention,
Preferably dialkyl sulfosuccinate salt.The dialkyl sulfosuccinate salt is that the structure having is equivalent to sulfosuccinic acid
Two carboxyls in salt are converted to the compound of the structure of Arrcostab, can be by arbitrarily making as long as with the structure
The method of making obtains.Each alkyl in two alkylester moieties possessed by dialkyl sulfosuccinate salt is same or different to each other
But if in view of manufacture easily etc., then it is preferably identical to each other.It is in addition, above-mentioned in dialkyl sulfosuccinate salt
Alkyl can be with any one or both for straight-chain alkyl, can also any one or both be branched alkyl.As
The alkyl, it can be cited for example that methyl, ethyl, propyl, isopropyl, amyl, hexyl, heptyl, octyl group, 2- ethylhexyls, nonyl,
Decyl, undecyl, dodecyl etc..The viewpoints such as the PVA film further improved from the diffusivity for forming packaging medicament go out
It sends out, at least one of alkyl in dialkyl sulfosuccinate salt (preferably the two) is preferably the alkane of carbon atom number 6 ~ 12
The alkyl of base, more preferably carbon atom number 7 ~ 10.In addition, for the same reason, the alkane in dialkyl sulfosuccinate salt
At least one of base (preferably the two) is preferably the alkyl of straight-chain.
As the salt in above-mentioned dialkyl sulfosuccinate salt, inorganic salts, preferably sodium salt, sylvite, ammonium can be enumerated
Salt, more preferably sodium salt.
For the content of the water surface spreading agent in PVA film, from significantly more performance effect of the present invention and it can remain high
Mechanical properties so as to operability improve from the perspective of, the PVA relative to 100 mass parts is preferably more than 0.1 mass parts, more
It is more than preferably 1 mass parts, it is more than further preferably 3 mass parts, furthermore it is preferred that it is below mass part for 15, more preferably 14
Below mass part, further preferably 12 is below mass part.
[plasticizer]
As above-mentioned plasticizer, it can be cited for example that polyalcohol, as its concrete example, can enumerate ethylene glycol, glycerine, third
Glycol, diethylene glycol, two glycerine, triethylene glycol, tetraethylene glycol, trimethylolpropane, polyethylene glycol etc..PVA film can include
One or more of these plasticizer.Among these, it is preferably selected from glycerine, two glycerine and polyethylene glycol at least
It is a kind of.The number-average molecular weight of polyethylene glycol is not particularly limited, but from PVA compatibility, in addition from being led when preventing because exudation
From the perspective of the water-soluble decline of the film of cause, in the range of preferably 100 ~ 1000.
For the content of the plasticizer in PVA film, rear quick dissolving and packaging medicament in water are put into from being formed
The excellent PVA film of diffusivity from the perspective of, it is desirable that the range that the PVA relative to 100 mass parts is 10 ~ 40 mass %
Interior, which is preferably more than 12 mass parts, and it is more than more preferably 14 mass parts, furthermore it is preferred that it is below mass part for 38, it is more excellent
It is below mass part to be selected as 36.
[other ingredients]
When moisture-proof during adjusting mechanical strength, operation, dissolving when the absorption of water the speed of softness, in water
For the purpose of spreading required time etc., PVA film can also be made to include other high water solubilities other than starch and/or above-mentioned PVA
Molecule.
As starch, it can be cited for example that cornstarch, potato starch, sweet potato starch, wheaten starch, rice starch,
The native starches class such as tapioca, sago starch;Implement the producing starch that etherificate processing, esterification processing, oxidation processing etc. obtain
Class etc., particularly preferably producing starch class.
The content of starch in PVA film is preferably 15 below mass part, more preferably 10 relative to the PVA of 100 mass parts
It is below mass part.By making the content below mass part for 15, the impact resistance of PVA film improves, and step passability improves.
As other water soluble polymers other than PVA, it can be cited for example that dextrin, gelatin, animal glue, casein,
Shellac, Arabic gum, polyacrylamide, Sodium Polyacrylate, polyvinyl methyl ether, methyl vinyl ether and maleic anhydride are total to
Polymers, the copolymer of vinyl acetate and itaconic acid, polyvinylpyrrolidone, cellulose, cellulose acetate
(Acetylcellulose), acetyl tributyl cellulose, carboxymethyl cellulose, methylcellulose, ethyl cellulose, hydroxyethyl
Cellulose, sodium alginate etc..
