CN104629226A - Special cold-water instant packaging film for laundry detergent - Google Patents
Special cold-water instant packaging film for laundry detergent Download PDFInfo
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- CN104629226A CN104629226A CN201510036853.5A CN201510036853A CN104629226A CN 104629226 A CN104629226 A CN 104629226A CN 201510036853 A CN201510036853 A CN 201510036853A CN 104629226 A CN104629226 A CN 104629226A
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- film
- polyvinyl alcohol
- packing film
- cold water
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- Y—GENERAL 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
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
- Y02W90/00—Enabling technologies or technologies with a potential or indirect contribution to greenhouse gas [GHG] emissions mitigation
- Y02W90/10—Bio-packaging, e.g. packing containers made from renewable resources or bio-plastics
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Abstract
The invention discloses a special cold-water instant packaging film for a laundry detergent, and a method for preparing the film. The method comprises the following steps: with modified polyvinyl alcohol with the hydroxyethyl content being 1-3wt% as a main raw material, adding assistants such as a mixed plasticizer, an antioxidant and an anti-blocking agent; and preparing a water-soluble polyvinyl alcohol film by a molten curtain coating method. The trend of easy crosslinking in polyvinyl alcohol melting and processing at present is overcome by the modified polyvinyl alcohol and the mixed plasticizer; a water-soluble packaging material which is excellent in performance and can be completely dissolved at a room temperature is obtained; and the film can be applied to packing of liquid detergents, laundry detergents and the like.
Description
Technical field
The invention belongs to environmental friendliness water soluble package material, particularly relate to water-soluble packing film of a kind of hydroxyethyl modified polyvinyl alcohol (HEC-PVA) and preparation method thereof.
Background technology
Soluble polymeric films is usually used as the wrapping material of the products such as washing composition/medicament, the unit package bag prepared by water-solubility membrane can simplify the distribution in use of this series products, topple over, dissolve and quantitatively, user and chemical is avoided to occur directly to contact, safety and sanitation, simultaneously can more accurate measurement dosage, eliminate the needs that human consumer weighs this series products.Described unit package can also be avoided distributing analogous products from container, distributes confusion caused in toppling process.Therefore the unit package bag prepared by soluble polymeric films of this predetermined dose can provide easy-to-use for human consumer.
Usual human consumer, when using as analogous products such as washing liquids, considers for residing environment and energy cost angle, understands the colder water of choice for use and carries out washing or the operation such as dilution.Water temperature can between-4 ~ 35 DEG C under normal circumstances.Therefore one is needed can still to have complete water miscible film under cold water (water temperature less than 5 DEG C) environment.
PVA (PVOH) FILM has water-soluble (determining according to the trade mark) in various degree, and good mechanical strength, the transparency, solvent resistance, barrier properties for gases and be easy to film forming, be suitable for preparing the special cold water instant dissolving packing film of described washing liquid.
In the market, thisly usually can adopt wet processes in the preparation method of cold-water solution PVA (PVOH) FILM, the softening agent such as polyvinyl alcohol and at least one component water be mixed, again its deaeration is extruded to certain viscosity, processing film forming.The processing temperature of wet processes is generally below 100 DEG C, and this method is comparatively general.Domesticly many patents it to be made up of and processing units is reported, wherein Japanese synthetic chemistry patent CN100462392C discloses a kind of PVA (PVOH) FILM with cold water-soluble, adopt wet method, PVA, starch, softening agent, filler etc. are mixed with aqueous dispersions, casting film-forming at 90-100 DEG C.But wet processes on the one hand production efficiency low cost is high, on the other hand to humidity sensitive, the water droplet impact being in use easy to be subject to high humidity or contact causes described film physical strength to reduce even to stick together or moltenly to wear, and the water soluble film that this working method is produced is not easy to heat-sealing.Patent CN102762612A discloses a kind of improvement water-solubility membrane of the blend containing PVOH polymkeric substance, the polyvinyl alcohol of nominal viscosity 13.5 ~ 20cp and nominal viscosity is adopted to be less than the polyvinyl alcohol blend of 11cp, with glycerine, Sorbitol Powder, propylene glycol etc. are softening agent, prepare a kind of water soluble film with good water droplet resistance, its preparation technology mixes described polymkeric substance by water, softening agent and other auxiliary agents, again moisture is removed after cast film forming, the main plasticizer contained in film is made to be glycerine or Sorbitol Powder etc., although this method improves the heat sealability of film, but need to dry moisture under suitable condition after complicated process of preparation cast film forming, affect production efficiency.
