KR102616964B1 - Thermoplastic multilayer film for dental splints - Google Patents

Abstract

The present invention provides a center layer (A) with a thickness of 0.1 to 0.3 mm containing a thermoplastic polyurethane-based composition and a 0.2 layer formed on both sides of the center layer and containing glycol-modified polyethylene terephthalate (PolyEthylene Terephthalate-Glycol Modified, PETG). comprising first and second surface layers (B, B') having a thickness of from 0.5 mm to 0.5 mm;
Tensile strength according to ASTM D412 is 40 to 60 MPa, elongation is 200 to 400%, tensile modulus is 1500 to 2000 MPa, glass transition temperature is 78 to 85 ℃, and according to ASTM E 831 A thermoplastic multilayer film for dental splints having a thermal expansion coefficient of 150 to 170 ppm/°C;
The thermoplastic polyurethane-based composition includes 100 parts by weight of a polyol compound, 80 to 90 parts by weight of a diisocyanate compound, 1 to 10 parts by weight of a chain extender, and 1 to 10 parts by weight of an inorganic filler;
It relates to a thermoplastic multilayer film for dental splints that has excellent strength, elongation, and tensile modulus and low thermal strain.

Description

Thermoplastic multilayer film for dental splints}

The present invention provides excellent strength and elongation by forming a center layer (A) containing a thermoplastic polyurethane-based composition between the first and second surface layers (B, B') containing glycol-modified polyethylene terephthalate (PETG). and a thermoplastic multilayer film for dental splints having high tensile modulus and low thermal strain.

Dental splints are removable plastic dental aids that are at least partially adapted to the shape of the maxilla and/or mandible, such as bruxism splints, correction splints, such as retainers, These include aligners, mouthguards, bleaching splints, snoring splints, and splint-based temporary bridges.

More specifically, among correction splints, the aligner must be designed to fit over the teeth and apply translational or rotational forces to the teeth to promote movement of the correction teeth, and the retainer ( A retainer is a retaining device that stabilizes the position of the corrected teeth so that they do not deform. Additionally, dental protection devices such as mouth guards, bruxism splints, or dental splints must be able to dissipate impact forces to protect teeth from external forces, and at the same time, be flexible or thin enough to protect the teeth. It should not interfere with the natural occlusion of the teeth or interfere with speaking.

In order to accurately move teeth or protect teeth, these dental splints must have excellent strength, elongation, and tensile modulus and low thermal deformation performance.

Accordingly, conventionally, polymer films such as polypropylene (PP), polycarbonate (PC), and polyethylene terephthalate (PET) are manufactured in single to triple layers, and then softened by applying heat to form models with desired shapes such as teeth. We attempted to develop a dental splint that was stronger, lighter, and easier to use by molding it.

However, conventional dental splints still have the problem of being prone to loss of strength, wear, or deformation due to non-uniform thickness due to friction of teeth not only during manufacturing processes such as extrusion and thermoforming, but also during use, and in severe cases, tearing. This is the situation.

Republic of Korea Patent No. 10-1494273 Republic of Korea Patent No. 10-2150976 Republic of Korea Patent No. 10-2238313 Republic of Korea Patent No. 10-2279098

The present invention was devised to solve the above-mentioned problems, and one embodiment of the present invention is to prevent the thickness from becoming uneven or the strength from decreasing due to friction of teeth during use as well as during manufacturing processes such as extrusion and thermoforming. The aim is to provide a thermoplastic multilayer film for dental splints that prevents dental splints from being worn or deformed and at the same time provides excellent flexibility even at a thin thickness so as not to interfere with the natural occlusion of teeth and speaking.

The various problems to be solved by the present invention are not limited to the problems mentioned above, and other problems not mentioned will be clearly understood by those skilled in the art from the description below.

One embodiment of the present invention includes a central layer (A) having a thickness of 0.1 to 0.3 mm containing a thermoplastic polyurethane-based composition and formed on both sides of the central layer, comprising polyethylene terephthalate (PolyEthylene Terephthalate-Glycol Modified, PETG). It comprises first and second surface layers (B, B') having a thickness of 0.2 to 0.5 mm containing;

Tensile strength according to ASTM D412 is 40 to 60 MPa, elongation is 200 to 400%, tensile modulus is 1500 to 2000 MPa, glass transition temperature is 78 to 85 ℃, and according to ASTM E 831 A thermoplastic multilayer film for dental splints having a thermal expansion coefficient of 150 to 170 ppm/°C;

The thermoplastic polyurethane-based composition is a thermoplastic multilayer film for dental splints containing 80 to 90 parts by weight of a diisocyanate compound, 1 to 10 parts by weight of a chain extender, and 1 to 10 parts by weight of an inorganic filler, based on 100 parts by weight of the polyol compound. to provide.