The content of other water soluble polymers other than PVA in PVA film is preferably 15 relative to the PVA of 100 mass parts
Below mass part, more preferably 10 is below mass part.By make the content be it is 15 below mass part, the water solubility of PVA film and point
Property is dissipated to improve.
It can make PVA film further suitably containing processing stabilizers, weatherabilities such as filler, copper compounds as needed
Stabilizer, colorant, ultra-violet absorber, light stabilizer, antioxidant, antistatic agent, fire retardant, other thermoplastic resins,
Lubricant, fragrance, antifoaming agent, deodorant, incremental agent, remover, releasing agent, reinforcing agent, crosslinking agent, mould inhibitor, preservative, knot
The additives such as crystallization rate delayed-action activator, aftermentioned surfactant.
The proportion of the total of PVA, water surface spreading agent and plasticizer in PVA film is excellent in terms of the quality based on PVA film
It is selected as more than 80 mass %, more preferably more than 90 mass %, further preferably more than 95 mass %.
The thickness of PVA film is not particularly limited, but from the viewpoint of being taken into account intensity and water solubility, preferably 1 μm or more,
More preferably 5 μm or more, further preferably 10 μm or more, furthermore it is preferred that for 100 μm hereinafter, more preferably 75 μm hereinafter, into
One step is preferably less than 60 μm.
The shape of PVA film is not particularly limited, and can enumerate quadrangle (such as rectangle, square etc.), circle, triangle
The shapes such as shape can be suitably set by PVA film according to the present invention in the form of etc., but from can be continuously manufactured by, can be with
From the perspective of easily carrying out keeping with the state of circumvolution into web-like, transport, the preferably film of strip.The PVA film of strip
Length is not particularly limited, but from processing when productivity viewpoint grade, preferably more than 1m, more preferably 100m with
On, further preferably more than 1000m.As the upper limit of the length, it can be cited for example that 10000m.On the other hand, strip
The width of PVA film is it is not also specifically limited, but from the viewpoint grade of productivity during processing, preferably more than 50cm is more excellent
It is selected as more than 80cm, further preferably more than 100cm.As the upper limit of the width, it can be cited for example that 5m.The PVA film exists
It can be used during use using severing as desirable size etc..
The manufacturing method of PVA film of the present invention is not particularly limited, can be preferably using the thickness for making the PVA film after film
Become manufacturing method evenly with width, such as following film stostes can be used to be manufactured:The above-mentioned of PVA film will be formed
PVA, water surface spreading agent, plasticizer and as needed will also be in above-mentioned starch, other water soluble polymers and additive etc.
One or more are dissolved in the film stoste obtained in liquid medium;Include PVA, water surface spreading agent, plasticizer, Yi Jigen
According to needing also to melt comprising one or more of starch, other water soluble polymers, additive and liquid medium etc. and PVA
The film stoste of change.When the film stoste contains at least one of starch, other water soluble polymers and additive, preferably will
These ingredients equably mix.
As for being film-made the aforesaid liquid medium of the preparation of stoste, it can be cited for example that water, dimethyl sulfoxide, dimethyl methyl
Amide, dimethylacetylamide, N-Methyl pyrrolidone, ethylene glycol, glycerine, propylene glycol, diethylene glycol, triethylene glycol, tetrem two
Alcohol, trimethylolpropane, ethylenediamine, diethylenetriamines etc., can use these one or more of.Wherein,
From the viewpoint of the load applied to environment, recyclability, preferably water.
The volatilization score of stoste is film-made (due to volatile ingredients such as the liquid mediums that volatilizees, evaporate and be removed during film
Content ratio in stoste is film-made) it is different according to film-forming method, film forming condition etc., but in general it is preferred that for 50 ~ 95 matter
In the range of measuring %, in the range of more preferably 55 ~ 90 mass %, in the range of further preferably 60 ~ 85 mass %.By making
The volatilization score for being film-made stoste is more than 50 mass %, and being film-made the viscosity of stoste will not become excessively high, can successfully be filmed
Filtering, deaeration when prepared by stoste, become the few PVA film of easy to manufacture foreign matter, shortcoming.On the other hand, by making film stoste
Volatilization score be 95 mass % hereinafter, film stoste concentration will not become too low, become easily industrially to manufacture PVA film.
