CN113974869B - 一种多层聚合物膜片及牙科器具 - Google Patents
一种多层聚合物膜片及牙科器具 Download PDFInfo
- Publication number
- CN113974869B CN113974869B CN202111177815.3A CN202111177815A CN113974869B CN 113974869 B CN113974869 B CN 113974869B CN 202111177815 A CN202111177815 A CN 202111177815A CN 113974869 B CN113974869 B CN 113974869B
- Authority
- CN
- China
- Prior art keywords
- polymer
- layer
- multilayer
- phthalic acid
- film
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
- 229920000642 polymer Polymers 0.000 title claims abstract description 32
- 229920001634 Copolyester Polymers 0.000 claims abstract description 10
- 239000004433 Thermoplastic polyurethane Substances 0.000 claims abstract description 8
- -1 aliphatic amino acid Chemical class 0.000 claims abstract description 8
- 229920002803 thermoplastic polyurethane Polymers 0.000 claims abstract description 8
- 125000003118 aryl group Chemical group 0.000 claims abstract description 7
- 150000003951 lactams Chemical class 0.000 claims abstract description 7
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 claims abstract description 5
- 125000002723 alicyclic group Chemical group 0.000 claims abstract description 5
- 239000005038 ethylene vinyl acetate Substances 0.000 claims abstract description 3
- 229920001200 poly(ethylene-vinyl acetate) Polymers 0.000 claims abstract description 3
- 229920006254 polymer film Polymers 0.000 claims description 11
- RLSSMJSEOOYNOY-UHFFFAOYSA-N m-cresol Chemical compound CC1=CC=CC(O)=C1 RLSSMJSEOOYNOY-UHFFFAOYSA-N 0.000 claims description 8
- 229920002635 polyurethane Polymers 0.000 claims description 8
- 239000004814 polyurethane Substances 0.000 claims description 8
- 229920006020 amorphous polyamide Polymers 0.000 claims description 7
- 238000004519 manufacturing process Methods 0.000 claims description 6
- IGSBHTZEJMPDSZ-UHFFFAOYSA-N 4-[(4-amino-3-methylcyclohexyl)methyl]-2-methylcyclohexan-1-amine Chemical compound C1CC(N)C(C)CC1CC1CC(C)C(N)CC1 IGSBHTZEJMPDSZ-UHFFFAOYSA-N 0.000 claims description 4
- 239000004215 Carbon black (E152) Substances 0.000 claims description 3
- 229930195733 hydrocarbon Natural products 0.000 claims description 3
- 150000002430 hydrocarbons Chemical class 0.000 claims description 3
- 238000002360 preparation method Methods 0.000 claims description 3
- 239000004721 Polyphenylene oxide Substances 0.000 claims description 2
- 229920000728 polyester Polymers 0.000 claims description 2
- 229920000570 polyether Polymers 0.000 claims description 2
- 239000000126 substance Substances 0.000 claims description 2
- 239000000463 material Substances 0.000 abstract description 67
- 239000004952 Polyamide Substances 0.000 abstract description 27
- 229920002647 polyamide Polymers 0.000 abstract description 27
- 239000012528 membrane Substances 0.000 abstract description 17
- 229920005597 polymer membrane Polymers 0.000 abstract description 3
- FEUISMYEFPANSS-UHFFFAOYSA-N 2-methylcyclohexan-1-amine Chemical compound CC1CCCCC1N FEUISMYEFPANSS-UHFFFAOYSA-N 0.000 abstract description 2
- 239000010410 layer Substances 0.000 description 45
- 230000000052 comparative effect Effects 0.000 description 19
- 239000002356 single layer Substances 0.000 description 17
- 238000012360 testing method Methods 0.000 description 16
- 238000000034 method Methods 0.000 description 11