Therefore in this context, in order to effectively improve heat sealability and the production efficiency of water soluble film, the invention provides one can quick and complete dissolving in cold water, have the washing liquid special cold water instant dissolving packing film of good heat sealability and high comprehensive performance, the preparation method of described packing film is fusion extrusion casting method, processing temperature is between 150 ~ 250 DEG C.
The separate unit packing bag that the special cold water instant dissolving packing film of described washing liquid can be made into.This packing bag also can be used for holding the such as sanitising agent, washing composition, medicament etc. that comprise such as powder, gel, cream, liquid, tablet or its any combination except washing liquid.This combination can be load in mixture in same unit package bag, and also wherein component separately can be packaged in different units packaging, this is also one of advantage of this unit package.
Summary of the invention
Should give explanation:
One, except as otherwise noted, the weight of component and the per-cent of whole film weight determined in term " wt% " under being intended to relate to drying regime.Except as otherwise noted, all measurements are all carried out at 25 DEG C.
Two, water-soluble test, is sample film being cut into 5cm × 5cm size, is fixed by this sample fixture, be then impregnated in contain 1 premium on currency beaker in, record the complete dissolution time of sample under agitator agitation condition.
For existing issue, the invention provides production formula and the preparation technology of the special cold water instant dissolving packing film of a kind of washing liquid, mix under the condition not having water by hydroxyethyl modified polyvinyl alcohol and other auxiliary agents, under certain temperature (generally between 150 ~ 250 DEG C), directly extrude casting film-forming.Because film introduces a large amount of alcohols or amine softening agent in advance in the course of processing, the agent of film forming post-plasticization is dispersed in HEC-PVA matrix and forms hydrogen bond with the hydroxyl in HEC-PVA, make a small amount of water droplet can not break film internal hydrogen bond structure thus enhance the resistance to water droplet of film, not affecting the water-soluble of film and mechanical property simultaneously.In addition, strengthened the melt strength of PVA by HEC modification, make the easier forming process of film, enhance the thermostability in the course of processing, improve the mechanical property of film simultaneously, effectively prevent inner softening agent from moving.
The special cold water instant dissolving packing film composition of washing liquid
Washing liquid of the present invention special cold water instant dissolving packing film contains the hydroxyethyl modified polyvinyl alcohol of at least one, the HEC-PVA resinoid of alcoholysis degree 70 ~ 99%, the polymerization degree 500 ~ 2400, softening agent, oxidation inhibitor and other auxiliary, processing aid etc.
The special cold water instant dissolving packing film of the washing liquid that the present invention relates to contains 50 ~ 99wt% polyvinyl alcohol (HEC-PVA) resin, for being not limited to that alcoholysis degree is 70 ~ 99%, the polymerization degree is any one in the HEC-PVA resin of 500 ~ 2400, is preferably any one in the HEC-PVA resin of alcoholysis degree 87 ~ 89%, the polymerization degree 1500 ~ 2000.The water-soluble height with its alcoholysis degree of polyvinyl alcohol has very big difference, alcoholysis degree be 87 ~ 89% HEC-PVA water-soluble best, alcoholysis degree be more than 99% HEC-PVA be only dissolved in the hot water of 95 DEG C.The acetate that the HEC-PVA remnant of partial alcoholysis (88%) is hydrophobic, because the volume that acetate is very large weakens intermolecular and intramolecular hydrogen bond, and substantially improve the water-soluble of polyvinyl alcohol, make alcoholysis degree be 87 ~ 89% the solubleness of HEC-PVA in water and dissolution rate best.The HEC-PVA of alcoholysis degree 99% is due to hydrogen bond action very strong between hydroxyl, and slightly soluble under normal temperature, is only dissolved in hot water, and the HEC-PVA that alcoholysis degree is lower makes because acetate content increases water-solublely greatly to decline.In addition, alcoholysis degree too low (lower than 70%) then can not ensure its good film-forming properties, but certain plasticization effect can be reached compared with the HEC-PVA of low alcoholysis level with higher alcoholysis degree HEC-PVA is composite, because alcoholysis degree is different, hydrophobicity acetate and the hydrophilic hydroxy group ratio contained by HEC-PVA is different, cause the surface tension of HEC-PVA, the physical properties such as degree of crystallinity and fusing point changes, the degree of crystallinity of HEC-PVA and fusing point are different and different with remaining acetate distribution, even if when remaining acetate content is identical, with the disorder of its distribution, crystallinity declines, melting temperature (Tm) reduces.
