WO2010058876A1 - Film de mousse polyuréthane thermoplastique - Google Patents

Film de mousse polyuréthane thermoplastique Download PDF

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Publication number
WO2010058876A1
WO2010058876A1 PCT/KR2008/007553 KR2008007553W WO2010058876A1 WO 2010058876 A1 WO2010058876 A1 WO 2010058876A1 KR 2008007553 W KR2008007553 W KR 2008007553W WO 2010058876 A1 WO2010058876 A1 WO 2010058876A1
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WO
WIPO (PCT)
Prior art keywords
tpu
layer
foam
film
copolymer
Prior art date
Application number
PCT/KR2008/007553
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English (en)
Inventor
Hee-Dae Park
Original Assignee
Hee-Dae Park
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Filing date
Publication date
Application filed by Hee-Dae Park filed Critical Hee-Dae Park
Publication of WO2010058876A1 publication Critical patent/WO2010058876A1/fr

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Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C44/00—Shaping by internal pressure generated in the material, e.g. swelling or foaming ; Producing porous or cellular expanded plastics articles
    • B29C44/20—Shaping by internal pressure generated in the material, e.g. swelling or foaming ; Producing porous or cellular expanded plastics articles for articles of indefinite length
    • B29C44/22—Shaping by internal pressure generated in the material, e.g. swelling or foaming ; Producing porous or cellular expanded plastics articles for articles of indefinite length consisting of at least two parts of chemically or physically different materials, e.g. having different densities
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
    • B29C48/03—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor characterised by the shape of the extruded material at extrusion
    • B29C48/07—Flat, e.g. panels
    • B29C48/08—Flat, e.g. panels flexible, e.g. films
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
    • B29C48/16—Articles comprising two or more components, e.g. co-extruded layers
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
    • B29C48/16—Articles comprising two or more components, e.g. co-extruded layers
    • B29C48/18—Articles comprising two or more components, e.g. co-extruded layers the components being layers
    • B29C48/21—Articles comprising two or more components, e.g. co-extruded layers the components being layers the layers being joined at their surfaces
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
    • B29C48/25—Component parts, details or accessories; Auxiliary operations
    • B29C48/30—Extrusion nozzles or dies
    • B29C48/305—Extrusion nozzles or dies having a wide opening, e.g. for forming sheets
    • B29C48/307—Extrusion nozzles or dies having a wide opening, e.g. for forming sheets specially adapted for bringing together components, e.g. melts within the die
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29D—PRODUCING PARTICULAR ARTICLES FROM PLASTICS OR FROM SUBSTANCES IN A PLASTIC STATE
    • B29D7/00—Producing flat articles, e.g. films or sheets
    • B29D7/01—Films or sheets
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
    • B29K2075/00—Use of PU, i.e. polyureas or polyurethanes or derivatives thereof, as moulding material