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 10
- 238000005299 abrasion Methods 0.000 description 10
- 238000012937 correction Methods 0.000 description 10
- 238000006243 chemical reaction Methods 0.000 description 8
- 239000000203 mixture Substances 0.000 description 8
- 239000002245 particle Substances 0.000 description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 7
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 description 6
- 230000014759 maintenance of location Effects 0.000 description 6
- 238000010998 test method Methods 0.000 description 5
- 230000000694 effects Effects 0.000 description 4
- 238000001125 extrusion Methods 0.000 description 4
- QQVIHTHCMHWDBS-UHFFFAOYSA-N isophthalic acid Chemical compound OC(=O)C1=CC=CC(C(O)=O)=C1 QQVIHTHCMHWDBS-UHFFFAOYSA-N 0.000 description 4
- 230000008569 process Effects 0.000 description 4
- 229920001169 thermoplastic Polymers 0.000 description 4
- 238000010521 absorption reaction Methods 0.000 description 3
- 230000009471 action Effects 0.000 description 3
- 230000009286 beneficial effect Effects 0.000 description 3
- 238000001816 cooling Methods 0.000 description 3
- 239000013078 crystal Substances 0.000 description 3
- 239000000155 melt Substances 0.000 description 3
- ACVYVLVWPXVTIT-UHFFFAOYSA-N phosphinic acid Chemical compound O[PH2]=O ACVYVLVWPXVTIT-UHFFFAOYSA-N 0.000 description 3
- 229920003023 plastic Polymers 0.000 description 3
- 239000004033 plastic Substances 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 2
- 150000001412 amines Chemical class 0.000 description 2
- 230000005540 biological transmission Effects 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 238000005260 corrosion Methods 0.000 description 2
- 230000007797 corrosion Effects 0.000 description 2
- 238000002425 crystallisation Methods 0.000 description 2
- 230000008025 crystallization Effects 0.000 description 2
- 239000008367 deionised water Substances 0.000 description 2
- 229910021641 deionized water Inorganic materials 0.000 description 2
- 229920001971 elastomer Polymers 0.000 description 2
- 239000000806 elastomer Substances 0.000 description 2
- 239000011261 inert gas Substances 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 239000002985 plastic film Substances 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 239000004332 silver Substances 0.000 description 2
- 229910052709 silver Inorganic materials 0.000 description 2
- 238000010186 staining Methods 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 239000002344 surface layer Substances 0.000 description 2
- UQXNEWQGGVUVQA-UHFFFAOYSA-N 8-aminooctanoic acid Chemical compound NCCCCCCCC(O)=O UQXNEWQGGVUVQA-UHFFFAOYSA-N 0.000 description 1
- JHWNWJKBPDFINM-UHFFFAOYSA-N Laurolactam Chemical compound O=C1CCCCCCCCCCCN1 JHWNWJKBPDFINM-UHFFFAOYSA-N 0.000 description 1
- 239000004677 Nylon Substances 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 230000002238 attenuated effect Effects 0.000 description 1
- 239000012752 auxiliary agent Substances 0.000 description 1
- 238000005452 bending Methods 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 230000006835 compression Effects 0.000 description 1