The thermoplastic polyurethane-based composition includes 80 to 90 parts by weight of a diisocyanate compound, 1 to 10 parts by weight of a chain extender, 1 to 10 parts by weight of an inorganic filler, 0.1 to 5 parts by weight of triethyl citrate, and silyl based on 100 parts by weight of the polyol compound. Containing 0.1 to 5 parts by weight of oxalate and 0.1 to 5 parts by weight of a tetravinylcyclotetra siloxane compound represented by the following formula (1);

The inorganic filler may include 90 to 120 parts by weight of zinc sulfide, 1 to 10 parts by weight of beidellite, and 1 to 10 parts by weight of zinc silicate, based on 100 parts by weight of silica.

[Formula 1]

In [Formula 1] above,

R may be the same or different from each other, and each independently represents H, a C1 to C6 alkyl group, or a hydroxy group.

The polyol compound is a mixture of polytetramethylene ether glycol with a number average molecular weight of 500 to 2000 and polyester polyol with a number average molecular weight of 3000 to 5000 in a weight ratio of 1:0.2 to 0.5;

The polyester polyol may be at least one selected from the group consisting of polyethylene succinate polyol, polybutylene succinate polyol, polyethylene sebacate polyol, polybutylene sebacate polyol, and mixtures thereof.

The silyl oxalate may be represented by the following formula (2).

[Formula 2]

In [Formula 2] above,

R' and R" may be the same or different from each other, and each independently represents a C1 to C6 alkyl group, a vinyl group, a phenyl group, or a combination thereof.

The thermoplastic polyurethane-based composition may further include 0.1 to 5 parts by weight of valienamine represented by the following formula (3).

[Formula 3]

According to the thermoplastic multilayer film for dental splints according to an embodiment of the present invention, a thermoplastic polyurethane-based composition is contained between the first and second surface layers (B, B') containing glycol-modified polyethylene terephthalate (PETG). By forming the center layer (A), it is possible to provide a thermoplastic multilayer film for dental splints with excellent strength, elongation and tensile modulus and low thermal strain.

This has the effect of providing excellent strength and low thermal deformation performance to the teeth, allowing the teeth to be moved accurately, preventing the corrected teeth from being deformed, and effectively protecting the teeth from external shock. In addition, it is possible to effectively prevent dental splints from being worn or deformed due to uneven thickness or decreased strength due to friction of teeth not only during manufacturing processes such as extrusion and thermoforming, but also during use. At the same time, it has excellent elongation and tensile elasticity, and can provide excellent flexibility even at a thin thickness, which has the effect of not interfering with the natural occlusion of teeth and speaking.

Figure 1 shows a schematic cross-sectional view of a thermoplastic multilayer film for dental splints according to an embodiment of the present invention.

Hereinafter, embodiments of the present invention will be described in detail. However, this is presented as an example, and the present invention is not limited thereby, and the present invention is only defined by the scope of the claims to be described later.

One embodiment of the present invention includes a central layer (A) having a thickness of 0.1 to 0.3 mm containing a thermoplastic polyurethane-based composition and formed on both sides of the central layer, comprising polyethylene terephthalate (PolyEthylene Terephthalate-Glycol Modified, PETG). It comprises first and second surface layers (B, B') having a thickness of 0.2 to 0.5 mm containing;

Tensile strength according to ASTM D412 is 40 to 60 MPa, elongation is 200 to 400%, tensile modulus is 1500 to 2000 MPa, glass transition temperature is 78 to 85 ℃, and according to ASTM E 831 A thermoplastic multilayer film for dental splints having a thermal expansion coefficient of 150 to 170 ppm/°C;

The thermoplastic polyurethane-based composition provides a thermoplastic multilayer film for dental splints comprising 100 parts by weight of a polyol compound, 80 to 90 parts by weight of a diisocyanate compound, 1 to 10 parts by weight of a chain extender, and 1 to 10 parts by weight of an inorganic filler. .