Definitions

  • the present invention relates to a method for manufacturing a high frequency welding Thermoplastic
  • TPU film used in the various industrial fields. More particularly, the present invention relates to a method for manufacturing a high frequency welding TPU foam film, for manufacturing a single-layer film constituted of a foam layer or a multi-layer film constituted of a foam layer and a non-foam layer in an extrusion method to realize the lightweight and surface uniformity of a TPU film, and a TPU foam film manufactured by the method.
  • the shoe industrial fields use various materials for ornament of shoes upper.
  • a technology for screen printing a polyvinyl chloride or polyurethane film in various colors and then welding the printed film to shoes upper using a high frequency welding method has been widely used.
  • This high frequency work enables a brilliant design of a shoe and enables a design of a three-dimensional effect, thus making a great contribution to advanced shoes.
  • a polyvinyl chloride film has been much used by reason of a low manufacturing cost but, in recent years, its use is very strictly limited because of environmental regulation getting more serious.
  • Thermoplastic PolyUrethane (TPU) films have been much used.
  • TPU is a very excellent material that makes it possible to manufacture films of various ranges of shoreness without using plasticizer and can keep excellent elasticity and durability even at very low temperature.
  • TPU is excellent in physical property, but its relatively high price is a burden to the cost of shoe manufacture.
  • polyurethane film materials have a high specific gravity of about 1.2 and thus, if a large quantity is used, it causes an increase of the whole weight of a shoe, having bad influence on the recent trend of shoe lightweight.
  • FIG. 1 is a schematic diagram illustrating a cylinder, an adapter, and a dice of a construction of a T-dice extrusion device for manufacturing a multi-layer Thermoplastic PolyUrethane (TPU) foam film according to the present invention
  • FIG. 2 is a diagram illustrating a multi-layer TPU foam film according to an exemplary embodiment of the present invention.
  • FIG. 3 is a diagram illustrating a construction of a multi-layer TPU foam film according to another exemplary embodiment of the present invention. Disclosure
  • the present invention is directed to a Thermoplastic PolyUrethane (TPU) foam film that substantially obviates one or more of the problems due to limitations and disadvantages of the related art.
  • TPU Thermoplastic PolyUrethane
  • An object of the present invention is to manufacture a high frequency welding TPU film through T-die extrusion not a calendar process while foaming TPU using a foam for TPU lightweight, and provide not only a method for manufacturing a TPU film constituted of a single layer but also a manufacturing method of a high-frequency welding TPU foam film for foaming only a middle layer or bottom layer without foaming a top layer, thus being able to manufacture a multilayer foam film whose surface smoothness is very excellent, and a TPU foam film manufactured by the method.
  • Another object of the present invention is to provide a method for manufacturing a TPU foam film by a single work by co-extruding, not laminating, a multi-layer film through a multi-layer film extruder, and a TPU foam film manufactured by the method.
  • a further object of the present invention is to provide a method for manufacturing a high frequency welding TPU foam film, for realizing not only lightweight of a TPU film but also uniformity of a surface and thickness of the film, and a TPU foam film manufactured by the method.
  • TPU Thermoplastic PolyUrethane
  • the method includes filling each chamber with TPU, filling remaining chambers excepting one chamber among the chambers with auxiliary workability controlling resin such as Styrene-Butadiene- Styrene (SBS) copolymer, Ethylene-VinylAcetate (EVA) copolymer, and Styrene-AcryloNitrile (SAN) copolymer and a foam, foaming the TPU, simultaneously extruding the foam TPU and non-foam TPU by the T-die extruder, and forming a top layer as a non-foam layer and forming a bottom layer as a foam layer.
  • auxiliary workability controlling resin such as Styrene-Butadiene- Styrene (SBS) copolymer, Ethylene-VinylAcetate (EVA) copolymer, and Styrene-AcryloNitrile (SAN) copolymer and a foam
  • SBS Styrene-Butadiene- St
  • the high frequency welding TPU film may have a specific gravity of 0.6 to 1.1.
  • An auxiliary workability controlling resin such as SBS copolymer, EVA copolymer, and SAN copolymer may control a viscosity of extruded resin by 5 to 20 weight parts for 95 to 80 weight parts of the TPU.
  • An exemplary embodiment of the present invention is to realize curing of a high frequency welding Thermoplastic PolyUrethane (TPU) film frequently used in a shoe manufacturing process, and also realize a method for manufacturing a high frequency welding TPU foam film, for manufacturing not only a single-layer film foamed and lighted but also a multi-layer foam film whose surface smoothness is very excellent by selectively foaming only a middle layer or bottom layer excepting a top layer, thus reducing a specific gravity of the whole film.
  • a foam for foaming TPU when manufacturing the TPU into a high frequency welding film should be disclosed in detail and in addition, a detailed composition constituting a TPU film together with the foam should be described.
  • a detail of an extrusion condition for manufacturing a TPU foam film in an extrusion (i.e., co-extrusion) method using a general T-die extruder should be disclosed.
  • a composition of a TPU foam film constituted as a multiple layer as aforementioned should be disclosed in detail.
  • An exemplary embodiment of the present invention uses a general capsule type foam that is commercialized and is in use.
  • the foam contains organic materials having a low boiling point at its interior and its exterior is protected with an acrylic or vinyl resin capsule.
  • the foam has a capsule size of a few microns or less, and a variety of foam products depending on a foaming start temperature and a foaming maximum temperature have been marketed.
  • An exemplary embodiment of the present invention selects and uses a foam that can be used in a TPU film extruding process among the foam products.
  • an exemplary embodiment of the present invention uses a foam whose foaming start temperature is 120 0 C or more and whose foaming maximum temperature is within 150 0 C to 180 0 C.
  • a method for manufacturing a film according to an exemplary embodiment of the present invention manufactures a film in an extrusion method using a T-die extruder not in a film process using a conventional calendar, and uses a multilayer extruder for extruding a two-layer film as well as a single-layer film.
  • an exemplary embodiment of the present invention uses a multi-layer extruder for co- extruding a maximum three-layer film.