- 238000007906 compression Methods 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 230000003670 easy-to-clean Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 238000010528 free radical solution polymerization reaction Methods 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 238000007731 hot pressing Methods 0.000 description 1
- 238000010030 laminating Methods 0.000 description 1
- 238000003475 lamination Methods 0.000 description 1
- 239000004611 light stabiliser Substances 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 239000006082 mold release agent Substances 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 229920001778 nylon Polymers 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 238000005498 polishing Methods 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 229920003225 polyurethane elastomer Polymers 0.000 description 1
- 238000005096 rolling process Methods 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 238000007493 shaping process Methods 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 229920006344 thermoplastic copolyester Polymers 0.000 description 1
- 229920002725 thermoplastic elastomer Polymers 0.000 description 1
- 239000004416 thermosoftening plastic Substances 0.000 description 1
- 238000013022 venting Methods 0.000 description 1
- 239000004636 vulcanized rubber Substances 0.000 description 1
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L77/00—Compositions of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Compositions of derivatives of such polymers
- C08L77/02—Polyamides derived from omega-amino carboxylic acids or from lactams thereof
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61C—DENTISTRY; APPARATUS OR METHODS FOR ORAL OR DENTAL HYGIENE
- A61C7/00—Orthodontics, i.e. obtaining or maintaining the desired position of teeth, e.g. by straightening, evening, regulating, separating, or by correcting malocclusions
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61C—DENTISTRY; APPARATUS OR METHODS FOR ORAL OR DENTAL HYGIENE
- A61C7/00—Orthodontics, i.e. obtaining or maintaining the desired position of teeth, e.g. by straightening, evening, regulating, separating, or by correcting malocclusions
- A61C7/08—Mouthpiece-type retainers or positioners, e.g. for both the lower and upper arch
-
- 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
- B29C48/14—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor characterised by the particular extruding conditions, e.g. in a modified atmosphere or by using vibration
- B29C48/146—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor characterised by the particular extruding conditions, e.g. in a modified atmosphere or by using vibration in the die
-
- 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
- B29C48/88—Thermal treatment of the stream of extruded material, e.g. cooling
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/06—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/06—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material
- B32B27/08—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/30—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers
- B32B27/306—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers comprising vinyl acetate or vinyl alcohol (co)polymers
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/34—Layered products comprising a layer of synthetic resin comprising polyamides