A schematic cross-sectional view of the thermoplastic multilayer film for dental splints according to one embodiment of the present invention is shown in Figure 1.

The thermoplastic multilayer film for dental splints according to one embodiment of the present invention is formed on both sides of the central layer (A) with a thickness of 0.1 to 0.3 mm containing a thermoplastic polyurethane-based composition, and glycol-modified polyethylene terephthalate ( It comprises first and second surface layers (B, B') with a thickness of 0.2 to 0.5 mm containing PolyEthylene Terephthalate-Glycol Modified (PETG).

The thermoplastic multilayer film for dental splints can be manufactured by methods commonly used in the art, and the manufacturing method is not particularly limited, but thermoforming of the thermoplastic multilayer film such as co-extrusion, laminating, etc. It can be manufactured by a method. At this time, the thermoforming may be performed in the range of 150 to 300 °C.

First, the central layer (A) contains a thermoplastic polyurethane-based composition and may have a thickness of 0.1 to 0.3 mm.

This central layer (A) independently contains a thermoplastic polyurethane-based composition comprising 100 parts by weight of a polyol compound, 80 to 90 parts by weight of a diisocyanate compound, 1 to 10 parts by weight of a chain extender, and 1 to 10 parts by weight of an inorganic filler. So; The tensile strength according to ASTM D412 may be 20 to 50 MPa, the elongation may be 350 to 650%, and the thickness may be 0.1 to 0.3 mm.

More specifically, the polyol compound reacts with the diisocyanate compound to improve excellent strength, elongation, and tensile modulus.

These polyol compounds are commonly used in the art and are not particularly limited in type, but non-limiting examples of the polyol compounds include polytetramethylene ether glycol with a number average molecular weight of 500 to 2000 and a number average molecular weight of 500 to 2000. More preferably, a mixture of 3000 to 5000 polyester polyols at a weight ratio of 1:0.2 to 0.5 can be used. As a result, the effect of improving elongation and tensile modulus can be further improved.

At this time, the polyester polyol may be one or more selected from the group consisting of polyethylene succinate polyol, polybutylene succinate polyol, polyethylene sebacate polyol, polybutylene sebacate polyol, and mixtures thereof.

Hereinafter, the content of other components constituting the thermoplastic polyurethane-based composition is based on 100 parts by weight of the polyol compound.

The diisocyanate compound reacts with the polyol compound and functions to improve excellent strength, elongation, and tensile modulus.

These diisocyanate compounds are commonly used in the art and are not particularly limited in type, but non-limiting examples of the diisocyanate compounds include naphthalene diisocyanate (NDI; Naphthalene-1,5-diisocyanate), Paraphenylene diisocyanate (PPDI), tolidine diisocyanate (TODI), diphenyl methane diisocyanate (MDI), toluene diisocyanate (TDI), hexamethylene diisocyanate (HDI; hexamethylene diisocyanate), dicyclohexylmethane diisocyanate (H12MDI; dicyclohexylmethane diisocyanate), isophorone diisocyanate (IPDI; Isoporone diisocyanate), and mixtures thereof may be used.

The diisocyanate compound is preferably contained in the range of 80 to 90 parts by weight based on 100 parts by weight of the polyol compound. If the content of the diisocyanate compound is too small, there is a problem that the above-mentioned improvement effect may be insufficient, and if the content of the diisocyanate compound is too high, there is a problem that the hardness may increase too much and flexibility may decrease.

The chain extender increases the degree of crosslinking, improves viscosity, and improves excellent strength, melt strength, thermoplasticity, and thermoformability.

These chain extenders are commonly used in the art and are not particularly limited in type, but non-limiting examples of the chain extenders include ethylene glycol, 1,2-propylene glycol, and 1,3-propane. Diol, 1,4-butanediol, 1,6-hexanediol, diethylene glycol, 2-methyl-1,3-propanediol, 3-methyl-1,5-pentanediol, 2,2-dimethyl-1,3 -At least one diol-based chain extension selected from the group consisting of propanediol, 2,2,4-trimethyl-1,5-pentanediol, 2-methyl-2-ethyl-1,3-propanediol, and mixtures thereof You can use je.

The chain extender is preferably contained in the range of 1 to 10 parts by weight based on 100 parts by weight of the polyol compound. If the content of the chain extender is too small, there is a problem that the above-mentioned improvement effect may be insufficient, and if the content of the chain extender is too large, there is a problem that the hardness may increase too much and the flexibility may decrease.

