CN117183536A - Multilayer polymer film and dental appliance - Google Patents
Multilayer polymer film and dental appliance Download PDFInfo
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- CN117183536A CN117183536A CN202311124088.3A CN202311124088A CN117183536A CN 117183536 A CN117183536 A CN 117183536A CN 202311124088 A CN202311124088 A CN 202311124088A CN 117183536 A CN117183536 A CN 117183536A
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- polymeric film
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- multilayer polymeric
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- 229920006254 polymer film Polymers 0.000 title claims abstract description 10
- 229920000642 polymer Polymers 0.000 claims abstract description 74
- 239000000463 material Substances 0.000 claims abstract description 40
- 238000012545 processing Methods 0.000 claims abstract description 15
- 238000001125 extrusion Methods 0.000 claims abstract description 8
- 238000000034 method Methods 0.000 claims abstract description 8
- 229920001971 elastomer Polymers 0.000 claims abstract description 5
- 239000000806 elastomer Substances 0.000 claims abstract description 5
- 239000004952 Polyamide Substances 0.000 claims description 23
- 229920002647 polyamide Polymers 0.000 claims description 23
- 229920002635 polyurethane Polymers 0.000 claims description 23
- 239000004814 polyurethane Substances 0.000 claims description 23
- 229920001634 Copolyester Polymers 0.000 claims description 12
- 229920005597 polymer membrane Polymers 0.000 claims description 6
- 229920000089 Cyclic olefin copolymer Polymers 0.000 claims description 2
- 229920006020 amorphous polyamide Polymers 0.000 claims description 2
- 238000010030 laminating Methods 0.000 claims description 2
- 239000000853 adhesive Substances 0.000 abstract description 4
- 230000001070 adhesive effect Effects 0.000 abstract description 4
- 239000010410 layer Substances 0.000 description 94
- 239000002245 particle Substances 0.000 description 10
- 230000000052 comparative effect Effects 0.000 description 9
- 239000004433 Thermoplastic polyurethane Substances 0.000 description 7
- 229920002803 thermoplastic polyurethane Polymers 0.000 description 7
- 210000000214 mouth Anatomy 0.000 description 5
- 239000012528 membrane Substances 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- 238000012937 correction Methods 0.000 description 3
- 238000009826 distribution Methods 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 239000011229 interlayer Substances 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 239000008188 pellet Substances 0.000 description 3
- 239000002356 single layer Substances 0.000 description 3
- 239000002344 surface layer Substances 0.000 description 3
- 241001391944 Commicarpus scandens Species 0.000 description 2
- 230000009471 action Effects 0.000 description 2
- 238000004043 dyeing Methods 0.000 description 2
- 239000005038 ethylene vinyl acetate Substances 0.000 description 2
- 210000003128 head Anatomy 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 239000000155 melt Substances 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 229920001200 poly(ethylene-vinyl acetate) Polymers 0.000 description 2
- 229920000728 polyester Polymers 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 238000007493 shaping process Methods 0.000 description 2
- 238000010998 test method Methods 0.000 description 2
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 1
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 description 1
- 230000003796 beauty Effects 0.000 description 1
- 238000005452 bending Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000007765 extrusion coating Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920006149 polyester-amide block copolymer Polymers 0.000 description 1
- 229920005644 polyethylene terephthalate glycol copolymer Polymers 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 229920003225 polyurethane elastomer Polymers 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- 239000000779 smoke Substances 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 229920006344 thermoplastic copolyester Polymers 0.000 description 1
- 208000004371 toothache Diseases 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
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- Laminated Bodies (AREA)
Abstract
The invention discloses a multilayer polymer film and a dental appliance: the multilayer polymeric film of the present invention comprises a layer a polymer and a layer B polymer. The layer A polymer is an elastomer material, the tensile elastic modulus is 50-900MPa, and the processing temperature is 245-265 ℃; the polymer of the layer B is hard material, the tensile elastic modulus is more than 1000-2000MPa, and the processing temperature is 240-275 ℃. The A layer polymer and the B layer polymer can be directly co-extrusion laminated, and the adhesive strength grade of the A layer polymer and the B layer polymer is 0 grade according to the GB/T9286 method. Dental appliances made from the multilayer polymeric film of the present invention have good stain resistance when worn intraoral.
Description
Technical Field
The invention belongs to the technical field of high polymer materials, and relates to a multi-layer polymer membrane and a dental appliance.
Background
Invisible appliances are favored by people for a convenient and hygienic user experience. Existing appliance membranes are typically made from Thermoplastic Polyurethane (TPU) or polyester materials such as PETG and PCTG. Their security and effectiveness has been fully verified. However, both materials have some drawbacks when used alone: the thermoplastic polyurethane hardness is too high and the patient is wearing the polyurethane appliance at an early stage with a high probability of tooth pain, which can reduce patient comfort and compliance. Polyester material hardness is moderate, but because the material is easy to break under the action of stress, the material can cause higher restarting rate, and the progress of corrective treatment is greatly influenced. Leading appliance companies are using multiple layers of film to produce appliances.