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/36—Layered products comprising a layer of synthetic resin comprising polyesters
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/40—Layered products comprising a layer of synthetic resin comprising polyurethanes
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B33/00—Layered products characterised by particular properties or particular surface features, e.g. particular surface coatings; Layered products designed for particular purposes not covered by another single class
-
- 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
- B29C2948/00—Indexing scheme relating to extrusion moulding
- B29C2948/92—Measuring, controlling or regulating
- B29C2948/92504—Controlled parameter
- B29C2948/92609—Dimensions
- B29C2948/92647—Thickness
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2250/00—Layers arrangement
- B32B2250/24—All layers being polymeric
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2250/00—Layers arrangement
- B32B2250/40—Symmetrical or sandwich layers, e.g. ABA, ABCBA, ABCCBA
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2307/00—Properties of the layers or laminate
- B32B2307/50—Properties of the layers or laminate having particular mechanical properties
- B32B2307/536—Hardness
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2307/00—Properties of the layers or laminate
- B32B2307/50—Properties of the layers or laminate having particular mechanical properties
- B32B2307/54—Yield strength; Tensile strength
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2307/00—Properties of the layers or laminate
- B32B2307/50—Properties of the layers or laminate having particular mechanical properties
- B32B2307/554—Wear resistance
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2307/00—Properties of the layers or laminate
- B32B2307/70—Other properties
- B32B2307/714—Inert, i.e. inert to chemical degradation, corrosion
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2307/00—Properties of the layers or laminate
- B32B2307/70—Other properties
- B32B2307/732—Dimensional properties
- B32B2307/737—Dimensions, e.g. volume or area
- B32B2307/7375—Linear, e.g. length, distance or width
- B32B2307/7376—Thickness
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2535/00—Medical equipment, e.g. bandage, prostheses, catheter
-
- 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
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
-
- 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
Landscapes
- Health & Medical Sciences (AREA)
- Engineering & Computer Science (AREA)
- Mechanical Engineering (AREA)
- Oral & Maxillofacial Surgery (AREA)
- Dentistry (AREA)
- Epidemiology (AREA)
- Life Sciences & Earth Sciences (AREA)
- Animal Behavior & Ethology (AREA)
- General Health & Medical Sciences (AREA)
- Public Health (AREA)
- Veterinary Medicine (AREA)
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Chemistry (AREA)
- Physics & Mathematics (AREA)
- Thermal Sciences (AREA)
- Polymers & Plastics (AREA)
- Medicinal Chemistry (AREA)
- Materials For Medical Uses (AREA)
- Dental Tools And Instruments Or Auxiliary Dental Instruments (AREA)
- Laminated Bodies (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Dental Preparations (AREA)
