CN105500854A - Water-soluble packaging film and uses thereof - Google Patents

Water-soluble packaging film and uses thereof Download PDF

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Publication number
CN105500854A
CN105500854A CN201410490615.7A CN201410490615A CN105500854A CN 105500854 A CN105500854 A CN 105500854A CN 201410490615 A CN201410490615 A CN 201410490615A CN 105500854 A CN105500854 A CN 105500854A
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China
Prior art keywords
water
soluble
film
system resin
packing membrane
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Pending
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CN201410490615.7A
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Chinese (zh)
Inventor
谢文祥
林威
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3M Innovative Properties Co
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3M Innovative Properties Co
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Priority to CN201410490615.7A priority Critical patent/CN105500854A/en
Publication of CN105500854A publication Critical patent/CN105500854A/en
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    • YGENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02WCLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
    • Y02W90/00Enabling technologies or technologies with a potential or indirect contribution to greenhouse gas [GHG] emissions mitigation
    • Y02W90/10Bio-packaging, e.g. packing containers made from renewable resources or bio-plastics

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Abstract

The invention discloses a water-soluble packaging film, which contains a water-soluble substrate film, wherein at least a side surface of the film is provided with a hydrophobic film containing a fluorinated acrylic resin. The invention further discloses a preparation method of the water-soluble packaging film, and a water-soluble container prepared by using the water-soluble packaging film.