Multilayer appliances proposed by Align technology (crypto) comprise an inner layer of hard copolyester, first and second outer layers of soft thermoplastic polyurethane elastomer, the inner layer of hard material being surrounded by the first and second outer layers. The bending elastic modulus of the outer layer soft polyurethane elastomer is greater than 241.4MPa, the Shore hardness is in the range of 60A-85D, and the thickness is in the range of 25-100 microns. The structure uses the soft polyurethane outer layer, and in the using process, the outer layer material is easy to damage and dye, thereby influencing the functions and the beauty. Bei Yi A material Co-Ltd (US 10549511B 2) provides a three-layer polymer film which is of sandwich construction, with an outer layer of thermoplastic copolyester material and a central layer of thermoplastic polyurethane elastomer, commercially available as Zendura TM FLX. It is known from the patent and the product description that the three-layer structure of the product has good dyeing resistance of the surface material and can provide excellent stress maintaining effect. However, the surface layer copolyester has poor mechanical properties, and silver lines and cracks are easily generated by the copolyester under the action of stress. The research shows that the appliance made of the material is also easy to generate surface damage, influences the experience of a user, and further also influences the correction progress and the correction effect.
Prior patent CN 114652465A discloses a multi-layer polymeric film and dental appliance, the film comprising a layer a polymer, a layer B polymer and a layer C polymer. The material of the layer A is copolyester, the material of the layer B is ethylene-vinyl acetate copolymer, and the material of the layer C is copolyester or polyamide. The layer B polymer is located between the layer a polymer and the layer C polymer. However, the adhesive force between the ethylene-vinyl acetate copolymer of the B layer material and the surface layer material is weak, and meanwhile, the fluidity fluctuation of the middle layer material is large and the layer thickness distribution is uneven during coextrusion processing because the processing temperature of the vinyl acetate is far lower than that of polyester and polyamide of the surface layer.
Furthermore, the known solutions use polyurethanes and copolyesters with a large processing temperature difference, typically greater than 30 ℃, which cannot be directly laminated by coextrusion, usually produced using extrusion coating. This results in insufficient adhesion between the multiple layers of polymers and a significant decrease in the yield of the article.
Disclosure of Invention
In order to solve the technical problems, the invention provides a better appliance membrane material, and provides a multi-layer polymer membrane and a dental appliance.
Specifically, the aim of the invention is achieved by the following technical scheme:
the invention provides a multilayer polymer film sheet, which comprises a layer A polymer and a layer B polymer; the layer A polymer is an elastomer material, the tensile elastic modulus is 50-900MPa, and the processing temperature is lower than 245-265 ℃; the polymer of the layer B is hard material, the tensile elastic modulus is 1000-2000MPa, and the processing temperature is 240-275 ℃.
The layer A polymer comprises polyurethane and polyamide, wherein the Shore hardness of the polyurethane is 75A-70D; in the layer A polymer, the mass fraction of polyamide is 30-70%.
The polyamide is in a transparent or translucent form.
The B layer polymer comprises at least one of copolyester, microcrystalline polyamide, amorphous polyamide, polyurethane and cycloolefin polymer.
The Shore hardness of the layer B polymer is 75D-85D.
As one embodiment of the present invention, the total thickness of the multilayer polymeric film sheet is 400 micrometers to 2500 micrometers. The thickness of the layer A polymer accounts for 10-30% of the total thickness of the multi-layer polymer film.
The tensile elastic modulus of the multilayer polymer membrane is 1000-1800MPa.
The a layer polymer thickness is 40 to 250 microns; preferably 100 to 200 microns. When the thickness of the polymer layer A is too thick, the overall elastic modulus of the material is low, so that the correction force is insufficient; when the thickness of the A layer is too thin, the strength of the A layer is insufficient, so that the A layer is easy to break, and when the thickness of the A layer is too thin, the experience of a patient when the patient wears the device is also affected.
The multilayer polymer film is prepared by laminating the layer A polymer and the layer B polymer by adopting a coextrusion mode (extrusion at respective temperature, and the temperature difference cannot exceed 30 ℃).
The mode of coextrusion is in-mold coextrusion.
The present invention also relates to a dental appliance made from the aforementioned multi-layer polymeric film sheet, conforming to one or more teeth.