Abstract
本发明公开了一种多层聚合物膜片及牙科器具;本发明的膜片包含A层聚合物和B层聚合物。所述A层材料为聚酰胺,其包含以下基团:(1)36摩尔%至40摩尔%的4,4‑亚甲基双(2‑甲基环己烷胺)、(2)36摩尔%至40摩尔%的芳香族二羧酸,所述芳香族二羧酸为1,3‑苯二甲酸(IPA)和/或1,4‑苯二甲酸(TPA),(3)20摩尔%至28摩尔%的脂环族或脂肪族氨基酸或内酰胺。B层聚合物位于两层A层聚合物之间。B层材料由热塑性聚氨酯、乙烯‑醋酸乙烯共聚物或共聚聚酯中的至少一种组成。
Description
技术领域
本发明属于高分子材料技术领域,涉及一种多层聚合物膜片及牙科器具。
背景技术
无托槽牙颌矫治器是一种计算机辅助设计和制作的活动矫正装置,它包含序列连续的多个弹性透明矫治装置,通过不断的小范围推动牙移动达到牙齿矫正的目的。上述矫治器通常由热塑性塑料膜片热压成型,经过切割和打磨等工序制备而成。佩戴者通常每1周或每2周更换一副矫治器,整个矫治过程可持续数十月。在矫治的不同阶段仅部分牙齿移动,另外的牙齿作为支抗。在设计规则一定的前提下,选择合适的热塑性塑料膜片,就可以控制矫治力的大小,同时也能控制矫治力作用的时间。矫治速度的快慢和矫治效果是否理想,较大程度上取决于所使用的热塑性塑料膜片的性能。
矫治器用膜片需要具有较好的应力保持性能,以便在1到2周的佩戴时间内,提供用于牙齿移动的作用力。同时,矫治器用膜片应能够抵抗牙齿咬合破坏和应力开裂,以避免佩戴过程中矫治器的破坏和断裂。此外,为提供美观性,矫治器膜片还应能够抵挡食物玷污,并易于清洁和消毒。
为应对上述要求,矫治器材料的开发已经从单种材料的单层结构向多种材料多层结构演变。多种材料复合使用,有利于取长补短,实现更好的综合性能。
Align technology(隐适美)公司是首先推出多层材料矫治器的公司,根据其专利(US9655691B2)披露,其提供了一种牙科器具,具有多层结构,包含硬质共聚酯内层,第一和第二软质热塑性聚氨酯弹性体外层,内层硬质材料被第一和第二外层包裹。外层软质聚氨酯弹性体的弯曲弹性模量大于241.4MPa,邵氏硬度范围为60A-85D,厚度范围为25-10微米。第一和第二的软质热塑性聚氨酯其压缩永久变形大于40%(70℃,24小时),中间层共聚酯材料在90-100%湿度下,24小时内应力松弛大于10%。根据临床反馈,该种材料制成的矫治器易于摘戴,矫治力适中,具有较好的佩戴舒适感。但这种结构使用了软质聚氨酯外层,在使用过程中,外层材料容易破损和染色,影响了功能和美观。
贝伊材料有限责任公司(US10549511B2)提供了一种三层聚合物材料,其采用三明治结构,外层A和C为热塑性共聚聚酯材料,B层中心层为热塑性聚氨酯弹性体。该种材料结构可以避免表层材料的染色,同时提供出色的应力保持效果。但因表层共聚聚酯力学性能欠佳,在应力作用下,共聚聚酯易产生银纹和断裂。研究发现,由该种材料制成的矫治器同样易产生表面破损,影响使用者的体验感,进一步的也会影响矫治进度和矫治效果。
发明内容
为解决上述问题,提供更好的矫治器膜片材料,本发明提供了一种多层聚合物膜片及牙科器具。
聚酰胺材料(俗称尼龙)具有优异的力学性能和化学性能,其机械强度高、韧性好、耐磨性佳、具有自润滑性,耐油性和耐溶剂性佳。通用的聚酰胺材料如PA6,PA66或PA12为不透明或半透明材料,不适用于无托槽矫治器的制作。且这类材料吸水性高,饱和吸水率可达到9~12%,在潮湿环境中力学性能大幅下降。透明聚酰胺是一种具备特殊结构的无定型或者微结晶聚合物,无定型透明聚酰胺分子链上通常含有侧基或环结构,以此破坏分子链规整性,使得它不结晶,不影响可见光传播;微晶聚酰胺的晶体大小只能达到纳米级别,也不会影响到可见光传播。上述两种机制可实现聚酰胺材料的透明性。透明聚酰胺不影响美观性,因而可以考虑被用来制备矫治器。不同配方的透明聚酰胺,其性能差异较大。
本发明发现,当采用改性的聚酰胺材料作为矫治器膜片材料时,可提供出色的应力保持和耐磨耗性。这种改性的聚酰胺材料包含(1)36摩尔%至40摩尔%的4,4-亚甲基双(2-甲基环己烷胺)、(2)36摩尔%至40摩尔%的芳香族二羧酸,所述芳香族二羧酸为1,3-苯二甲酸(IPA)和/或1,4-苯二甲酸(TPA),(3)20摩尔%至28摩尔%的脂环族或脂肪族氨基酸或内酰胺。基于这种特殊改性的聚酰胺材料的多层材料,显现出了优异的应力保持性能和耐磨耗性。同时,该种材料表面摩擦系数更低,更有利于矫治器的摘戴,整体提供了更佳的矫治效果和佩戴体验感。
具体而言,本发明的目的是通过以下技术方案实现的:
本发明提供了一种多层聚合物膜片,包含A层聚合物和B层聚合物;
A层聚合物为非晶聚酰胺;
B层聚合物为热塑性聚氨酯、乙烯-醋酸乙烯共聚物、共聚聚酯中的至少一种;
B层聚合物位于两层A层聚合物之间。
作为本发明的一个实施方案,所述A层聚合物的硬度范围为45D到87D。
作为本发明的一个实施方案,所述A层聚合物由如下物质聚合而成:(1)4,4-亚甲基双(2-甲基环己烷胺)、(2)芳香族二羧酸,所述芳香族二羧酸为1,3-苯二甲酸(IPA)和/或1,4-苯二甲酸(TPA),(3)脂环族或脂肪族氨基酸或内酰胺。其中,脂肪族氨基酸的结构通式NH2-R-COOH,其中,R为C5-C35的支链或环脂族烃。内酰胺结构通式如下:
作为本发明的一个实施方案,所述A层聚合物的吸水率低于5%,优选的吸水率低于3.5%,特别优选的吸水率低于3%。
作为本发明的一个实施方案,所述A层聚合物相对粘度大于1.45,测试方法为在20℃下在0.5%的间甲酚溶液中根据ISO 307标准测试。
在一些实施例中,所述芳香族二羧酸为1,3-苯二甲酸(IPA)和1,4-苯二甲酸(TPA)的混合,其中TPA最多占芳香族二酸总量的50%。在本发明的体系中,1,3-苯二甲酸和1,4-苯二甲酸共用,避免分子链过分规整,从而形成结晶,影响制品的透明度。
本发明中可用的非晶聚酰胺可由已知的方法制备,例如熔融聚合法和溶液聚合法。适合的方法包括,但不限于下面的步骤:第一步制备低聚物,将1,4-苯二甲酸或1,3-苯二甲酸或者两者的混合物与胺基化合物缩合得到二酸低聚物。该反应通常在惰性气体和压力下进行,边反应边搅拌。反应温度保持在260~310℃,压力为一个大气压或者30bar。每1摩尔1,4-苯二甲酸或1,3-苯二甲酸或者两者混合物所使用的胺基化合物的用量为0.8~2摩尔。第二步在大气压下向二酸低聚物中加脂环族或脂肪族氨基酸或内酰胺,在250~310℃下反应。反应通常在惰性气体氛围中进行,在真空和/或大气压下和/或在最高为20bar下进行。每1摩尔1,4-苯二甲酸或1,3-苯二甲酸或者两者混合物对应使用的脂肪族氨基酸或内酰胺的用量为0.6-1.5摩尔。
第二步反应中通常使用催化剂如磷酸和次磷酸。在这步反应中根据需要补加1,4-苯二甲酸和/或1,3-苯二甲酸。总体来说,1,4-苯二甲酸的摩尔含量不超过1,4-苯二甲酸和1,3-苯二甲酸总量的50%。同时,第二步反应中可能会加入光稳定剂、稳定剂、增塑剂、脱模剂等助剂。
作为本发明的一个实施方案,所述多层聚合物膜片的总厚度为400微米至1500微米,其中,B层聚合物的厚度为50至1000微米,优选100至800微米,更优选150至500微米。
作为本发明的一个实施方案,所述A层聚合物耐受乙醇腐蚀。
作为本发明的一个实施方案,所述多层聚合物膜片,其拉伸弹性模量大于800MPa,优选的大于1000MPa。在一些实施例中,所述多层聚合物膜片的拉伸弹性模量为800-4500MPa,优选1000-4500MPa。
作为本发明的一个实施方案,所述热塑性聚氨酯为聚醚型或聚酯型聚氨酯,邵氏硬度范围为40D-85D。