Film stoste preferably comprises surfactant.By the way that comprising surfactant, Film making properties improve the thickness so as to PVA film
The uneven generation of degree is inhibited, and PVA film become easily from for film metallic roll, band stripping.By living comprising surface
Property agent film stoste manufacture PVA film when, surfactant can be contained in the PVA film.The type of above-mentioned surfactant
Be not particularly limited, but by the viewpoint grade of the fissility from metallic roll, band, preferably anionic surfactant or
Nonionic surfactant.
As anionic surfactant, the carboxylic acid type suitably such as potassium laurate;Polyoxyethylene lauryl ether
The sulfuric acid ester types such as sulfate, octyl sulfate;Sulfonic acid types such as dodecyl benzene sulfonate etc..
As nonionic surfactant, the alkyl ether type suitably such as polyoxyethylene oleyl ether;Polyoxy second
The alkyl phenyls ether type such as alkene octyl phenyl ether;The alkyl esters such as polyoxyethylene laurate;Polyoxyethylene laural base amino ethers etc.
Alkyl amine type;The alkylamides type such as polyoxyethylene laural amide;The polypropylene glycols ether type such as polyoxyethylene poly-oxygen propylene aether;Lauroyl
The alkylol amide types such as diethanol amine, oleoyl diethanol amine;Allyl phenyls ether type such as polyoxyalkylene allyl phenyl ether etc..
These surfactants can be used alone or combine two or more use.
When being film-made stoste comprising surfactant, content is excellent relative to the PVA contained by the film stoste of 100 mass parts
It is selected as in the range of 0.01 ~ 5 mass parts, in the range of more preferably 0.02 ~ 4 mass parts, particularly preferably 0.05 ~ 3 mass parts
In the range of.By making the content for more than 0.01 mass parts, Film making properties and fissility further improve.On the other hand, pass through
Make the content below mass part for 5, surfactant can be inhibited to ooze out into the surface of PVA film and sticked together, operability drop
It is low.
As film-forming method when above-mentioned film stoste being used to manufacture PVA film, it can be cited for example that casting film method, extrusion
Film method, film by wet method, gel film method etc..These film-forming methods can be adopted only with a kind of or combination is two or more
With.Among these film-forming methods, casting film method, squeezing out film method, thickness and width is uniform and physical property is good due to that can obtain
PVA film, therefore preferably.To the PVA film that film obtains, it can be dried, be heat-treated as needed.
The example of specific manufacturing method as PVA film, such as can be industrially preferably by following methods:Make
Machine mold etc. is applied with T-shaped slit die, hopper plate, I- molds, lip, above-mentioned film stoste is equably sprayed or is cast in positioned at most
On the surrounding face of the rotation of upstream side and heated the first roller (or band), make volatile ingredient from spray or be cast in this first
Evaporation is then being configured at one of side downstream so as to be dried on the face of the side of film on the surrounding face of roller (or band)
Or it is further dried or makes it through among hot-air drying device on multiple rotation and the surrounding face of heated roller
It is further dried, is then batched by devices for taking-up.Drying based on heated roller and based on hot-air drying device
Drying appropriately combined can be implemented.
For PVA film, the purpose of for the sliding for improving its surface, coarse processing preferably is implemented to surface.As thick
It is coarse can to enumerate online (online) that roller or the rough surface taken are transferred on film in film for the method for rough processing
Facture, the method for implementing embossing processing after the film that film obtains temporarily is wound on roller etc..Implement what coarse processing obtained
The arithmetic average height (Ra) in face is preferably 0.5 μm or more, more preferably 1 μm or more.As the upper of arithmetic average height (Ra)
Limit, for example, from the viewpoint of pinhole resistance be 10 μm.If arithmetic average height (Ra) is difficult to be filled less than 0.5 μm
The sliding divided.In addition, for maximum height (Rz), preferably 1 μm or more, more preferably 3 μm or more.As maximum high
Spend (Rz) the upper limit, such as from the viewpoint of pinhole resistance be 20 μm.If maximum height (Rz) is difficult to less than 0.5 μm
Obtain sufficient sliding.It should be explained that in this specification, arithmetic average height (Ra) and maximum height (Rz) are JIS B
0601:2001 are defined.