Compared with the prior art, the invention has the following beneficial effects:
1. based on the multilayer polymer membrane, the layer A polymer is prepared by mixing the polyamide and the polyurethane, wherein the polyamide has good heat resistance, and the processing temperature of the layer A polymer is improved, so that the layer A polymer and the layer B polymer can be directly co-extruded and laminated, the production process is stable, and the polyurethane component has good cohesiveness, so that the interlayer combination is firm; based on the multilayer polymer film sheet, the layer A polymer and the layer B polymer have dyeing resistance and provide better aesthetic effect when being worn in the oral cavity;
2. based on the multilayer polymer membrane, the layer A polymer comprises polyurethane and polyamide, wherein the Shore hardness of the polyurethane is 75A-70D, the mass content of the polyurethane is 30-70%, the wear resistance of polyamide components is good, and the layer A polymer blended with the polyamide has better wear resistance and is not easy to penetrate layers when worn in oral cavity;
3. the multilayer polymeric film sheet according to the present invention has improved modulus properties and may provide a more comfortable wearing experience.
Detailed Description
The present invention will be described in detail with reference to examples. The following examples will assist those skilled in the art in further understanding the present invention, but are not intended to limit the invention in any way. It should be noted that several modifications and improvements can be made by those skilled in the art without departing from the inventive concept. These are all within the scope of the present invention.
In the following examples and comparative examples:
m895, smoke counter vanity, thermoplastic polyurethane;
TR90, swiss Ai Mansi, amorphous transparent polyamide;
tritan MP100, izeman, USA, a copolyester;
isoplast 2530, us road blob, thermoplastic polyurethane.
The preparation method of the multilayer polymer films of each example and comparative example is a coextrusion mode, wherein the material particles of the layer A and the material particles of the layer B are firstly dehumidified and dried until the moisture content of the materials is lower than 500ppm; and then respectively putting into different extruders for extrusion molding, wherein the layer A material and the layer B material form a multilayer structure in a die head in a melt combination mode, and the multilayer structure material is cooled and shaped to a required thickness by a shaping roller.
The specific process is as follows:
1. the polyurethane and polyamide particles of the polymer in layer A are respectively put into 2 dehumidifying dryers (dew point is lower than-40 ℃), heating temperatures are set to be 70+/-5 ℃ and 90+/-5 ℃ respectively, and the two particles are dried until the moisture content of the two particles is lower than 500ppm. According to the proportions shown in Table 1, two kinds of dried pellets were fed simultaneously into a twin-screw extruder (aspect ratio: 36-44, rotation speed: 100-150 rpm), and pelletized at the extrusion temperature shown in Table 1, and the obtained pellets were used as layer A polymer pellets.
2. And respectively putting the material particles of the layer A polymer and the material particles of the layer B polymer into 2 dehumidifying dryers (the dew point is lower than-40 ℃), setting the heating temperature to be 80-90 ℃, and drying until the moisture content of the two particles is lower than 500ppm. Putting the dried material particles of the layer A polymer into an extruder A, and putting the material particles of the layer B polymer into an extruder B; the processing temperature of the extruder A is set as the extrusion temperature of the polymer of the layer A, and the processing temperature of the extruder B is set as the extrusion temperature of the polymer of the layer B;
3. after the layer A polymer and the layer B polymer in the extruder are fully plasticized, the two polymers are extruded simultaneously through a coextrusion die, and the layer A polymer and the layer B polymer form a multilayer structure in a melt combination mode in a die head. The thickness of the layer a polymer and the layer B polymer in each example is determined by the size of the mold runner opening. The multi-layer structural material is cooled and shaped to the required thickness by a shaping roller.
TABLE 1
The performance test results are shown in Table 2 below:
tensile modulus test method referring to the method of GB/T1040.3-2006 determination of Plastic tensile Property, the device tensile speed was set at 50mm/min. Type 5 samples were used.
The residual stress test method after 24 hours is as follows: the tensile modulus test bars described in this application were drawn to 101.5% strain, the strain was maintained for 24 hours, and the decay curve of the upward pull of the bars was recorded during the break. The test environment was in a 37 ℃ water bath.
The adhesive force rating test was carried out according to the method of GB/T9286-2021, and the test results were classified into 6 ratings according to 0,1,2,3,4,5, wherein 0 rating indicates the best interlayer adhesion and 5 rating indicates the worst interlayer adhesion.
The results show that:
the layer A of comparative example 1 adopts a single component of soft polyurethane, and the stain resistance of the prepared multi-layer polymer is not ideal because the soft polyurethane has poor stain resistance. In addition, the processing temperature of the polymer of comparative example 1 was much lower than that of the polymer of layer B (temperature difference >30 ℃ C.), and the polymer of layer A was heated to cause viscosity fluctuation during coextrusion, resulting in poor appearance and thickness uniformity of the product.