The polyvinyl alcohol resin contained in the special cold water instant dissolving packing film of the washing liquid related in the present invention also has the hydroxyethyl alternatively base of 1wt% ~ 3wt%, and its PVA matrix resin is the PVA resin manufactured by known method.Namely can be vinyl ester compound polymerization and the vinyl ester base polymer obtained carries out saponification and the PVA resin obtained.The present invention's polyvinyl alcohol used is that white particle is even, and its aqueous solution is raw without insoluble produce.
The softening agent contained in the washing liquid that the present invention relates to special cold water instant dissolving packing film is a kind of softening agent compound, effectively can reduce the processing temperature of polyvinyl alcohol, prevent polyvinyl alcohol from occurring to lump or produce the brilliant point being unfavorable for polyvinyl alcohol dissolution in high temperature working processes, the softening agent that the present invention relates to has but is not limited to following several: ethylene glycol, 1, 2-propylene glycol, glycerol, Glycerol dimer, sorbyl alcohol, mannitol, Xylitol, polyoxyethylene glycol, TriMethylolPropane(TMP), tetramethylolmethane, urea, acrylamide, polymeric amide, trimeric cyanamide, XU 61518.10, amine hydroxybenzene, erucicamide, glycerin fatty acid ester, one or more mixing in stearate, wherein be preferably ethylene glycol, glycerol, sorbyl alcohol, polyoxyethylene glycol, tetramethylolmethane, urea.
Content for softening agent is not particularly limited, but relative to total amount 100 weight part of HEC-PVA resinoid (A), be preferably 1 ~ 45 weight part, be more preferably 5 ~ 40 weight parts, plasticizer loading is poor less than plasticization effect during 1 weight part, causes film to plastify the not exclusively water-soluble and mechanical property of impact.Plasticizer loading is more than 45 parts, and softening agent easily moves.
Containing oxidation inhibitor in the special cold water instant dissolving packing film of the washing liquid that the present invention relates to, described oxidation inhibitor comprises primary antioxidant and Synergistic stabilizer.
Primary antioxidant is in order to prevent the thermal-oxidative degradation of HEC-PVA in melt-processed process, improve its discoloration-resistant under high temperature process condition and processing stability simultaneously, alkylphenol compounds can be adopted, alkylidene group phenolic compound, alkyl bisphenol compounds, hydroxy phenyl acrylic ester compound, aminophenols, thiobisphenol compounds, wherein preferably adopt Hinered phenols antioxidant, described Hinered phenols antioxidant can be illustrated but is not limited to octadecyl 3-(3, 5-di-tert-butyl-hydroxy phenyl) propionic ester, four [β-(3, 5-di-tert-butyl-hydroxy phenyl) propionic acid] pentaerythritol ester, N, N '-bis--[3-(3, 5-di-tert-butyl-hydroxy phenyl) propionyl] hexanediamine, 4-[(4, the pungent sulfenyl-1 of 6-bis-, 3, 5-triazine-2-base) amino]-2, 6-DI-tert-butylphenol compounds, N, N '-bis--[3-(3, 5-di-tert-butyl-hydroxy phenyl) propionyl] one or more in hydrazine.
Synergistic stabilizer can the effective hydroperoxide etc. that produce when being subject to hot shearing effect of decomposing H EC-PVA, hydroxy ester compounds can be adopted, saturated acid ester compound, monothioester compounds, phosphite ester compound, be preferably phosphite ester kind antioxidant, described phosphite ester kind antioxidant can be illustrated but is not limited to tricresyl phosphite (2, 4-di-tert-butyl-phenyl) ester, two (2, 4-di-tert-butyl-phenyl) pentaerythritol diphosphites, two (2, 4, 6-tri-tert phenyl) pentaerythritol diphosphites, two (2, 6-di-t-butyl-4-aminomethyl phenyl) one or more in pentaerythritol diphosphites.