Description

Soluble packing membrane and uses thereof
Technical field
System of the present invention is about a kind of soluble packing membrane, and the water-soluble container made by described packaging film.
Background technology
Cleaning agent component system occurs in a variety of forms on the market, and modal form is powder and liquid form, and the cleaning agent occurred with lozenge form is also quite by favorable comment.In recent years, pack laundry detergents with water-soluble film and be made into unit quantity pouch as seen, drop in water with described pouch during use, the packaging film through described pouch after a period of time can first dissolve, and therefore makes the content in pouch dissolve in water or disperse and used.The advantage of this kind of unit quantity pouch is directly to contact laundry detergents when using, and the amount of the content comprised due to pouch is a fixed amount, therefore person easy to use need not calculate its use amount, avoid dropping into excessive laundry detergents and cause waste, or input amount deficiency makes cleaning effect not good; In addition, the packaging film of pouch need not be processed after a procedure, comparatively easy.In addition, the situation that the packaging of unit quantity pouch also can avoid child to eat cleaning agent by mistake occurs.Moreover applying unit amount pouch also can keep clean environment, because of use powder detergent or liquid cleaner, and washing machine or cleaning agent storing place can not be made dirty.Generally speaking, the cleaner packing of pouch has been use liquid cleaner and has used.But the cleaner packing of current used pouch is limited to the restriction of packaging material, and in cleaning agent, the content of moisture content can not be too high, is usually less than the percentage by weight of 10%, in order to avoid affect the preservation of pouch.Cleaning agent water content in pouch needs low, and namely this represent that cleaning agent need comprise other higher compositions, therefore will be higher with the price of the cleaner packing of pouch existence, this problem run into for the cleaner packing making pouch existence at present.
Summary of the invention
One embodiment of the invention system is about a kind of soluble packing membrane, and it comprises a kind of water insoluble substrate film, and at least one side surface of described film has the hydrophobic film comprising and fluoridize acryl system resin.
Another embodiment of the present invention system is about a kind of method preparing soluble packing membrane, and it comprises:
There is provided a kind of water insoluble substrate film, the material system of wherein said water insoluble substrate film comprises and is selected from by following the group formed: the ethers of polyvinyl alcohol, polyvinyl alcohol copolymer, polyacrylic acid and salt thereof, alkylcellulose, alkylcellulose and ester class, carboxymethyl cellulose, hydroxy alkyl cellulose ester, polymethylacrylic acid, polyacrylamide, acrylic acid/maleic anhydride copolymers, polyvinylpyrrolidone, starch, glycerine, gelatin and composition thereof;
Acryl system resin solution is fluoridized in preparation, and described solution comprises fluoridizes acryl system resin and at least one solvent;
At least one side surface of described water insoluble substrate film applies described in one deck and fluoridize acryl system resin solution; And
By the water insoluble substrate film drying through fluoridizing the coating of acryl system resin solution, directly by this on described water insoluble substrate film, forming a continuous print comprise the hydrophobic film fluoridizing acryl system resin.
Another embodiment of the present invention system is about a kind of water-soluble container, wherein said container system formed by a kind of soluble packing membrane, described soluble packing membrane comprises a kind of water insoluble substrate film, at least one side surface of described film has the hydrophobic film comprising and fluoridize acryl system resin, and described soluble packing membrane have comprise the hydrophobic film fluoridizing acryl system resin a side-line as the inner side of described water-soluble container.
Another embodiment of the present invention system is about the purposes of soluble packing membrane of the present invention, and described soluble packing membrane can be used for making container, especially for making water-soluble container.
Another embodiment of the present invention system is about the little bag-shaped cleaning agent of one, it is the water-soluble container comprising a cleaning agent and a soluble packing membrane and formed, described soluble packing membrane comprises a kind of water insoluble substrate film, at least one side surface of described film has the hydrophobic film comprising and fluoridize acryl system resin, and described soluble packing membrane has the side-line that comprises the hydrophobic film fluoridizing acryl system resin as the inner side of described water-soluble container contacts with described cleaning agent.
Based on the explanation in the purposes enumerated and present disclosure, have the knack of other purposes various that this operator can imagine soluble packing membrane of the present invention.
Other aspects and specific embodiment are also contained in the present invention.Foregoing summary and following embodiment are also not intended to limit the invention to any certain specific embodiments, and are that only plan describes specific embodiments more of the present invention.
Accompanying drawing explanation
Fig. 1 shows the schematic diagram of an embodiment of soluble packing membrane of the present invention.
Fig. 2 shows the schematic diagram of an embodiment of water-soluble container of the present invention.
Fig. 3 shows water droplet through fluoridizing the coating of acryl system resin solution and without the situation of fluoridizing on the polyvinyl alcohol film of acryl system resin solution coating.