作为本发明的一个实施方案,所述多层聚合物膜片,通过共挤出层合。在一些实施例中,所述A层聚合物和B层聚合物分别挤出成型后,以层合的方式形成多层结构,制得所述多层聚合物膜片。可选择分配器共挤或者模内共挤,优选模内共挤的层合方式。
本发明还涉及一种牙科器具,由前述多层聚合物膜片制成,与一颗或多颗牙齿共形。
与现有技术相比,本发明具有如下有益效果:
1)基于本发明的特殊改性的聚酰胺材料的多层材料,显现出了优异的应力保持性能和耐磨耗性能;
2)基于本发明的特殊改性的聚酰胺材料的多层材料,表面摩擦系数更低,更有利于矫治器的摘戴,整体提供了更佳的矫治效果和佩戴体验感;
3)基于本发明的特殊改性的聚酰胺材料的多层材料,相较于单层结构的材料,其具有更好的柔性,更易于摘戴;
4)基于本发明的特殊改性的聚酰胺材料的多层材料,具有抗乙醇腐蚀的功能,由其制成的器具可以使用医用酒精进行消毒,更有利于使用者的健康。
附图说明
通过阅读参照以下附图对非限制性实施例所作的详细描述,本发明的其它特征、目的和优点将会变得更明显:
图1为单层产品应力松弛测试结果;
图2为对比例应力松弛测试结果;
图3为实施例应力松弛测试结果。
具体实施方式
下面结合实施例对本发明进行详细说明。以下实施例将有助于本领域的技术人员进一步理解本发明,但不以任何形式限制本发明。应当指出的是,对本领域的普通技术人员来说,在不脱离本发明构思的前提下,还可以做出若干调整和改进。这些都属于本发明的保护范围。
以下实施例中涉及的改性聚酰胺EPA-1和EPA-2的投料配比为:
(1)EPA-1:48.2kg4,4-亚甲基双(2-甲基环己烷胺)(分子量238.42)、17.0kg 1,4-苯二甲酸(分子量166.131)、17.0kg 1,3-苯二甲酸(分子量166.131)和28.8kg十二内酰胺(分子量197.317)、30kg去离子水和11g次磷酸(50%溶液)。将上述物质在容器中预先混合,氮气钝化后将混合物加热到230℃,然后将混合物吸入反应容器。搅拌状态下将混合物加热到295℃,并在20bar压力下保持4小时。然后将压力降到大气压,并进行排气。将熔体流出至水浴降温,边降温边造粒。所得粒子经除湿干燥至水份含量低于0.05%,可用于挤出生产膜片。在20℃下,所得粒子在0.5%的间甲酚溶液中的粘度为1.52。
(2)EPA-2:48.2kg 4,4-亚甲基双(2-甲基环己烷胺)(分子量238.42)、34.0kg1,3-苯二甲酸(分子量166.131)和23.2kg 1,8-氨基辛酸(分子量159.226)、25kg去离子水和8g次磷酸(50%溶液)。EPA-2的反应条件与EPA-1一致。所得粒子需除湿干燥至水份含量低于0.05%后方可用于挤出生产膜片。在20℃下,所得粒子在0.5%的间甲酚溶液中的粘度为1.46。
各实施例、对比样品的多层聚合物膜片的制备方法为共挤出方式,具体过程为,先将A层材料粒子和B层材料粒子除湿干燥8小时以上,使得两种材料的水分含量低于0.05%。然后分别投入两台不同的挤出机挤出成型,A层材料和B层材料在模头中以熔体结合的方式形成多层结构,上述多层结构材料经定型辊冷却定型至需要的厚度。
性能测试结果如下表2:
表2
*对比例1应力衰减严重,仅测试了6小时应力松弛。
拉伸弹性模量测试方法参照《GB/T 1040.3-2006塑料拉伸性能的测定》的方法,设备拉伸速度设置50mm/min。采用5型试样。
弯曲弹性模量测试方法参照《GB/T 9341-2008塑料弯曲性能的测定》规定的方法进行测试。
抗撕裂强度测试方法参考《GB/T 529-2008硫化橡胶或热塑性橡胶撕裂强度的测定》中方法B,实验程序(a)进行测试,其中制备样本按标准中5.1.2进行,样本厚度以产品实际厚度为准,拉伸速度为500±50mm/min。
按照《GB/T 5478-2008塑料滚动磨损试验方法》测试膜片材料的磨耗值,采用CS10磨轮,计量磨耗1000转之后的磨耗值。
应力松弛测试方法为:取本案所述拉伸弹性模量测试样条,拉伸至101.5%应变,保持该应变24小时,记录该断时间内样条上拉力的衰减曲线。测试环境为37℃水浴中。
图1、2、3为各实施例、对比例、单层产品的应力保持比率对比示意图;对比例1,2和3类似专利US10549511B2中的实施例。表1揭示了各对比例的材料结构组成。对比例1使用了3层聚氨酯结构,即表层为硬质聚氨酯,内层为软质聚氨酯。图2为材料应力松弛的测试结果,从图2可以看到,对比例1这种结构的材料应力松弛严重,仅6小时后,其残余应力仅为初始应力的18%。单层产品3为由对比例1的外层硬质聚氨酯制成,从图1可以看到该种材料本身应力松弛较严重,当使用该种材料组合为多层材料时,其应力松弛进一步恶化。
对比例2、对比例4和对比例5使用了微晶聚酰胺材料制备了一种三层膜片,由该微晶聚酰胺制成的单层材料为单层产品2。对比例2、对比例4和对比例5中间层选用不同的材料。从图2可以看出,该微晶聚酰胺单层膜片的应力松弛较严重,在24小时应力松弛测试后,膜片的残余应力仅为初始应力的38%。对比例2、对比例4和对比例5的三层膜片应力松弛略小于单层产品2,24小时应力松弛测试后,三种膜片的残余应力分别为初始应力的46%、49%和42%。可见,不管如何更换中间层材料,其制成的多层膜片应力衰减依然比较严重。微晶聚酰胺分子链无支链,分子链结构规整易产生结晶,但因其晶区较小,不影响材料的透明性,因此可用于隐形矫治器的制作。本发明人对该微晶聚酰胺的研究发现,该种材料的应力衰减较快,与常用的硬质聚氨酯(例如单层产品3)无显著差异。推测正是因为微晶区的存在,导致了应力衰减较快的结果。此外,该种微晶聚酰胺不能耐受乙醇,不易使用医用酒精(75%乙醇溶液)进行消毒,不便于佩戴者消毒。
对比例3使用了共聚聚酯制备了一种三层膜片。从图2可以看出,该实施方案的膜片应力松弛较小,24小时应力松弛测试后,对比例3膜片的残余应力为初始应力的65%。值得注意的是,共聚聚酯材料的耐磨耗性较差,表2揭示的该种材料Taber研磨测试下的磨耗值明显高于其他对照品,较高的磨耗值通常意味着使用过程中材料更易损耗和破裂。而且在持续应力作用下,该种材料易产生银纹从而导致材料的力学性能失效。这两个缺点可能会影响矫治治疗的进展。
实施例1和实施例2为改性聚酰胺EPA-1和EPA-2制备的三层膜片。从图3可以看到,两者的应力松弛非常小。在24小时的应力松弛测试后,所述实施例1和实施例2膜片中的残余应力分别为初始应力的78%和74%。由改性聚酰胺EPA-1制成的单层膜片,其应力松弛较小,在24小时的应力松弛测试后,EPA-1单层膜片中的残余应力为初始应力的72%。
实施例3和实施例4为以市购的两种非晶聚酰胺制备的多层膜片。由该两种非晶聚酰胺制备的单层膜片为单层产品4和单层产品5。在24小时的应力松弛测试后,实施例3和实施例4的两种膜片的残余应力分别为初始应力的62%和55%。与此对应的单层产品4和单层产品5,24小时的应力松弛测试后的残余应力为初始应力的58%和52%。与实施例1和实施例2相比,该市购的两种非晶聚酰胺应力松弛更严重,但优于对比例2、对比例4和对比例5。
实施例5为改性聚酰胺EPA-1与共聚聚酯Tritan MX710共挤出制备的多层膜片。从图3可以看到,这种组合的材料具有良好的应力保持性能。在24小时的应力松弛测试后,实施例5膜片中的残余应力为初始应力的71%。由于EPA-1和Tritan MX710的硬度均较高,实施例5的材料体感较硬,舒适度低于其余实施例。但这两种材料的加工温度接近,给生产加工带来了便利,生产工艺更稳定,有利于降低生产成本。
综合上述内容,本发明的实施例具有更低的应力松弛率,耐磨耗性能优越,是一种理想的矫治器用膜片。
以上对本发明的具体实施例进行了描述。需要理解的是,本发明并不局限于上述特定实施方式,本领域技术人员可以在权利要求的范围内做出各种变形或修改,这并不影响本发明的实质内容。