The special cold water instant dissolving packing film of the washing liquid that the present invention relates to is except forming containing HEC-PVA, softening agent and oxidation inhibitor, wherein also containing multiple auxiliary, processing aid etc., as comprising but be not limited to releasing agent, Nano compound, antiblocking agent and other functional ingredient, its content is applicable to the desired use of film.
Releasing agent can be illustrated but is not limited to lipid acid and their salt, fatty alcohol, fatty ester, aliphatic amide, aliphatic amine-acetic acid salt and fatty amide, is preferably lipid acid, soap and aliphatic amine-acetic acid salt.In the embodiment of a type, content about 0.01 ~ 2.5wt% when releasing agent is preferably soap in packing film, is preferably 0.1 ~ 1.5wt%.
Antiblocking agent can be illustrated but is not limited to one or more in starch, water soluble starch, cross-linked cellulose, Walocel MT 20.000PV, silicon-dioxide, metal oxide, calcium carbonate, talcum, clay, mica, diatomite, kaolin, asbestos, gypsum, graphite, glass hollow bead, granulated glass sphere, rhombspar, carbon black, wilkinite, montmorillonite, calcium chloride, citrate of lime.In the embodiment of a type, the preferred water miscible antiblocking agent of antiblocking agent.
In the soluble packing membrane that the present invention relates in addition, other water-soluble polymers can be added within the scope without prejudice to the object of the present invention, as can be enumerated but being not limited to sodium polyacrylate, polyethylene oxide, Polyvinylpyrolidone (PVP), dextrin, chitosan, chitin, methylcellulose gum, Natvosol etc., or other additives such as rust-preventive agent, tinting material.
The concrete preparation method of washing liquid special cold water instant dissolving packing film
The special cold water instant dissolving packing film of the washing liquid that the present invention relates to is obtained by melting curtain coating after melt extruding preparation HEC-PVA pellet again, also adopts and can obtain by an extrusion moulding.In the embodiment of a type, the invention discloses and a kind ofly melt extrude the complete processing preparing cold water instant dissolving packing film, packing film preparation process:
(1) polyvinyl alcohol raw material, softening agent, oxidation inhibitor, releasing agent, antiblocking agent are mixed in 25 ~ 150 DEG C of temperature ranges;
(2) mixture in step (1) is joined in double-screw extruding pelletizing machine, extruding pelletization within the scope of 120 ~ 250 DEG C.
(3) by the pellet obtained in step (2) within the scope of 150 ~ 250 DEG C 15 ~ 60% relative humidity under extrude blown film or curtain coating, obtain the packing film that thickness is 0.01 ~ 0.18mm.
The step that an another kind of extrusion moulding prepares the working method of washing liquid special cold water instant dissolving packing film is as follows:
A polyvinyl alcohol raw material, softening agent, oxidation inhibitor, releasing agent, antiblocking agent mix by () in 25 ~ 150 DEG C of temperature ranges, obtain the pre-plasticising masterbatch of polyvinyl alcohol;
B pre-for the polyvinyl alcohol obtained in step (a) plasticising masterbatch directly joins in an extrusion shaping machine by (), within the scope of 150 ~ 250 DEG C 50% relative humidity under extrude blown film or curtain coating, obtain the packing film that thickness is 0.01 ~ 0.18mm.
For the working method of a this extrusion moulding, the secondary of polyvinyl alcohol effectively can be avoided by hot-work, decrease operating process and personnel cost.A described extrusion shaping machine is made up of feeder, twin screw (length-to-diameter ratio L/D=28 ~ 60: 1, screw rod nominal diameter 30 ~ 90mm), Melt Pump, curtain coating head and curtain coating subsidiary engine or blown-film die and blown film subsidiary engine.
In the special cold water instant dissolving packing film of the washing liquid that the present invention relates to, packing film thickness is different with purposes difference, and packing film thickness is preferably 0.01 ~ 0.18mm, is particularly preferably 0.02 ~ 0.08mm.When thickness is less than 0.01mm, packing film physical strength is poor, and on the contrary more than 0.18mm, the cold-water solution speed of packing film can be affected, and masking efficiency also declines thereupon.