Fig. 4 shows after soluble packing membrane of the present invention is dissolved in the water, the hydrophobic property produced after being applied to glass.
Detailed description of the invention
Please refer to Fig. 1, the schematic diagram of an embodiment of its display soluble packing membrane of the present invention, described soluble packing membrane 10 comprises a kind of water insoluble substrate film 1, at least one side surface of described film has the hydrophobic film 2 comprising and fluoridize acryl system resin.Although the side that described soluble packing membrane 10 illustrates described water insoluble substrate film 1 has the hydrophobic film 2 comprising and fluoridize acryl system resin on the surface, but the both side surface of in other embodiments, described water insoluble substrate film each self-forming can comprise the hydrophobic film fluoridizing acryl system resin.
In one embodiment of this invention, water insoluble substrate film system is made by the material that can be dissolved or dispersed in rapidly in aqueous environments, the material of water insoluble substrate film not special restriction, the material being applicable to water insoluble substrate film of the present invention includes but not limited to polyvinyl alcohol (PVA), polyvinyl alcohol copolymer, polyacrylic acid and salt thereof, alkylcellulose, the ethers of alkylcellulose and ester class, carboxymethyl cellulose, hydroxy alkyl cellulose ester (such as, hydroxyethylcellulose), polymethylacrylic acid, polyacrylamide, acrylic acid/maleic anhydride copolymers, polyvinylpyrrolidone, starch, glycerine, gelatin or its mixture etc.In a preferred embodiment, the material of water insoluble substrate film is polyvinyl alcohol.
In one embodiment of this invention, the method manufacturing water insoluble substrate film does not limit, and suitably can adopt the film-forming method known by general skill personage, such as, and the film-forming methods such as rubbing method, fusion method, damp process, casting method, blown film extrusion method.In a preferred embodiment, polyvinyl alcohol can be sent in extruder to prepare water insoluble substrate film.In a further preferred embodiment, plasticizer, single candy and/or polysaccharide, inorganic filler, spices, interfacial agent, pigment, UV stabilization agent, antioxidant etc. optionally can be added, so that the obtained substrate film with good aqueous solubility in manufacture thin, water soluble membrane process.If needed, by each condition such as mixing changing the degree of polymerization of thin-film material, saponification degree and additive, can control the character such as the mechanical strength of film, moisture resistance, those skilled in the art knows how according to the mechanical strength or the moisture resistance that adjust film needed for it.
In one embodiment of this invention, fluoridize acryl system resin system can not need easily can form film through extra heat cure process and be covered in any substrate surface.In a preferred embodiment, consider the film forming ability not needing high-temperature process, the molecular weight system of fluoridizing acryl system resin with lower than 10000 for good.In a further preferred embodiment, acryl system resin is fluoridized including but not limited to fluoridizing polymethyl methacrylate, perfluor alkyl ethide methacrylate, polymethylacrylic acid perfluoroalkyl methyl esters, aliphatic fluoride polymer or its mixture etc.
In one embodiment of this invention, soluble packing membrane have at least 80 degree to water contact angle, better cording have at least 100 to spend to water contact angle.
One embodiment of the invention system is about a kind of method preparing soluble packing membrane, and it comprises: provide a kind of water insoluble substrate film; Acryl system resin solution is fluoridized in preparation, and described solution comprises fluoridizes acryl system resin and at least one solvent; At least one side surface of described water insoluble substrate film fluoridizes acryl system resin solution described in coating; And by the water insoluble substrate film drying through fluoridizing the resin solution coating of acryl system, the direct continuous print that formed on water insoluble substrate film comprises the hydrophobic film fluoridizing acryl system resin by this.
As mentioned above, water insoluble substrate film system is made by the material that can be dissolved or dispersed in rapidly in aqueous environments, the material of water insoluble substrate film not special restriction, the material being applicable to water insoluble substrate film of the present invention includes but not limited to polyvinyl alcohol, polyvinyl alcohol copolymer, polyacrylic acid and salt thereof, alkylcellulose, the ethers of alkylcellulose and ester class, carboxymethyl cellulose, hydroxy alkyl cellulose ester (such as, hydroxyethylcellulose), polymethylacrylic acid, polyacrylamide, acrylic acid/maleic anhydride copolymers, polyvinylpyrrolidone, starch, glycerine, gelatin or its mixture etc.In addition, the method manufacturing water insoluble substrate film does not limit, and suitably can adopt the film-forming method known by those skilled in the art, such as, and the film-forming methods such as rubbing method, fusion method, damp process, casting method, blown film extrusion method.
In one embodiment of this invention, fluoridize the solvent that acryl system resin solution comprises and include but not limited to hydrogen fluorine ether (hydrofluoroether).In another embodiment of the invention, fluoridize the solvent that acryl system resin solution comprises and include but not limited to methyl nine fluorine butyl ether (nonafluorobutylmethylether) and ethyl no nafluoro butyl ether (nonafluorobutylethylether).In the present invention, the mode of fluoridizing acryl system resin solution and be coated to water insoluble substrate film is not limited, suitably can adopt the coating method known by those skilled in the art in the invention, the such as mode such as rubbing method (such as, method of spin coating, immersion rubbing method or roll extrusion rubbing method), spray-on process, electrophoresis or ink-jet method.
