TW200840831A - Polyurethane composite material and application thereof - Google Patents

Abstract

The present invention provides a polyurethane-based composite material which comprises thermoplastic polyurethane (TPU) and filler. The thermoplastic polyurethane is formed through reaction of diisocyanate, polyol and a chain extender, each with a predetermined ratio. The present invention also discloses root canal filler.

Description

200840831 IX. INSTRUCTIONS OF THE INVENTION: TECHNICAL FIELD OF THE INVENTION The present invention relates to a composite material which is related to the use of a thermoplastic polyurethane composite material and its application in root canal sealing. [Prior Art] The ultimate goal of root canal treatment is to return the teeth to a healthy state with proper appearance and (4) function after the treatment has been repaired. The treatment can be divided into three phases: diagnosis, root canal preparation, and root canal filling (obturatibn). The root canal seal is the important one that is the most important one. The entire management system will be completed, and the pure village material will be sealed as close as possible to the cementy tooth and the essence. Dense sealing is the success of root canal treatment _ key - not only can reduce _ via the apical peripherema into the root canal system to avoid secondary infection (I ^ c〇ntami, ti〇n), and can Enclose the irritant that can not be removed during the debridement and modification of the root canal

Within the root canal system. The root canal filling mainly consists of at least one cone made of special material into the root canal opening, and then the cones are glued together by a seal j (sealer) to seal the opening. Fill it up. Current root canal sealing operations use Gutta-Percha (GP) or resilon with a sealer as a sealing material. Most of the surgery uses vertical or parallel extrusion and filling technology after heating. The principle is to use the plasticity of the rubber or resil〇n to be softened by heat, and the vertical force of the n (Piugger) is applied to the root tip in 200840831, and the colloid is applied. Squeezing densely packed with the sealant in the root canal system _, fine_tubes all the external openings (portals of exit), reaching the three-dimensional space "tight filling. The main defect of the traditional root canal filling material package" material biology The compatibility of CbioccMpatibiliW is not easy to be organized by bees. The dentist needs to precisely control the amount of colloids placed in the roots of the teeth during surgery to avoid excessive body parts from the root tip (_ oozing; the shape of the plastic machine after cooling is insufficient; The bonding of the material disk sealant (special_high class); the adhesion of the root wall (the wall esi〇n-good and the shrinking process during the cooling process) It is difficult to provide a seal-tight effect that creates a gap between the gums and the filler, which in turn causes micro-leakage (oieakage) phenomenon. The bacteria grow in _ and the material loosens to cause secondary (four) teeth. Develop high biocompatibility, low body Shrinkage hybrid disc root canal wall and the outline of the wheel heteroaryl, strict control of the rotation male mechanical Di ^ filler materials has become an important research directions. SUMMARY OF THE INVENTION

In view of the above-mentioned background of the invention, which meets the requirements of the industry, the present invention provides a polyurethane-based composite material and a method and application thereof. X The present invention is directed to providing a thermoplastic polyurethane sulphate 200840831 (Thermoplastic P〇lyurei:hane, τρυ) argon composite which can be modified by varying different diisocyanate 〇>i isocyanate and The reaction ratio of the alcohol (Poly〇i) adjusts the physical properties and the dropout properties of the finished material. Another object of the present invention is to apply the above-mentioned thermoplastic polyurethane composite material to a cone material of a root canal sealing material, wherein the main system of the above-mentioned cone material is the above-mentioned polyamino group. The formate composite's adjusts the physical properties and chemical properties of the finished product by changing the reaction ratio of the different diisocyanate to the polyfluorene, and mixing the anti-gj drug to make the antibacterial property. Accordingly, the present invention can meet the economic benefits and the utilization of the industry.

According to the above, the present invention discloses a polyurethane (PU) composite material, which is a thermoplastic polyurethane (TPU) and a filler. Mixed. The above thermoplastic polyaminophthalate comprises a linear polyurethane backbone, and the polyurethane backbone further comprises: a hard segment and a soft segment, wherein the hard segment is separated by a pair The isocyanate 3iiS〇cyanafe) is formed by reaction with a chain extender, and the soft segment is formed of a polyol. On the other hand, the above-mentioned spent polyaminophthalate composite material can be applied to a root canal sealing material. 200840831 [Embodiment] The present invention is directed to a Polyurethane (PU) composite material and its application.