The PVA film of the present invention is excellent due to putting into the diffusivity of rear quick dissolving and packaging medicament in water, because
This is preferably used as Drug packing film.As packaging medicament, pesticide, detergent (including bleaching agent) etc. can be enumerated, it is excellent
It is selected as pesticide.The specific type of pesticide is not particularly limited, but from the viewpoint of significantly more being played effect of the present invention, preferably
For big granula, the big granula of the float type on the water surface is floated on after particularly preferably spreading.The medicine packed with the PVA film of the present invention
The physical property of agent is not particularly limited, and can be acid, neutral or alkalinity.As the form of medicament, powdered, block can be enumerated
Shape, gel, liquid etc., but from the viewpoint of the diffusivity of medicament is excellent, it is preferably powdered or blocky.Packaged configuration
It is not particularly limited, but the shape of modular packaging that preferably medicament is packed and (preferably packed) with per unit amount
State.By the way that the PVA film of the present invention is packed medicament with film as Drug packing, the package body of the present invention is obtained.
Embodiment
Hereinafter, by embodiment, the present invention will be described in more detail, but the present invention not due to these embodiments by
Any restriction.It should be explained that the evaluation method used in following embodiment and comparative example is as shown below.
The model test of Drug packing
The PVA film manufactured in following embodiment or comparative example is subjected to damping in 24 hours under 20 DEG C, 65%RH.Then,
The polyethylene granule of 3 ~ 4mm φ of 2.5g is packed with conditioned PVA film.Specifically, to add in polyethylene granule
Part shape as 30mm × 30mm square mode, after three sides are sealed so as to make bag, thereto plus
Enter polyethylene granule, remaining one side is sealed, is thus packed.Then, 15 are added in into the basin of 18cm × 25cm
DEG C water until depth is 2cm, make to be packaged with the aforementioned bag floating of polyethylene granule on the water surface in the center of basin.It will be from making bag
The time that floating starts until PVA film dissolving starts to spread on the water surface so as to the polyethylene granule in bag on the water surface is made
For the broken bag time, the situation that the broken bag time is less than 80 seconds is determined as that dissolubility "○" (good), the situation more than 80 seconds are sentenced
It is set to dissolubility "×" (bad).In addition, the situation with camera from top shooting makes bag be floated on the water surface after 180 seconds, it will
Polyethylene granule relative to basin area (450cm2) diffuse to more than 80% situation be determined as diffusivity "○" (good), expand
It is dissipated to 60% and is determined as that diffusivity " △ " (slightly good), situation about diffusing to less than 60% are determined as less than 80% situation
Diffusivity "×" (bad).It should be explained that it is carried out in the judgement of diffusion by following manner:By (1 region of 25 deciles in basin
For 3.6cm × 5cm), simply by the presence of 1 polyethylene granule among such region got, then judge the region for diffusion.
[embodiment 1]
It makes comprising the PVA (homopolymer of vinyl acetate saponified) that the degree of polymerization is 1700, saponification degree is 88 moles of %
100 mass parts, 20 mass parts of glycerine, 0.1 mass parts of sodium laureth sulfate and the sulfo group as water surface spreading agent
The containing ratio of 5 mass parts of dioctyl succinate sodium and PVA are the aqueous solution of 10 mass %.By metallic roll of the aqueous solution at 80 DEG C
On be dried and remove after, the heat treatment of 1 minute, the PVA film that manufacture thickness is 40 μm are carried out at 100 DEG C.
Using obtained PVA film, implement the model test of Drug packing by the above method.Obtained result is shown in
Table 1.
[embodiment 2]
The usage amount of Sodium docusate is changed to 1 mass parts, in addition to this with side similarly to Example 1
The PVA film that formula manufacture thickness is 40 μm.
Using obtained PVA film, implement the model test of Drug packing by the above method.Obtained result is shown in
Table 1.
[embodiment 3]
The usage amount of Sodium docusate is changed to 10 mass parts, in addition to this with similarly to Example 1
Mode manufactures the PVA film that thickness is 40 μm.
Using obtained PVA film, implement the model test of Drug packing by the above method.Obtained result is shown in
Table 1.