Please refer to Fig. 1, in one embodiment of this invention, the thickness of water insoluble substrate film 1 is about 20 to about 100 microns.In a preferred embodiment, the thickness of water insoluble substrate film 1 is about 40 to about 80 microns.
In one embodiment of this invention, the thickness comprising the hydrophobic film 2 fluoridizing acryl system resin on the surface, side of water insoluble substrate film 1 is about 0.1 to about 1 micron.In a preferred embodiment, the thickness comprising the hydrophobic film 2 fluoridizing acryl system resin on the surface, side of water insoluble substrate film 1 is about 0.12 to about 0.6 micron.
Please refer to Fig. 2, the schematic diagram of one embodiment of its display water-soluble container of the present invention, described water-soluble container 20 is formed by water insoluble substrate film 1, and described soluble packing membrane have comprise the hydrophobic film 2 fluoridizing acryl system resin a side-line as the inner side of described water-soluble container, described water-soluble container comprises cleaning agent component 3, and described hydrophobic film 2 is contact with described cleaning agent component 3.
In one embodiment of this invention, the shape of water-soluble container is not particularly limited, and described water-soluble container can be pouch, pouch or other injection molded shapes.
In one embodiment of this invention, water-soluble container of the present invention can be used as pouch, and pouch shape is not particularly limited.In another embodiment of the invention, water-soluble container is built with cleaning agent component, to make a kind of little bag-shaped cleaning agent, described cleaning agent component includes but not limited to floor cleaner, laundry detergents, bath lavatory cleaning agent, furniture detergent, glass cleaner or other family expenses or non-domestic cleaning agent etc.; Certainly, the application of water-soluble container of the present invention is not limited to above-mentioned aspect, and for example, the cleaning agent component be installed in the water-soluble container of little bag-shaped cleaning agent also can be human body cleaning agent, such as: shower cleaning agent, shampoo, breast etc. of washing one's hands.In another embodiment of the invention, pouch system is for packing laundry detergents.
In one embodiment of this invention, the form being filled to the cleaning agent component of water-soluble container can be the forms, particularly liquid form such as liquid state, powdery, paste, colloidal.In another embodiment of the invention, the laundry detergents of any liquid form or other household cleaners make pouch with soluble packing membrane of the present invention is advantageous particularly.
In one embodiment of this invention, be packaged in the cleaning agent in water-soluble container of the present invention, if with the total amount of cleaning agent for benchmark, its water content can be at most 50 % by weight, goodly can be 40 % by weight, goodly can be 30 % by weight.
In one embodiment of this invention, cleaning agent component contains at least one interfacial agent, wherein said interfacial agent can be selected from non-ionic surfactant, anionic surfactant, cationic interfacial agent, zwitterionic surfactant or its combination, and when it is packaged in water-soluble container of the present invention, its water content had meets above-mentioned requirement.
In one embodiment of this invention, cleaning agent component can be packaged in water-soluble container of the present invention by any known method, these method for makings comprise by necessity and optionally composition mixing, and the mixture of all acquisitions to be packaged in water-soluble container of the present invention.
In one embodiment of this invention, the method for making not special restriction of water-soluble container.In a preferred embodiment, can use form fill seal machine that soluble packing membrane of the present invention is transformed into container, for example, heat sealing method can be used in automatic-packaging, or use adhesive agent to make wrapping film bag, then cleaning agent component is packaged in bag, and then uses heat sealing method or adhesive agent packaging bag to be sealed.
The present invention can some forms and mode realize, example embodiment of the present invention is shown in description provided hereinafter, only these embodiments are not used to limit the present invention, and the modification that any personage being familiar with this skill can reach easily and change are category of the present invention.
The enforcement of above related invention, we are by with following embodiment explanation.
Example:
Prepare a kind of polyvinyl alcohol (PVA) film, described PVA film can be dissolved in the water at 5 DEG C of temperature.In addition, prepare two kinds and fluoridize acryl system resin solution: 3MNovec1700 (solution density is 1.5g/mL) and 3MNovec2708 (1.4g/mL), what wherein 3MNovec1700 comprised 2% percentage by weight fluoridizes acryl system resin, and what 3MNovec2708 then comprised 8% percentage by weight fluoridizes acryl system resin.Then use rod coater two kinds to be fluoridized acryl system resin-coating on PVA film, the wet-film thickness of coating is about 7 microns, then by the PVA film drying through fluoridizing the resin solution coating of acryl system.
Spray method of testing (AATCC193Test)
Spray method of testing can assist judgment object for the repellence of waterborne liquid, and its waterborne liquid repellence score criteria is as shown in table 1:
Table 1 sprays the score criteria of method of testing
Waterborne liquid repellence score criteria Test liquid forms
0 Failure, 98% water
1 98: 2/ water: isopropyl alcohol (vol: vol)