In the embodiment of a type, when the thickness of the special cold water instant dissolving packing film of described washing liquid is 0.02mm, it is under the condition of 10 DEG C in water temperature, the complete water-soluble time is no more than 30s, when thickness is 0.08mm, the complete water-soluble time is no more than 120s, and when thickness is 0.04mm, the complete water-soluble time is no more than 45s.
Packing film surface can be level and smooth in addition, or also can carry out embossing process to the surface of film.Determine according to the preparation situation of packing bag.
Separate unit packing bag
The separate unit packing bag prepared by the special cold water instant dissolving packing film of washing liquid that the present invention relates to, comprise the unit of at least one sealing, in the embodiment that there is multiple separate unit, each unit can comprise identical or different composition, as can be illustrated but being not limited to powder, gel, cream, liquid, tablet or its any combination.
This separate unit packing bag can be prepared by any suitable equipment and method, prepares as illustrated but be not limited to vertical-type filling, horizontal type filling or drum-type filling technique.These class methods can be that continous way is produced, and adopt the method for heating film to increase its ductility, can give prominence to the advantage of the special cold water instant dissolving packing film of the washing liquid prepared in the present invention to greatest extent.
The mould of manufacturing cell's packing bag can have any shape and outward appearance, in the embodiment of a type, uses vacuum method to be sucked by film in the mould established in advance, to be sucked by film in mould and to apply the vacuum take-off of short period of time.Therefore the size and dimension of mould also can change if needed, but its final volume can be 10 ~ 500ml or 25 ~ 300ml, and carries out corresponding size adjustment to mould.
The method that the separate unit packing bag that the present invention relates to adopts heat-sealing shaping obtains, and both heat is put on film, and any appropriate ways can be adopted to apply heat, as can be enumerated but being not limited to snead process, indirect heating method.
Described direct heating refers to that heat is given to film surface by direct heating unit altogether.Described indirect heating method refers to and carries out heating as Infrared Heating to film by other means.
Thermosealed method can be utilized only to carry out heat treatment to sealing area.Typical temperature setting range at 120 ~ 250 DEG C, preferably at 150 ~ 180 DEG C.
The concrete forming method of separate unit packing bag
In the embodiment of a type, the working method of the unit package bag that the present invention relates to is:
(1) film is cut into suitable size at least two to stack together.
(2) method of heat-seal is adopted overlay film to be closed at least one unit package of suitable size
(3) unit package is filled
(4) heat seal
Unit package bag of the present invention can fill multiple not containing or a small amount of different compositions containing water, and pouch dissolves hardly and removes other solvents except water-soluble.
The present invention's useful point is compared with prior art:
1. the present invention and prior art are as compared with the patent of application number CN100462392, CN102762612A, employ and melt extrude complete processing, improve production efficiency.
2. compared with polyvinyl alcohol, hydroxyethyl modified polyvinyl alcohol has more excellent thermoplastic processability, solves the problem that polyvinyl alcohol in the course of processing is easily cross-linked.
3. film has good heat sealability.
Embodiment
Be further elaborated the present invention below in conjunction with embodiment, the embodiment provided is only illustrates the present invention, instead of in order to limit the scope of the invention.
embodiment 1
Remember by weight:
To fill a prescription above; by polyvinyl alcohol raw material, softening agent, oxidation inhibitor, releasing agent, Nano compound, antiblocking agent in high-speed mixer; 2000rpm; 70 DEG C mix after; gained mixture is joined screw slenderness ratio L/D=45: 1; in screw diameter Φ 35mm extruding granulator, extruding pelletization within the scope of 120 ~ 250 DEG C.
By the pellet obtained in step (2) within the scope of 150 ~ 250 DEG C 50% relative humidity under extrude curtain coating, obtain the special cold water instant dissolving packing film of washing liquid that thickness is 0.035mm.
The correlation performance parameters of packing film is as shown in the table:
embodiment 2
To fill a prescription above; by polyvinyl alcohol raw material, softening agent, oxidation inhibitor, releasing agent, Nano compound, antiblocking agent in high-speed mixer; 2000rpm; 70 DEG C mix after; gained mixture is joined screw slenderness ratio L/D=60: 1; in screw diameter Φ 65mm extruding granulator, extruding pelletization within the scope of 120 ~ 250 DEG C.