[embodiment 4]
As water surface spreading agent, sulfosuccinic is substituted using 5 mass parts of sulfosuccinic acid two (2- ethylhexyls) ester sodium
In addition to this 5 mass parts of dioctyl phthalate sodium manufacture the PVA film that thickness is 40 μm in a manner of similarly to Example 1.
Using obtained PVA film, implement the model test of Drug packing by the above method.Obtained result is shown in
Table 1.
[embodiment 5]
The usage amount of glycerine is changed to 35 mass parts, thickness is in addition to this manufactured in a manner of similarly to Example 3 is
40 μm of PVA film.
Using obtained PVA film, implement the model test of Drug packing by the above method.Obtained result is shown in
Table 1.
[embodiment 6]
The use of the degree of polymerization is 1700, saponification degree is containing for 88 moles of %, 2- acrylamide-2-methylpro panesulfonic acid sodium units
There is PVA (copolymer of vinyl acetate and 2- acrylamide-2-methylpro panesulfonic acid sodium saponified) 100 of the rate for 2 moles of %
Mass parts are come to substitute the degree of polymerization be 1700, the PVA (homopolymer of vinyl acetate saponified) 100 that saponification degree is 88 moles of %
In addition to this mass parts manufacture the PVA film that thickness is 40 μm in a manner of similarly to Example 1.
Using obtained PVA film, implement the model test of Drug packing by the above method.Obtained result is shown in
Table 1.
[embodiment 7]
Substitute 20 mass parts of glycerine using 10 mass parts of glycerine and two glycerine, 10 mass parts, in addition to this with embodiment
6 same modes manufacture the PVA film that thickness is 40 μm.
Using obtained PVA film, implement the model test of Drug packing by the above method.Obtained result is shown in
Table 1.
[embodiment 8]
It is replaced using 10 mass parts of glycerine, two glycerine, 10 mass parts and number-average molecular weight for 400 5 mass parts of polyethylene glycol
For 20 mass parts of glycerine, the PVA film that thickness is 40 μm is in addition to this manufactured in a manner of similarly to Example 6.
Using obtained PVA film, implement the model test of Drug packing by the above method.Obtained result is shown in
Table 1.
[comparative example 1]
Without using Sodium docusate, it is 40 μm that thickness is in addition to this manufactured in a manner of similarly to Example 1
PVA film.
Using obtained PVA film, implement the model test of Drug packing by the above method.Obtained result is shown in
Table 1.
[comparative example 2]
Substitute 5 mass parts of Sodium docusate using 10 mass parts of Sodium Allyl Sulfonate, in addition to this with
1 same mode of embodiment manufactures the PVA film that thickness is 40 μm.
Using obtained PVA film, implement the model test of Drug packing by the above method.Obtained result is shown in
Table 1.
[comparative example 3]
The usage amount of glycerine is changed to 5 mass parts, it is 40 that thickness is in addition to this manufactured in a manner of similarly to Example 1
μm PVA film.
Using obtained PVA film, implement the model test of Drug packing by the above method.Obtained result is shown in
Table 1.
[comparative example 4]
Without using Sodium docusate, in addition to this by with comparative example 3 it is same in a manner of manufacture thickness as 40 μm
PVA film.
Using obtained PVA film, implement the model test of Drug packing by the above method.Obtained result is shown in
Table 1.
[table 1]
As can be known from the above results, meet present invention provide that embodiment 1 ~ 8 PVA film water solubility and diffusivity it is excellent
It is different.
Claims (6)
1. polyvinyl alcohol film, it includes polyvinyl alcohol, water surface spreading agent, plasticizer and surfactant, the content phases of plasticizer
For 100 mass parts polyvinyl alcohol for 10 ~ 40 mass parts, the content of water surface spreading agent relative to 100 mass parts polyethylene
Alcohol is below mass part more than 3 and 15, wherein, water surface spreading agent is dialkyl sulfosuccinate salt.
2. polyvinyl alcohol film according to claim 1, wherein, at least one in the alkyl in dialkyl sulfosuccinate salt
Person is the alkyl that carbon atom number is 6 ~ 12.
3. polyvinyl alcohol film according to claim 1, wherein, at least one in the alkyl in dialkyl sulfosuccinate salt
Person is the alkyl of straight-chain.
4. polyvinyl alcohol film according to claim 1 is Drug packing film.