The inorganic filler functions to achieve excellent strength and constant thickness while being thin, and to have low thermal deformation.

The type of the inorganic filler is not particularly limited as it is commonly used in the art, but non-limiting examples of the inorganic filler include those containing silica.

The inorganic filler may preferably include 100 parts by weight of silica, 90 to 120 parts by weight of zinc sulfide, 1 to 10 parts by weight of beidellite, and 1 to 10 parts by weight of zinc silicate.

The inorganic filler is preferably contained in the range of 1 to 10 parts by weight based on 100 parts by weight of the polyol compound. If the content of the inorganic filler is too small, the improvement effect may be insufficient, and if the content of the inorganic filler is too high, flexibility and thermoformability may be reduced.

More specifically, the silica functions to improve adhesion with the first and second surface layers (B, B') to create a multilayer film with excellent strength.

The silica has an average particle diameter of 10 to 30 μm, and the surface of which has been modified by fluorine treatment can be preferably used.

More specifically, the silica, the surface of which has been modified by the fluorine treatment, is mixed with ammonium fluoride (NH ₄ F), ammonium difluoride (NH ₄ HF ₂ ), and hydrogen fluoride (HF) in 100 parts by weight of distilled water at a temperature of 40 to 60 ° C. ) and mixtures thereof, adding and stirring 10 to 50 parts by weight of silica to an aqueous solution of 0.01 to 0.10 parts by weight of one or more fluorine compounds to prepare a silica slurry; Distilling the silica slurry under reduced pressure and drying it in an oven to obtain dried fluorine-treated silica powder; and heat-treating the dried fluorine-treated silica powder at a temperature of 300 to 500° C. to obtain silica whose surface has been modified by fluorine treatment. This not only further improves the above-mentioned improvement effect, but also improves the tensile modulus and effectively prevents discoloration of the film over time.

Hereinafter, the content of other components constituting the inorganic filler is based on 100 parts by weight of the silica.

The zinc sulfide functions to achieve excellent strength and constant thickness while being thin.

The zinc sulfide is preferably contained in the range of 90 to 120 parts by weight based on 100 parts by weight of the silica. If the content of zinc sulfide is too small, there is a problem that the improvement effect described above may be insufficient, and if the content of zinc sulfide is too high, there is a problem that thermoformability may be reduced.

The beidellite functions to have excellent strength and low thermal strain.

The beidellite is preferably contained in the range of 1 to 10 parts by weight based on 100 parts by weight of the silica. If the content of beidellite is too small, there is a problem that the improvement effect may be insufficient, and if the content of beidellite is too high, there is a problem that flexibility may be reduced. .

The zinc silicate functions to improve adhesion with the first and second surface layers (B, B') to create a multilayer film with excellent strength.

The zinc silicate is preferably contained in the range of 1 to 10 parts by weight based on 100 parts by weight of the silica. If the zinc silicate content is too small, the improvement effect may be insufficient, and if the zinc silicate content is too high, the thermoformability may be reduced.

In addition, in order to further improve the above-described improvement effect, the thermoplastic polyurethane composition contains 0.1 to 5 parts by weight of triethyl citrate, 0.1 to 5 parts by weight of silyl oxalate, and 0.1 to 0.1 to 5 parts by weight of a tetravinylcyclotetrasiloxane compound represented by the following formula (1). It may further include 5 parts by weight.

That is, the thermoplastic polyurethane-based composition includes 100 parts by weight of a polyol compound, 80 to 90 parts by weight of a diisocyanate compound, 1 to 10 parts by weight of a chain extender, 1 to 10 parts by weight of an inorganic filler, 0.1 to 5 parts by weight of triethyl citrate, and silyl It may contain 0.1 to 5 parts by weight of oxalate and 0.1 to 5 parts by weight of a tetravinylcyclotetra siloxane compound represented by the following formula (1).

[Formula 1]

In [Formula 1] above,

R may be the same or different from each other, and each independently represents H, a C1 to C6 alkyl group, or a hydroxy group.

More specifically, the triethyl citrate functions to soften the composition to maintain a constant thickness and achieve excellent thermoforming performance without tearing.