2 95: 5/ water: isopropyl alcohol (vol: vol)
3 90: 10/ water: isopropyl alcohol (vol: vol)
4 80: 20/ water: isopropyl alcohol (vol: vol)
5 70: 30/ water: isopropyl alcohol (vol: vol)
6 60: 40/ water: isopropyl alcohol (vol: vol)
7 50: 50/ water: isopropyl alcohol (vol: vol)
8 40: 60/ water: isopropyl alcohol (vol: vol)
The dish of a 25mm diameter is cut into sheet material for testing by Capillary Flow porometry.Described same sample is also used to test water permeability under stress.These data present in Table 1.
Example 1:
On the surface of prepared film sample is dripped, different test liquids carries out spray test, after waiting for for 10 seconds, observes and obtains repellence mark.Find after tested, the PVA film through Novec2708 coating can reach the aqueous solution repellence of mark 8; PVA film through Novec1700 coating can reach the aqueous solution repellence of mark 7.Known via described test result, use the water-soluble container obtained by soluble packing membrane of the present invention, because it has excellent in water repellence, therefore can the water content of cleaning agent component in hoisting container, that is component content in addition to water can reduce in expression cleaning agent, the cost of the cleaning agent therefore packed with water-soluble container of the present invention will reduce, and this is benefit of the present invention.
Example 2:
Water droplet on the surface of prepared sample is dripped, measures water droplet in the contact angle (contactangle) of sample surface.Fig. 3 display is through fluoridizing the coating of acryl system resin solution and without the test result of PVA film of fluoridizing the resin solution coating of acryl system.Fig. 3 (a) shows, and water droplet is dispersed in soon without fluoridizing on the PVA film of acryl system resin solution coating, and damages described PVA film.Fig. 3 (b) shows, and the contact angle of water droplet on PVA film apply through Novec1700 is about 88 degree, but the angle increasing contact angle along with the time reduces, and this is start to infiltrate PVA film because of water droplet.Fig. 3 (c) shows, and the contact angle of water droplet on the PVA film applied through Novec2708 is about 102 degree.
Example 3:
Known through above-mentioned example, PVA film through fluoridizing the resin solution coating of acryl system has a water resisting property, but consider for being used for making detergent pouch by the described PVA film through fluoridizing the coating of acryl system resin solution, therefore its solubility system in water is quite important.After tested, after approximately passing through 155 seconds without the PVA film fluoridizing the resin solution coating of acryl system, can be dissolved in the water completely; After the PVA film of Novec1700 coating approximately passes through 168 seconds, can be dissolved in the water completely; After the PVA film of Novec2708 coating approximately passes through 253 seconds, can be dissolved in the water completely.Significantly, during through costing containing the PVA film fluoridizing the resin solution process of acryl system of higher concentration, the more time could be dissolved in the water completely, but described longer number of seconds is still can accept in time range.
Example 4:
Get one block of glass, respectively by without fluoridize acryl system resin-coating PVA film, through Novec1700 coating PVA film and through Novec2708 coating PVA Film Fractionation in water, and with glass surface described in these aqueous solution wipings, then water droplet is dripped on described glass surface, observe water droplet form.Fig. 4 (a) shows, and water droplet form is on the glass surface defeated and dispersed, and this illustrates without fluoridizing the PVA Film Fractionation of acryl system resin in water, after using described solution cleaning glass window surface, can't form hydrophobic diaphragm at glass surface.
By the PVA Film Fractionation that applies through Novec1700 in water, use described solution cleaning glass window surface, then drip water droplet on the glass surface and observe water droplet form, result is as shown in Fig. 4 (b).Compared to the globule form of Fig. 4 (a), the globule form of Fig. 4 (b) is more complete.
By the PVA Film Fractionation that applies through Novec2708 in water, use described solution cleaning glass window surface, then drip water droplet on the glass surface and observe water droplet form, result is as shown in Fig. 4 (c).Compared to the water droplet form of Fig. 4 (a) and Fig. 4 (b), the water droplet form of Fig. 4 (c) is more complete.
According to the above results; to have after the PVA Film Fractionation comprising the hydrophobic film fluoridizing acryl system resin forms solution in water; use described solution wiping (or clean) body surface; can form a hydrophobic protective layer on described body surface, this is benefit of the present invention.
Announcement of the present invention is intended to explain how to be formed and to use various according to embodiments of the invention, and unrestricted of the present invention real, be intended to and appropriate category and spirit of the present invention.More than discuss and be not intended for detailed or the present invention be limited to disclosed clear and definite form.In view of above teaching, it is possible for revising or changing.Can select and describe embodiment to provide the best illustration to principle of the present invention and practical application, and making to have the knack of the technology person and can utilize the present invention in various embodiments and there are the various changes being suitable for the specific use expected.When according to through just, legal and the range of rational delegation of power is explained time, all these revise and change in the category defined by appended claim and its equivalents all of the present invention, can be revised these in the unsettled period of this application case of patent and revise and change.