5. polyvinyl alcohol film according to claim 4, wherein, medicament is pesticide or detergent.
6. package body is formed to pack medicament with the polyvinyl alcohol film described in claim 4 or 5.
Applications Claiming Priority (5)
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JP2014021165 | 2014-02-06 | ||
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JP2014-044531 | 2014-03-07 | ||
PCT/JP2015/052003 WO2015118978A1 (en) | 2014-02-06 | 2015-01-26 | Polyvinyl alcohol film |
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KR (1) | KR102229234B1 (en) |
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JP2017119434A (en) * | 2015-12-25 | 2017-07-06 | 日本合成化学工業株式会社 | Water-soluble film, medicine package, and manufacturing method of water-soluble film |
CN111712533B (en) * | 2017-12-22 | 2023-02-28 | 株式会社可乐丽 | Polyvinyl alcohol film, film roll, and method for producing film roll |
CN111954695B (en) * | 2018-04-10 | 2023-07-28 | 株式会社爱赛璐 | Water-soluble film |
JP7165724B2 (en) * | 2018-04-27 | 2022-11-04 | 株式会社クラレ | Polyvinyl alcohol film and method for producing polarizing film using the same |
JPWO2020031969A1 (en) * | 2018-08-07 | 2021-08-10 | 積水化学工業株式会社 | Water-soluble packaging film and packaging |
JP7119913B2 (en) * | 2018-10-31 | 2022-08-17 | 三菱ケミカル株式会社 | Film coating composition, solid formulation and method for producing solid formulation |
CN113227225B (en) * | 2018-12-28 | 2023-09-29 | 株式会社可乐丽 | Water-soluble film and package |
JP7217295B2 (en) * | 2018-12-28 | 2023-02-02 | 株式会社クラレ | Water-soluble film and packaging |
WO2020138444A1 (en) * | 2018-12-28 | 2020-07-02 | 株式会社クラレ | Water-soluble film and package |
WO2021145021A1 (en) * | 2020-01-14 | 2021-07-22 | 株式会社アイセロ | Water-soluble film, and medicine-enclosing packaging capsule material having same |
CN115777001A (en) * | 2020-06-29 | 2023-03-10 | 株式会社可乐丽 | Water-soluble film and package |
EP4174116A1 (en) * | 2020-06-29 | 2023-05-03 | Kuraray Co., Ltd. | Water-soluble film and packaging |
CN116368076A (en) * | 2021-10-01 | 2023-06-30 | 株式会社可乐丽 | Water-soluble film, method for producing same, and package |
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JPS5615202A (en) * | 1979-07-13 | 1981-02-14 | Kureha Chem Ind Co Ltd | Agricultural drug composition |
JP3118352B2 (en) | 1993-10-27 | 2000-12-18 | 株式会社クラレ | Water-soluble film for agricultural chemical packaging |
JPH0940834A (en) | 1995-07-28 | 1997-02-10 | Unitika Chem Kk | Polyvinyl alcohol film |
JPH10265302A (en) * | 1997-03-27 | 1998-10-06 | Nissan Chem Ind Ltd | Granular agrochemical for submerged application |
JP2002012504A (en) * | 2000-04-28 | 2002-01-15 | Sankyo Co Ltd | Biodegradable floating foam on water surface having high oil absorbability, method for producing the same and composition containing the same |
JP5122040B2 (en) * | 2000-07-13 | 2013-01-16 | 株式会社クラレ | Polyvinyl alcohol-based water-soluble film and method for producing the same |
JP2003026504A (en) * | 2001-05-10 | 2003-01-29 | Sds Biotech:Kk | Urea-containing agrochemical solid formulation and method for producing the same |
JP4565803B2 (en) * | 2002-11-07 | 2010-10-20 | 日本合成化学工業株式会社 | Polyvinyl alcohol film and method for producing the same |
KR20100002719A (en) * | 2008-06-30 | 2010-01-07 | 주식회사 엘지화학 | A manufacturing method of polyvinylalcohol film, a polyvinylalcohol film formed therefrom and a polarizer having the same |
CN102286183B (en) * | 2011-06-17 | 2013-09-11 | 包头市恒瑞新材料科技有限公司 | Plastic polyvinyl alcohol (PVA) resin and preparation method thereof |
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KR20160118226A (en) | 2016-10-11 |
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