The triethyl citrate is preferably contained in the range of 0.1 to 5 parts by weight based on 100 parts by weight of the polyol compound. If the content of triethyl citrate is too small, there is a problem that the above-mentioned improvement effect may be insufficient, and if the content of triethyl citrate is too high, there is a problem that the thermoformability may be reduced due to excessive softening.

The silyl oxalate functions to prevent agglomeration of the composition, improve elongation, and further improve adhesion with the first and second surface layers (B, B') to create a multilayer film with excellent strength.

The above effect can be further improved by using the silyl oxalate represented by the following formula (2).

[Formula 2]

In [Formula 2] above,

R' and R" may be the same or different from each other, and each independently represents a C1 to C6 alkyl group, a vinyl group, a phenyl group, or a combination thereof.

More specifically, the silyl oxalate is one or more selected from the group consisting of dimethylsilyl oxalate, vinylphenylsilyl oxalate, methylvinylsilyl oxalate, diphenylsilyl oxalate, and mixtures thereof to achieve the above-described effect. can be further improved.

The silyl oxalate is preferably contained in the range of 0.1 to 5 parts by weight based on 100 parts by weight of the polyol compound. If the content of the silyl oxalate is too small, the improvement effect may be insufficient, and if the content of the silyl oxalate is too high, the elastic modulus may be reduced.

The tetravinylcyclotetra siloxane compound represented by the formula (1) provides tensile modulus and improves adhesion with the first and second surface layers (B, B') to create a multilayer film with excellent strength. .

The tetravinylcyclotetrasiloxane compound represented by Formula 1 is preferably contained in the range of 0.1 to 5 parts by weight based on 100 parts by weight of the polyol compound. If the content of the tetravinylcyclotetra siloxane compound represented by Formula 1 is too small, there is a problem that the improvement effect may be insufficient, and if the content of the tetravinylcyclotetra siloxane compound represented by Formula 1 is too high. There is a problem that it is difficult to expect any further improvement effect and price competitiveness may be reduced.

In addition, the thermoplastic polyurethane-based composition may further include 0.1 to 5 parts by weight of valienamine represented by the following formula (3) in order to provide excellent adhesive strength, tensile modulus, and low thermal deformation.

[Formula 3]

Meanwhile, the first and second surface layers (B, B') formed on both sides of the center layer are each independently a film containing polyethylene terephthalate (PolyEthylene Terephthalate-Glycol Modified, PETG). There is no particular limitation. However, as a non-limiting example of the film containing the glycol-modified polyethylene terephthalate (PolyEthylene Terephthalate-Glycol Modified, PETG), the tensile strength according to ASTM D412 is 40 to 60 MPa, and the elongation is 100 to 200%, One with a thickness of 0.2 to 0.5 mm can be preferably used.

The thermoplastic multilayer film for dental splints according to one embodiment of the present invention has a tensile strength of 40 to 60 MPa according to ASTM D412, an elongation of 200 to 400%, a tensile modulus of 1500 to 2000 MPa, and a glass transition temperature ( Glass transition temperature) may be 78 to 85°C, and the thermal expansion coefficient according to ASTM E 831 may be 150 to 170 ppm/°C. In other words, it is possible to provide a thermoplastic multilayer film for dental splints with excellent strength, elongation, and tensile modulus and low thermal strain.

This has the effect of providing excellent strength and low thermal deformation performance to the teeth, allowing the teeth to be moved accurately, preventing the corrected teeth from being deformed, and effectively protecting the teeth from external shock. In addition, it is possible to effectively prevent dental splints from being worn or deformed due to uneven thickness or decreased strength due to friction of teeth not only during manufacturing processes such as extrusion and thermoforming, but also during use. At the same time, it has excellent elongation and tensile elasticity, and can provide excellent flexibility even at a thin thickness, which has the effect of not interfering with the natural occlusion of teeth and speaking.

Above, the present invention has been described in detail with preferred embodiments, but the present invention is not limited to the above embodiments, and various modifications may be made by those skilled in the art within the scope of the technical idea of the present invention. This is possible.

[Production Example 1]

Preparation of polyol compounds

Polytetramethylene ether glycol with a number average molecular weight of 2000 was used.

[Production Example 2]

Preparation of polyol compounds

A mixture of polytetramethylene ether glycol with a number average molecular weight of 1000 and poly(ethylene succinate) glycol with a number average molecular weight of 4000 at a weight ratio of 1:1 was used.