Claims (16)

1. a soluble packing membrane, it comprises a kind of water insoluble substrate film, and at least one side surface of described film has the hydrophobic film comprising and fluoridize acryl system resin.
2. soluble packing membrane according to claim 1, wherein said acryl system resin of fluoridizing comprises and is selected from by the group that formed of the following: fluoridize polymethyl methacrylate, perfluor alkyl ethide methacrylate, polymethylacrylic acid perfluoroalkyl methyl esters, aliphatic fluoride polymer and composition thereof, and described in fluoridize the molecular weight of acryl system resin lower than 10000.
3. soluble packing membrane according to claim 1, wherein said packaging film have at least 80 degree to water contact angle.
4. soluble packing membrane according to claim 3, wherein said packaging film have at least 100 degree to water contact angle.
5. soluble packing membrane according to claim 1, the thickness of wherein said water insoluble substrate film is 20 to 100 microns.
6. soluble packing membrane according to claim 5, the thickness of wherein said water insoluble substrate film is 40 to 80 microns.
7. soluble packing membrane according to claim 1, the thickness of wherein said hydrophobic film is 0.1 micron to 1 micron.
8. soluble packing membrane according to claim 7, the thickness of wherein said hydrophobic film is 0.12 to 0.6 micron.
9. prepare a method for soluble packing membrane according to claim 1, it comprises
There is provided a kind of water insoluble substrate film, the material system of wherein said water insoluble substrate film comprises and is selected from by following the group formed: the ethers of polyvinyl alcohol, polyvinyl alcohol copolymer, polyacrylic acid and salt thereof, alkylcellulose, alkylcellulose and ester class, carboxymethyl cellulose, hydroxy alkyl cellulose ester, polymethylacrylic acid, polyacrylamide, acrylic acid/maleic anhydride copolymers, polyvinylpyrrolidone, starch, glycerine, gelatin and composition thereof; Acryl system resin solution is fluoridized in preparation, and described solution comprises fluoridizes acryl system resin and at least one solvent; At least one side surface of described water insoluble substrate film fluoridizes acryl system resin solution described in coating; And by the water insoluble substrate film drying through fluoridizing the coating of acryl system resin solution, directly by this on described water insoluble substrate film, forming a continuous print comprise the hydrophobic film fluoridizing acryl system resin.
10. method according to claim 9, wherein said solvent is hydrogen fluorine ether (hydrofluoroether).
11. methods according to claim 9, wherein said acryl system resin of fluoridizing comprises and is selected from by the group that formed of the following: fluoridize polymethyl methacrylate, perfluor alkyl ethide methacrylate, polymethylacrylic acid perfluoroalkyl methyl esters, aliphatic fluoride polymer and composition thereof, and described in fluoridize the molecular weight of acryl system resin lower than 10000.
12. 1 kinds of water-soluble containers, wherein said container system formed by soluble packing membrane according to claim 1, and described soluble packing membrane have comprise the hydrophobic film fluoridizing acryl system resin a side-line as the inner side of described water-soluble container.
13. water-soluble containers according to claim 12, wherein said container can be pouch, pouch or other injection molded shapes.
14. water-soluble containers according to claim 12, wherein said water-soluble container is built with cleaning agent component.
The purposes of 15. 1 kinds of soluble packing membranes according to claim 1, it is as water-soluble container.
16. 1 kinds little bag-shaped cleaning agents, it is the water-soluble container comprising a cleaning agent and soluble packing membrane according to claim 1 and formed, and described soluble packing membrane has the side-line that comprises the hydrophobic film fluoridizing acryl system resin as the inner side of described water-soluble container contacts with described cleaning agent.
CN201410490615.7A 2014-09-23 2014-09-23 Water-soluble packaging film and uses thereof Pending CN105500854A (en)

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Application Number Priority Date Filing Date Title
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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104709567B (en) * 2014-12-30 2017-05-17 宁波浩瑞印务有限公司 Microwave-specific food package bag and manufacturing method thereof
CN109642190A (en) * 2016-09-20 2019-04-16 株式会社 Lg 生活健康 Reinforce the pouch-shaped detergent of water resistance

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104709567B (en) * 2014-12-30 2017-05-17 宁波浩瑞印务有限公司 Microwave-specific food package bag and manufacturing method thereof
CN109642190A (en) * 2016-09-20 2019-04-16 株式会社 Lg 生活健康 Reinforce the pouch-shaped detergent of water resistance
US10781412B2 (en) 2016-09-20 2020-09-22 Lg Household & Health Care Ltd. Detergent in the form of a laundry storage envelope having enhanced resistance to water
CN109642190B (en) * 2016-09-20 2021-08-31 株式会社 Lg 生活健康 Bag-shaped detergent with enhanced water resistance

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Application publication date: 20160420