Claims (8)
2.根据权利要求1所述的多层聚合物膜片,其特征在于,所述非晶聚酰胺的硬度范围为45D-87D。
3.根据权利要求1所述的多层聚合物膜片,其特征在于,所述芳香族二羧酸为1,3-苯二甲酸和1,4-苯二甲酸,其中1,4-苯二甲酸占芳香族二酸总量≤50%。
4.根据权利要求1所述的多层聚合物膜片,其特征在于,所述A层聚合物相对粘度大于1.45,测试方法为在20℃下在0.5%的间甲酚溶液中根据ISO 307标准测试。
5.根据权利要求1所述的多层聚合物膜片,其特征在于,所述多层聚合物膜片的总厚度为400微米至1500微米;所述多层聚合物膜片的拉伸弹性模量大于800MPa。
6.根据权利要求1所述的多层聚合物膜片,其特征在于,所述热塑性聚氨酯为聚醚型或聚酯型聚氨酯,邵氏硬度范围为40D-85D。
7.一种根据权利要求1-6中任一项所述的多层聚合物膜片的制备方法,其特征在于,所述A层聚合物和B层聚合物采用模内共挤出的方式进行层合,制得所述多层聚合物膜片。
8.一种牙科器具,由如权利要求1-6中任一项所述的多层聚合物膜片制成,与一颗或多颗牙齿共形。
Priority Applications (5)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN202111177815.3A CN113974869B (zh) | 2021-10-09 | 2021-10-09 | 一种多层聚合物膜片及牙科器具 |
AU2022359601A AU2022359601A1 (en) | 2021-10-09 | 2022-03-31 | Multilayer polymer diaphragm and dental appliance |
EP22877761.1A EP4295807A1 (en) | 2021-10-09 | 2022-03-31 | Multilayer polymer diaphragm and dental appliance |
US18/281,972 US20240182711A1 (en) | 2021-10-09 | 2022-03-31 | Multilayer polymer sheet and dental appliance |
PCT/CN2022/084235 WO2023056735A1 (zh) | 2021-10-09 | 2022-03-31 | 一种多层聚合物膜片及牙科器具 |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN202111177815.3A CN113974869B (zh) | 2021-10-09 | 2021-10-09 | 一种多层聚合物膜片及牙科器具 |
Publications (2)
Publication Number | Publication Date |
---|---|
CN113974869A CN113974869A (zh) | 2022-01-28 |
CN113974869B true CN113974869B (zh) | 2023-04-14 |
Family
ID=79737999
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CN202111177815.3A Active CN113974869B (zh) | 2021-10-09 | 2021-10-09 | 一种多层聚合物膜片及牙科器具 |
Country Status (5)
Country | Link |
---|---|
US (1) | US20240182711A1 (zh) |
EP (1) | EP4295807A1 (zh) |
CN (1) | CN113974869B (zh) |
AU (1) | AU2022359601A1 (zh) |
WO (1) | WO2023056735A1 (zh) |
Families Citing this family (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN113974869B (zh) * | 2021-10-09 | 2023-04-14 | 上海恺皓科技有限公司 | 一种多层聚合物膜片及牙科器具 |
WO2023250488A1 (en) * | 2022-06-23 | 2023-12-28 | Bay Materials, Llc. | Dental appliances, materials constructions and improved treatment systems |
CN117485002A (zh) * | 2022-07-26 | 2024-02-02 | 上海优丽泰薄膜材料有限公司 | 一种高应力保持的多层聚合物膜、其制造方法及其制品 |
Citations (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN107810215A (zh) * | 2015-06-19 | 2018-03-16 | 斯特塔思有限公司 | 用于增材制造的水分散性聚合物 |
Family Cites Families (15)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CA1024292A (en) * | 1972-03-10 | 1978-01-10 | E.I. Du Pont De Nemours And Company | Process for producing high molecular weight copolyesters in the presence of diaryl esters |
US4013624A (en) * | 1972-03-20 | 1977-03-22 | E. I. Du Pont De Nemours And Company | Branched thermoplastic copolyesters |
US7641828B2 (en) * | 2004-10-12 | 2010-01-05 | Align Technology, Inc. | Methods of making orthodontic appliances |
CA2589070A1 (en) * | 2004-12-07 | 2006-06-15 | Lg Chem. Ltd. | Pipe having barrier property |
US9655691B2 (en) | 2012-05-14 | 2017-05-23 | Align Technology, Inc. | Multilayer dental appliances and related methods and systems |
CN102825875A (zh) * | 2012-08-24 | 2012-12-19 | 爱索尔(广州)包装有限公司 | 多层复合片材及其制备方法 |
KR101248249B1 (ko) * | 2012-11-06 | 2013-03-27 | 한국엔지니어링플라스틱 주식회사 | 치과용품 |
JP6048742B2 (ja) * | 2013-03-06 | 2016-12-21 | 三菱瓦斯化学株式会社 | 酸素吸収性医療用多層容器 |
US20200031993A1 (en) * | 2017-12-18 | 2020-01-30 | Stratasys, Inc. | Water dispersible polymer for use in additive manufacturing |