[Production Example 3]

Preparation of polyol compounds

A mixture of polytetramethylene ether glycol with a number average molecular weight of 1000 and poly(ethylene succinate) glycol with a number average molecular weight of 4000 at a weight ratio of 1:0.3 was used.

[Production Example 4]

Preparation of silica with surface modification by fluorine treatment

At a temperature of 50°C, 30 parts by weight of silica (average particle diameter: 17 μm) was added to an aqueous solution of 100 parts by weight of distilled water and 0.07 parts by weight of ammonium difluoride (NH ₄ HF ₂ ), and then stirred for 5 hours to form silica. A slurry was prepared. After distilling the silica slurry under reduced pressure, it was dried in an oven at 75° C. to obtain dried fluorine-treated silica powder. Thereafter, the dried fluorine-treated silica powder was heat-treated at a temperature of 450° C. for 7 hours to obtain silica whose surface was modified by fluorine treatment.

[Examples and Comparative Examples]

Master batches containing a thermoplastic polyurethane-based composition prepared with the ingredients and contents shown in Table 1 below and a comparative composition were prepared, respectively. On one side of the first surface layer (B) prepared as a substrate, the thermoplastic polyurethane-based composition and the comparative composition were melt-extruded at a temperature of 260° C. to form a central layer (A) in a film state. At this time, the first surface layer (B) prepared as the substrate used was SK Chemical's SKYGREEN S2008 film containing polyethylene terephthalate-Glycol Modified (PETG). The film for the first surface layer (B) had a tensile strength of 50 MPa according to ASTM D412, an elongation of 140%, and a thickness of 0.3 mm.

Meanwhile, the formed central layer (A) in the form of a film was melt-extruded to a thickness of 0.2 mm without any additional materials, and a separate central layer (A) for measuring physical properties was formed. For the central layer (A) for measuring these physical properties, the tensile strength, elongation, and average thickness according to ASTM D412 were measured and are shown in Table 1 below.

Thereafter, the second surface layer (B') is laminated on the other side of the center layer (A), and co-extruded and laminated at a temperature of 200 ° C, thereby forming the first surface layer (B) / center layer (A) )/A multilayer film for forming dental aids that was laminated with the second surface layer (B') was manufactured. At this time, SK Chemical's SKYGREEN S2008 film containing polyethylene terephthalate-Glycol Modified (PETG) was used as the film for the laminated second surface layer (B'). The film for the second surface layer (B') had a tensile strength of 50 MPa according to ASTM D412, an elongation of 140%, and a thickness of 0.3 mm.

Thermoplastic polyurethane-based composition (category: parts by weight) Example 1 Example 2 Example 3 Comparative Example 1 Comparative example 2 polyol compounds 100
[Production Example 2] 100
[Production Example 2] 100
[Production Example 3] 100
[Production Example 1] 100
[Production Example 2] Diisocyanate compound_
Diphenylmethane diisocyanate 85 85 85 85 85 Chain extender_diethylene glycol 5 5 5 5 5 Triethyl citrate 2.5 2.5 2.5 - 2.5 Dimethylsilyl oxalate 1.5 - One - - Vinylphenylsilyl oxalate - 1.5 0.5 tetravinylcyclotetra
Siloxane compound [Formula 1;
R is a hydroxy group] 1.5 1.5 1.5 - - Valienamine [Formula 3] - - 2 - - inorganic filler 7 7 7 7 7 (part by weight) Silica (average particle size:
17 μm) 100
[Ordinary silica powder] 100
[Production Example 4] 100
[Production Example 4] 100
[Ordinary silica powder] 100
[Ordinary silica powder] zinc sulfide 100 100 100 - - Beidellite 8 8 8 - 8 zinc silicate 7 7 7 - - Physical properties of the central layer (A) ASTM D412 Tensile strength (MPa) 41.3 43.2 44.6 36.9 38.3 Elongation rate (%) 400 470 520 310 370 Average thickness (mm) 0.2 0.2 0.2 0.2 0.2

[Test example]

Below, experimental results are shown comparing the characteristics of the Examples according to the present invention and Comparative Examples 1 and 2 so that the characteristics of the thermoplastic multilayer film for dental splints manufactured according to Examples 1 to 3 can be more easily understood. will be.

Evaluation of physical properties of multilayer films

The test results for the physical properties of the thermoplastic multilayer films for dental splints prepared according to Examples 1 to 3 and the comparative multilayer films prepared according to Comparative Examples 1 and 2 are shown in Table 2 below.