By the pellet obtained in step (2) within the scope of 150 ~ 250 DEG C 50% relative humidity under extrude curtain coating, obtain the special cold water instant dissolving packing film of washing liquid that thickness is 0.045mm.
The correlation performance parameters of packing film is as shown in the table:
Claims (11)
1. the special cold water instant dissolving packing film of washing liquid, described packing film contains hydroxyethyl modified polyvinyl alcohol resin 60 ~ 85wt%, softening agent 15 ~ 35wt%, antioxidant 0.1 ~ 1.5wt%, other surpluses such as auxiliary, processing aid.
2. as described in the appended claim 1, containing hydroxyethyl modified polyvinyl alcohol resin in washing liquid special cold water instant dissolving packing film, described hydroxyethyl modified polyvinyl alcohol resin be ethoxyl content at 1wt% ~ 3wt%, alcoholysis degree between 87 ~ 89%, the polymerization degree between 1300 ~ 2000 any one or multiple.
3., as described in the appended claim 1, containing softening agent in the special cold water instant dissolving packing film of washing liquid, described softening agent is one or more in ethylene glycol, glycerol, sorbyl alcohol, polyoxyethylene glycol, tetramethylolmethane, urea, methane amide, ethanamide.
4. as described in the appended claim 1, containing antioxidant in the special cold water instant dissolving packing film of washing liquid, described antioxidant comprises primary antioxidant and Synergistic stabilizer.
5. primary antioxidant is octadecyl 3-(3 as claimed in claim 4; 5-di-tert-butyl-hydroxy phenyl) propionic ester, four [β-(3; 5-di-tert-butyl-hydroxy phenyl) propionic acid] pentaerythritol ester, N; N '-bis--[3-(3; 5-di-tert-butyl-hydroxy phenyl) propionyl] hexanediamine, 4-[(the pungent sulfenyl-1,3 of 4,6-bis-; 5-triazine-2-base) amino] one or more in-2,6 di t butyl phenol.
6. Synergistic stabilizer is tricresyl phosphite (2 as claimed in claim 4,4-di-tert-butyl-phenyl) ester, two (2,4-di-tert-butyl-phenyl) pentaerythritol diphosphites, two (2,4,6-tri-tert phenyl) pentaerythritol diphosphites, one or more in two (2,6-di-t-butyl-4-aminomethyl phenyl) pentaerythritol diphosphites.
7., as the cold water instant dissolving packing film in aforementioned claim as described in any one, thickness is between 0.02 ~ 0.08mm, and the complete dissolution time in 10 DEG C of water is between 30 ~ 120s.
8. as described in aforementioned claim 1, auxiliary and processing aid are antiblocking agent, rust-preventive agent, tinting material.
9. as described in patent requirements 8, antiblocking agent is one or more in starch, water soluble starch, cross-linked cellulose, Walocel MT 20.000PV, Natvosol, calcium chloride, citrate of lime.
10. the working method preparing washing liquid special cold water instant dissolving packing film is as follows:
(1) polyvinyl alcohol raw material, softening agent, oxidation inhibitor, releasing agent, antiblocking agent are mixed in 25 ~ 150 DEG C of temperature ranges, obtain the pre-plasticising masterbatch of polyvinyl alcohol;
(2) pre-for the polyvinyl alcohol obtained in step (1) plasticising masterbatch is directly added in an extrusion shaping machine, within the scope of 150 ~ 250 DEG C 50% relative humidity under extrude blown film or curtain coating, obtain the packing film that thickness is 0.02 ~ 0.08mm.
11. extrusion shaping machines as described in patent requirements 10 are made up of feeder, twin screw (length-to-diameter ratio L/D=28 ~ 60: 1, screw rod nominal diameter 30 ~ 90mm), Melt Pump, curtain coating head and curtain coating subsidiary engine or blown-film die and blown film subsidiary engine.
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| CN111484696A (en) * | 2020-05-12 | 2020-08-04 | 周栋 | Plastic packaging film for producing washing condensation beads and preparation method and application thereof |
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| CN116368075A (en) * | 2020-12-15 | 2023-06-30 | 蒙诺苏尔有限公司 | Water-soluble film, water-soluble unit dose article, and methods of making and using the same |
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