  • a conventional single- layer extruder is unreasonable in that extrusion and lamination should be repeated several times to manufacture a multi-layer film.
  • a multi-layer extruder used in an exemplary embodiment of the present invention is a very efficient manufacturing device that can solve such repetitive extrusion at a time.
  • An exemplary embodiment of the present invention uses TPU materials including not only real TPU but also recycling TPU that is a recycle of a TPU film of a scrap state generated through a variety of paths after film processing.
  • the recycling TPU has been described in detail in Korean Patent Application No. 10-2008-113102 filed on November 14, 2008 by this applicant. Further, a method for manufacturing the recycling TPU is briefly described below. After pulverizing scrap generated in a high frequency process, the method extrudes the pulverized scrap while eliminating foreign materials, thus manufacturing the pulverized scrap in a pellet form. After mixing the scrap pellet with TPU that is raw material, the method extrudes the mixture while eliminating foreign materials, thus manufacturing recycling TPU.
  • a first exemplary embodiment of the present invention provides a method for manufacturing a TPU foam film constituted of a single layer.
  • Table 1 shows a detail of a composition and mixture ratio of each layer when manufacturing the TPU film.
  • SBS denotes Styrene-Butadiene-Styrene copolymer.
  • the SBS is added to increase a viscosity of resin so as to prevent a problem resulting from low viscosity during a production process such as a problem of thickness control because a viscosity of resin is excessively reduced after foam reaction.
  • an input of SBS of 5 weight parts or more (at this time, TPU is of 95 weight parts or more) is required.
  • TPU exceeds 20 weight parts (at this time, TPU exceeds 80 weight parts)
  • product turbidity increases due to a failure of compatibility with TPU, thus causing poor appearance. 15 weight parts are most appropriate.
  • EVA Ethylene-VinylAcetate copolymer
  • SAN Styrene- AcryloNitrile copolymer
  • a thickness control problem can be solved at the time of product production by using TPU itself having high viscosity without using SBS, EVA, SAN, etc.
  • the thickness control problem resulting from viscosity reduction can be solved by using TPU whose melt index is 7g/10min or less at 175 degrees and 2.16kg weight. That is, production is possible even without using SBS and, at a higher melt index, supplementary SBS is used, thus being able to achieve a viscosity increase effect.
  • An anti-yellowing master batch is of a Ultra-Violet (UV) absorber of 20%, an anti-oxidant of 20%, and TPU of 40%. Generally, the anti-yellowing master batch is used within a range of 1 to 5 weight parts and, most desirably, is used within 2 to 4 weight parts.
  • the white-color pigment master batch is of TiO 2 of 40%, an anti-oxidant of 1%, and TPU of 59%.
  • the anti-yellowing master batch and white-color pigment master batch constituted of such compositions are identically used in each of exemplary embodiments of the present invention below.
  • a foam is of a capsule type as above. The foam is slightly yellowed in color because of its characteristic and thus, its final product appearance gives feeling as if it is yellowed. Thus, in order to reduce such a phenomenon, an exemplary embodiment of the present invention slightly adds a white-color master batch to a middle layer for improvement.
  • a mixture constituted of the above compositions is filled in each chamber installed in a general three-layer film extruder (i.e., a well-known multi-layer T-die extruder) . After that, the mixture is foamed while being simultaneously extruded, thus manufacturing a single-layer foam film.
  • Table 2 shows an extrusion temperature condition of the extruder. Because a top layer, a middle layer, and a bottom layer of a TPU film have the almost similar mixing conditions, works are performed in the same temperature condition.
  • Top layer 170 175 180 185 185 185 180 180 180 180 180 180 180 180 180 180 180 180 180 180 180 180 180 180 180
  • a cylinder, an adapter, and a dice have heaters installed in each section.
  • the cylinder is divided into four parts for heater installation
  • the adapter is divided into two parts for heater installation
  • the dice is divided into five parts for heater installation.
  • the reason of installing a heater and differentiating temperature at each section is to improve workability. In detail, it is to prevent hardening of resin at both end parts, thus enabling a smooth extrusion of molten resin.
  • a single-layer TPU film manufactured according to the above compositions and extrusion temperature condition is of a shape in which both surfaces are identically foamed and thus a surface is partially opened.
  • the TPU film is difficult for single direct use and, desirably, a non-foam TPU film is laminated and is used after one surface is covered.
  • the single-layer TPU film shows a physical property enough to avoid a problem of a use for high frequency- welding. This is shown in Table 3 in detail.
  • a non-foam film is laminated for use in a high frequency process, thus getting a surface smooth. On this surface, printing is performed and then high frequency work is performed. After the high frequency work, a very clean surface is maintained, thus providing excellent appearance.
  • a second exemplary embodiment of the present invention provides a method for manufacturing a TPU foam film constituted of a single layer, and is to obtain the maximum foam rate by maximally increasing a quantity of foam compared to the first exemplary embodiment of the present invention.
  • Table 4 shows a detail of a composition and mixture ratio of the single-layer TPU foam film.
  • extrusion is performed in the same extrusion temperature condition as in the first exemplary embodiment of the present invention, and its test result is shown in Table
  • a third exemplary embodiment of the present invention provides a method for manufacturing a TPU foam film constituted of a multiple layer, and is to selectively foam only a middle layer and a bottom layer without foaming a top layer.
  • Table 6 shows a detail of a composition and mixture ratio of each layer when manufacturing the multi-layer TPU foam film.
  • Table 7 shows an extrusion temperature condition for extruding a three-layer TPU foam film in the mixing condition of Table 6.
  • the thus manufactured multi-layer TPU foam film is already covered with a non-foam film and thus, a separate non-foam film laminating process is not required.
  • a result of high frequency welding after a printing work on a top layer is a very clean surface and shows a very excellent appearance.