The layer A of comparative example 2 adopts a blend combination of polyurethane and copolyester, and the compatibility of the two components is poor, and no synergistic effect is caused, so that the adhesive force with the layer B is poor. Meanwhile, the two materials are incompatible, so that the obtained membrane is whitened, and the attractiveness is affected.
The layer A of the comparative example 3 adopts the blending combination of soft polyurethane and hard polyurethane, the coextrusion stability of the layer A and the layer B is high, and the layer thickness distribution is uniform. However, the film of this comparative example has a high modulus of elasticity and dental appliances made therefrom have poor comfort. In addition, the multilayer film of this comparative example is inferior in stain resistance.
The layer A of comparative example 4 is polyamide, the adhesiveness of polyamide and copolyester is poor, and the membrane obtained by coextrusion is layered and cannot be used for preparing an appliance.
The single layer sample 1 was made of polyamide, which has good overall properties, but the appliance made using the film had a thinner gingival margin thickness, which easily resulted in gingival margin breakage during use. The single layer sample 2 is made of copolyester, which has the disadvantage that the appliance made of it is prone to fracture when worn in the mouth. The single-layer sample 3 is made of high-hardness polyurethane, and has excellent mechanical properties, but the elastic modulus of the material is too large, so that the appliance made of the material has poor wearing comfort in the oral cavity.
The layer a polymers of examples 1-4 are blends of polyurethane and polyamide, and it can be seen that as the polyamide content increases (w/w%), the processing temperature of the layer a polymer increases, which reduces the difference in processing temperatures between the layer a and layer B polymers, so that the flowability of each of the two layers of material remains stable during coextrusion, improving the uniformity of the layer thickness distribution and the uniformity of the total thickness of the article. The layer A polymer adopts the blending combination of polyurethane and polyamide, so that the bonding force between the layer A polymer and the layer B polymer is better, and the grade of the bonding force of the layer A of the multilayer films in the embodiments 1-4 is 0 grade, namely the best grade; the blend combination of the A-stage polymers also improves the stain resistance and fracture resistance of the multilayer film. The multilayer polymers of examples 1-4 have a moderate modulus of elasticity and the appliances made therefrom provide improved comfort when worn in the mouth.
The foregoing describes specific embodiments of the present invention. It is to be understood that the invention is not limited to the particular embodiments described above, and that various changes and modifications may be made by one skilled in the art within the scope of the claims without affecting the spirit of the invention.
Claims (10)
1. A multilayer polymeric film comprising a layer a polymer and a layer B polymer; it is characterized in that the method comprises the steps of,
the layer A polymer is an elastomer material, the tensile elastic modulus is 50-900MPa, and the processing temperature is 245-265 ℃;
the polymer of the layer B is hard material, the tensile elastic modulus is more than 1000-2000MPa, and the processing temperature is 240-275 ℃.
2. The multilayer polymer film according to claim 1, wherein the layer a polymer comprises polyurethane and polyamide, wherein the polyurethane has a shore hardness of 75A-70d and the mass fraction of polyamide in the layer a polymer is 30-70%.
3. The multilayer polymeric film sheet of claim 2, wherein the polyamide is in a transparent or translucent form.
4. The multilayer polymeric film of claim 1, wherein the B layer polymer comprises at least one of a copolyester, a microcrystalline polyamide, an amorphous polyamide, a polyurethane, a cyclic olefin polymer, and wherein the B layer polymer has a shore hardness in the range of 75D-85D.
5. The multilayer polymeric film sheet of claim 1, wherein the total thickness of the multilayer polymeric film sheet is 400-2500 microns.
6. The multilayer polymeric film of claim 1, wherein the a layer polymer has a thickness of 40-250 microns, which is 10% -30% of the total thickness of the multilayer polymeric film.
7. The multilayer polymeric film sheet of claim 1, wherein the multilayer polymeric film sheet has a tensile elastic modulus of 1000 to 1800MPa.
8. A method of producing a multilayer polymeric film sheet according to any one of claims 1 to 7, comprising the steps of: and laminating the layer A polymer and the layer B polymer in a coextrusion mode to obtain the multilayer polymer membrane.
9. The method of claim 8, wherein the co-extrusion is in-mold co-extrusion.
10. A dental appliance made from the multi-layer polymeric film of any one of claims 1-7, conforming to one or more teeth.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202311124088.3A CN117183536A (en) | 2023-09-01 | 2023-09-01 | Multilayer polymer film and dental appliance |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202311124088.3A CN117183536A (en) | 2023-09-01 | 2023-09-01 | Multilayer polymer film and dental appliance |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN117183536A true CN117183536A (en) | 2023-12-08 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202311124088.3A Pending CN117183536A (en) | 2023-09-01 | 2023-09-01 | Multilayer polymer film and dental appliance |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN117183536A (en) |
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2023
- 2023-09-01 CN CN202311124088.3A patent/CN117183536A/en active Pending
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