Test Items Test Methods Example 1 Example 2 Example 3 Comparative Example 1 Comparative example 2 Tensile strength (MPa) ASTM D412 46 52 56 39 41 Elongation rate (%) ASTM D412 224 231 249 106 118 Tensile modulus
(MPa) ASTM D412 1730 1930 1970 1180 1260 glass transition temperature
(℃) Thermal analysis by DSC (q20 v24.11 build 124) 81.9 80.5 81.3 111.5 102.3 thermal expansion coefficient
(ppm/℃) ASTM E831 162 164 151 199 184

As can be seen in Table 2, the thermoplastic multilayer films for dental splints prepared according to Examples 1 to 3 exhibit excellent physical properties compared to the comparative multilayer films prepared according to Comparative Examples 1 and 2. I was able to confirm.

As described above, those skilled in the art to which the present invention pertains will understand that the present invention can be implemented in other specific forms without changing its technical idea or essential features. Therefore, all embodiments described above should be understood as illustrative and not restrictive. The scope of the present invention should be construed as including all changes or modified forms derived from the meaning and scope of the claims described below and their equivalent concepts rather than the detailed description above.

A: Center layer
B: first surface layer B': second surface layer

Claims (5)

A center layer (A) having a thickness of 0.1 to 0.3 mm containing a thermoplastic polyurethane-based composition and a center layer (A) having a thickness of 0.2 to 0.5 mm formed on both sides of the center layer and containing glycol-modified polyethylene terephthalate (PolyEthylene Terephthalate-Glycol Modified, PETG). It comprises first and second surface layers (B, B') of a thickness of;
Tensile strength according to ASTM D412 is 40 to 60 MPa, elongation is 200 to 400%, tensile modulus is 1500 to 2000 MPa, glass transition temperature is 78 to 85 ℃, and according to ASTM E 831 A thermoplastic multilayer film for dental splints having a thermal expansion coefficient of 150 to 170 ppm/°C;
The thermoplastic polyurethane-based composition is
A thermoplastic multilayer film for dental splints, comprising 80 to 90 parts by weight of a diisocyanate compound, 1 to 10 parts by weight of a chain extender, and 1 to 10 parts by weight of an inorganic filler, based on 100 parts by weight of the polyol compound.
According to paragraph 1,
The thermoplastic polyurethane-based composition is
Based on 100 parts by weight of polyol compound, 80 to 90 parts by weight of diisocyanate compound, 1 to 10 parts by weight of chain extender, 1 to 10 parts by weight of inorganic filler, 0.1 to 5 parts by weight of triethyl citrate, 0.1 to 5 parts by weight of silyl oxalate. and 0.1 to 5 parts by weight of a tetravinylcyclotetrasiloxane compound represented by the following formula (1);
The inorganic filler is
A thermoplastic multilayer film for dental splints, comprising 90 to 120 parts by weight of zinc sulfide, 1 to 10 parts by weight of beidellite, and 1 to 10 parts by weight of zinc silicate, based on 100 parts by weight of silica.
[Formula 1]

In [Formula 1] above,
R may be the same or different from each other, and each independently represents H, a C1 to C6 alkyl group, or a hydroxy group.
According to paragraph 1,
The polyol compound is
Polytetramethylene ether glycol with a number average molecular weight of 500 to 2000 and polyester polyol with a number average molecular weight of 3000 to 5000 are mixed in a weight ratio of 1:0.2 to 0.5;
The polyester polyol is
A thermoplastic multilayer film for dental splints, comprising at least one selected from the group consisting of polyethylene succinate polyol, polybutylene succinate polyol, polyethylene sebacate polyol, polybutylene sebacate polyol, and mixtures thereof.
According to paragraph 2,
The silyl oxalate is a thermoplastic multilayer film for dental splints, characterized in that it is represented by the following formula (2).
[Formula 2]

In [Formula 2] above,
R' and R" may be the same or different from each other, and each independently represents a C1 to C6 alkyl group, a vinyl group, a phenyl group, or a combination thereof.
According to paragraph 1,
The thermoplastic polyurethane-based composition is
A thermoplastic multilayer film for dental splints, further comprising 0.1 to 5 parts by weight of valienamine represented by the following formula (3).
[Formula 3]