  • the multi-layer TPU foam film manufactured in the mixing condition and extrusion temperature condition has a construction in which the top layer is constituted of a non-foam layer and the middle layer and bottom layer are constituted of foam layers.
  • Table 8 shows a detail of a physical property of the multi-layer TPU foam film.
  • a fourth exemplary embodiment of the present invention also provides a method for manufacturing a TPU foam film constituted of a multiple layer, and is to about double increase a quantity of use of a foam compared to the third exemplary embodiment of the present invention, thus reducing a specific gravity a little more.
  • Table 9 shows a detail of a composition and a composition ratio of the multi-layer TPU foam film, and extrusion is performed in the same extrusion temperature condition as in the third exemplary embodiment of the present invention.
  • a fifth exemplary embodiment of the present invention is to evaluate a minimum specific gravity producible with a maximum foam input.
  • Table 11 shows a composition and mixing ratio of a multi-layer TPU foam film
  • Table 12 shows a physical property of the multi-layer TPU foam film.
  • An extrusion temperature condition is the same as in the third exemplary embodiment of the present invention.
  • a conventional specific gravity of 1.20 of a film can reduce to 0.70, and more foam input leads to a failure of making excellent products because a difficulty to input raw materials into an extruder and a poor product appearance caused by excessive foam.
  • Each of exemplary embodiments below provides a detail of a composition and mixing ratio, an extrusion temperature condition, and a test result when manufacturing a multi-layer TPU foam film using the above recycling TPU.
  • recycling TPU is polyurethane resin that is a collection and recycle of scrap generated in a high frequency welding process of a shoe manufacturing process.
  • polyurethane When being repeatedly used, polyurethane is deteriorated in its physical property due to yellowing and anti-hydrolysis because of its characteristic. Therefore, the polyurethane resin is separately manufactured by mixing real TPU at a predetermined rate. Because of the scrap characteristic, the recycling TPU contains foreign materials such as ink in large quantities and thus is in an opaque state. Thus, the trend has no yellowing when using real TPU, thus getting a use of a white- color master batch unnecessary.
  • a middle layer and a bottom layer have the fully same mixture.
  • the middle layer and the bottom layer can have a different mixture without limit.
  • Table 13 shows a detail of a mixing ratio when using recycling TPU.
  • the recycling TPU is slightly different from real TPU in extrusion temperature.
  • the recycling TPU does not always have the same temperature condition as shown in Table 14, and a variation always exists more or less depending on a scrap state.
  • Table 14 below provides an extrusion temperature condition when using the recycling TPU.
  • Table 15 shows a detail of a physical property of a multi-layer TPU foam film according to the sixth exemplary embodiment of the present invention.
  • a seventh exemplary embodiment of the present invention is to use recycling TPU and increase a content of foam.
  • Table 16 shows a mixing ratio of each composition
  • Table 17 shows a detail of a test result. Extrusion is performed in the same extrusion temperature condition as in the sixth exemplary embodiment of the present invention.
  • a TPU foam film extruded with the mixing ratio can more reduce specific gravity similarly with a case using real TPU of the fourth exemplary embodiment of the present invention.
  • a product appearance is excellent because a top layer is covered with a non-foam layer.
  • a multi-layer TPU foam film is manufactured using colorless recycling TPU and its mixing ratio is shown in Table 18. Extrusion is performed in the same extrusion temperature condition as in the third exemplary embodiment of the present invention.
  • the eighth exemplary embodiment of the present invention separately manufactures the colorless recycling TPU by, upon recycling, mixing a constant quantity of real TPU with scrap like the colored recycling TPU referred in the sixth and seventh exemplary embodiments of the present invention. Also, in the eighth exemplary embodiment of the present invention, yellowing tendency can be felt because of transparency or semitransparency as in the first exemplary embodiment of the present invention. Thus, a white-color master batch is added.
  • recycling TPU uses scrap generated during an airbag manufacturing process.
  • Polyurethane used herein is generally within a range of shoreness of 9OA or more or less.
  • the polyurethane has much higher modulus than polyurethane having the shoreness of 85A or more or less of the above exemplary embodiments of the present invention.
  • a product appearance is very excellent as in the above exemplary embodiments of the present invention, and there is no particular problem even at a high frequency work after a printing work, and workability is excellent.
  • Table 19 shows the test result of the eighth exemplary embodiment of the present invention.
  • a ninth exemplary embodiment of the present invention is to co-extrude TPU whose only middle layer of the whole film is foamed and top layer and bottom layer are not foamed.
  • a top layer surface is not foamed and thus smooth, while a bottom layer surface is somewhat coarse because of a foam layer and its foamed state can be directly identified with the naked eye.
  • a film manufactured keeps smoothness at its both surfaces.
  • high frequency welding multi-layer foam films exemplified in the above exemplary embodiments of the present invention
  • lamination with a previously manufactured film having a different function for additional functionality in an extrusion step is possible.
  • a high frequency welding multi-layer foam film in which a foam film coming out of a T-die is laminated with a previously manufactured hot melt film and thus a hot melt layer is added to a lowermost layer can be manufactured.
  • an adhesive is coated on one surface of a high frequency film to increase a high frequency adhesive force before high frequency work and then, the high frequency work is executed, thus improving the adhesive force.
  • a high frequency welding Thermoplastic Polyurethane (TPU) film according to an exemplary embodiment of the present invention can be lighted in weight 20% or more, and can completely solve' a problem of a conventional TPU foam film that is a surface non-uniformity phenomenon. By this, it is possible to manufacture a high frequency welding TPU foam film of a low specific gravity that is very suitable as a high-frequency shoe material.
  • an exemplary embodiment of the present invention is a technology identically applicable to a recycling polyurethane resin as well as a real polyurethane resin, and has an advantage of being able to achieve remarkable cost saving and resource recycling.