US20210237364A1 (en) * | 2015-06-19 | 2021-08-05 | Stratasys, Inc. | Method of treating a dispersion of sulfopolymer |
JP7448295B2 (ja) * | 2017-05-31 | 2024-03-12 | ベイ マテリアルズ エルエルシー | 二重シェル歯科装置及び材料構成 |
CN108727810B (zh) * | 2018-05-23 | 2020-06-09 | 江苏金发科技新材料有限公司 | 长玻纤增强聚酰胺组合物及其制备方法 |
CN213167278U (zh) * | 2020-04-30 | 2021-05-11 | 上海顶鉴新材料科技有限公司 | 一种具有低温热再塑性的膜片及牙科器具 |
CN213649050U (zh) * | 2020-09-21 | 2021-07-09 | 杭州津源新材料有限公司 | 一种制作牙套用膜片及牙套 |
CN113974869B (zh) * | 2021-10-09 | 2023-04-14 | 上海恺皓科技有限公司 | 一种多层聚合物膜片及牙科器具 |
-
2021
- 2021-10-09 CN CN202111177815.3A patent/CN113974869B/zh active Active
-
2022
- 2022-03-31 AU AU2022359601A patent/AU2022359601A1/en active Pending
- 2022-03-31 US US18/281,972 patent/US20240182711A1/en active Pending
- 2022-03-31 WO PCT/CN2022/084235 patent/WO2023056735A1/zh active Application Filing
- 2022-03-31 EP EP22877761.1A patent/EP4295807A1/en active Pending
Patent Citations (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN107810215A (zh) * | 2015-06-19 | 2018-03-16 | 斯特塔思有限公司 | 用于增材制造的水分散性聚合物 |
Also Published As
Publication number | Publication date |
---|---|
EP4295807A1 (en) | 2023-12-27 |
US20240182711A1 (en) | 2024-06-06 |
CN113974869A (zh) | 2022-01-28 |
AU2022359601A1 (en) | 2023-09-28 |
EP4295807A9 (en) | 2024-02-14 |
WO2023056735A8 (zh) | 2023-10-05 |
WO2023056735A1 (zh) | 2023-04-13 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
CN113974869B (zh) | 一种多层聚合物膜片及牙科器具 | |
JP4264359B2 (ja) | 透明気体バリア積層体に用いる組成物 | |
TWI722597B (zh) | 具有改善模數性質之多層膜 | |
JP4123475B2 (ja) | 低吸水性ポリエーテルポリアミドエラストマー | |
TWI473834B (zh) | 具有改良光學性質之包含醯胺單元且包含醚單元的共聚物 | |
MX2008015652A (es) | Combinaciones y aleaciones con base en un amorfo para un copolimeo semi-cristalino que comprende unidades amida y que comprende unidades eter, estos materiales tienen propiedades opticas mejoradas. | |
JP2009526891A (ja) | 光学的特性が改良されたポリアミドブロックとポリエーテルブロックとを有するコポリマー | |
WO2001023458A1 (fr) | Elastomere thermoplastique, son utilisation et son procede de production | |
KR20130124596A (ko) | 이축연신된 통기성 필름, 이의 제조방법 및 이의 용도 | |
EP0244445A1 (en) | MULTILAYER STRUCTURES MADE OF POLYETHYLENE REEPHTHALATE AND ELASTOMERIC COPOLYESTER ETHERS. | |
MXPA94003135A (es) | Uso de una composicion laminada de un material textil. | |
JP2020502301A (ja) | 水蒸気透過性物品に押出成形可能なポリマー組成物 | |
TW202306756A (zh) | 薄膜及其製備方法、透光性層疊體、覆蓋膜以及多層電子設備 | |
EP2212109B1 (en) | Multilayer constructions | |
EP3129076A1 (fr) | Utilisation de peba à blocs longs pour la fabrication de tout ou partie d'un cathéter | |
CN114981341A (zh) | 薄膜、薄膜的制造方法、覆盖膜及多层电子设备 | |
JP2002121274A (ja) | 熱可塑性エラストマー、その用途及びその製造方法 | |
JP5104457B2 (ja) | 多層構造体 | |
JP2011126243A (ja) | 多層構造体 | |
JP7419370B2 (ja) | 物品の凹面状表面のトポグラフィーへの適用に有用な高分子シートとそれに関連する方法 | |
CN106739309A (zh) | 一种赋型聚氨酯复合薄膜及其制备方法 | |
KR20230066549A (ko) | 폴리아마이드 및 그로 이루어지는 성형체 및 필름, 및 해당 폴리아마이드의 제조 방법 | |
KR102328190B1 (ko) | 투명한 폴리에테르에스테르 엘라스토머 수지 및 이로부터 제조된 성형품 | |
US20220250362A1 (en) | Multilayer sheet | |
WO2024021171A1 (zh) | 一种高应力保持的多层聚合物膜、其制造方法及其制品 |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
PB01 | Publication | ||
PB01 | Publication | ||
SE01 | Entry into force of request for substantive examination | ||
SE01 | Entry into force of request for substantive examination | ||
GR01 | Patent grant | ||
GR01 | Patent grant |