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  • Engineering & Computer Science (AREA)
  • Mechanical Engineering (AREA)
  • Manufacturing & Machinery (AREA)
  • Extrusion Moulding Of Plastics Or The Like (AREA)

Abstract

La présente invention développe un procédé d'extrusion d'un film de mousse à travers une extrudeuse à filière en T, et permet de fabriquer un film de mousse monocouche et un film multicouche composé de deux couches ou de trois couches constitué d'une couche de mousse et d'une couche non-mousse. En particulier, le film monocouche pose des problèmes de stratification d'un film non-mousse dans la perspective d'une utilisation effective, mais une couche supérieure d'un film de mousse multicouche composé de deux couches ou de trois couches est co-extrudée sous forme de couche non-mousse, ce qui dispense d'une opération de stratification.
PCT/KR2008/007553 2008-11-20 2008-12-19 Film de mousse polyuréthane thermoplastique WO2010058876A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
KR10-2008-0115516 2008-11-20
KR1020080115516A KR100995452B1 (ko) 2008-11-20 2008-11-20 고주파 접착용 열가소성 폴리우레탄 발포 필름의 제조방법 및 상기 방법으로 제조된 열가소성 폴리우레탄 발포 필름

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KR20140147631A (ko) * 2013-06-20 2014-12-30 박희대 열가소성 폴리우레탄 핫멜트 필름의 제조방법 및 상기 방법으로 제조된 열가소성 폴리우레탄 핫멜트 필름
KR20150005092A (ko) * 2013-07-04 2015-01-14 박희대 열가소성 폴리우레탄 핫멜트 필름
KR102065849B1 (ko) * 2018-07-12 2020-01-13 황재우 착용물 접착용 폴리우레탄 발포시트 제조장치 및 상기 제조장치에 의해 제조된 폴리우레탄 발포시트

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