In the invention, a detailed step hip and its composition will be presented in the following description. Obviously, the riding of Shuming is not limited (4). The other party φ, a well-known composition or step list, is not described in the details to avoid the necessity of the present invention. The present invention will be described in detail below with reference to the detailed description of the present invention, and the invention may be widely practiced in other embodiments, and the details of the invention are defined by the following claims.第一 A first embodiment of the present invention discloses a polyurethane composite comprising - a thermoplastic polyurethane and a "filler." The above thermoplastic polyurethane S is intended to comprise a polyurethane polyurethane, and the polyurethane primary bond comprises a hard segment and a soft segment, and f, the hard segment is formed by using -bisisocyanate Formed by reacting with a chain extender, the soft chain segment is formed by a poly-amp; and the above-mentioned filler comprises an inorganic material, preferably, a zinc oxide fluoride bath gel R〇aiumin〇siiicategiass) and so on. On the one hand, the above-mentioned chain extension tanning agent can be selected as I 4-Butanediol (l, 4-BD). The above-mentioned double isocyanic acid vinegar can be an aromatic double isocyanic acid vinegar (aromatic peak espresso eS), circular double heterotrophic acid vinegar Calicyclic 200840831

Polyisocyanates), aliphatic polyisocyanates, or a combination thereof. Further description of the choice of diisocyanate can be as follows: (1) aromatic diisocyanate moiety: tolylene diisocyanate (TDI) (2,4- or 2,6-TDI), diphenylmethane diisocyanate (MDI) (4 , 4'- or 2, 4'-Mj)I), polymeric MDI, xylylene diisocyanate (XDI), naphtfiylene diisocyanate (NDI) (usually 1,5-NDI), paraphenylene diisocyanate (PPDI), tetramethy1xy1y1ene diisocyanate (TMXDI), Tolidine diisocyanate; (TODI), 3, 3'-dimethoxy-4, 4'-biphenylene diisocyanate, etc.; (2) cyclohexamethylene diisocyanate moiety: di'cyclohexylmethane di isocyanate (HMDI) (4, 4'- or 2, 4 '-HMDI), isopHorone di isocyanate (IPDI), i sopropy1i dene-b i s-(4-cyc1ohexy1i socyanate)(IPC), hydrogenated xylylene di isocyanate i(hydrogenated XDI), cyclohexylene diisocyanate (CHPI)(usually 1,4 -CHPI), 1,5-tetrahydonaphthalene di isocyanate, etc.; (3) aliphatic diisocyanate moiety: hexamethylene di isocyanate (HDI), lysine di isocyanate (LDI), 丨tetramethylene di isocyanate, and the like. Preferably, the diisocyanate is selected from one of the following groups or a combination thereof: a cyclic bisisocyanate or an aliphatic bis isocyanate. 200840831 The above polyalcohol may be a poly-ester polyol, a poly-ether polyol or a group thereof. Among them, the preferred choice of the polyester type polyol can be as follows: Polycaprolactone (PCL), Po1y (buty1ene-ad i pate) glycol (PBA),

Po1y(ethy1ene-ad i pate) glycol; (PEA),

Poly(ethy1ene-buty1ene-ad i pate) glycol (PEBA),

Poly(hexylene-adipate) glycol (PHAj et al; on the other hand, a preferred choice of polyether polyols can be as follows: Polyethylene Glycol (PEG) - Polypropylene Glycol (PPG) i Polytetramethylene

Glycol (PTMEG), Polytetramethylene丨Oxide (PTMO), etc. First Example Polyurethane Composites< Thermal Properties Comparison This example compares different types and weight ratios; polyalcohol, diisocyanate and chain extender to the final formed polyaminophthalic acid vinegar composite heat The effect of the properties, wherein the polyurethane resin comprises a thermoplastic polyurethane and a filler having a weight ratio of less than 0.5 (weight ratio of 3:7); the polyol used is P〇ly (butylene-adipate) glyC〇l (PBA) and the chain extender is 1,4-Butanediol (1,4-BD). The comparison results are shown in Table 1 below: 200840831 Table 1 Comparison of Thermal Properties of Polyurethane Composites Poly-ol/ diisocyanate / chain extender (TPU: 30wt% of total composite)

Melting point (C) \ HDI as diisocyanate IPDI as diisocyanate 1/160/0.5 1/1.36/0.3 1/112/0.1 48,6 (Composite 1P1.) 48,0 (Composite IP2.) 48.3 (Composite IP3.) 54.1 (Composite Η1;) 53,9 (Composite Η2;) 54.1 (Composite H3L) (TPU: 30wt% of total composite)

Commercial Gutta-Percha melting point is about 6 〇 · 〇 l °c; and commercial j.

ResiIon H is about 60· 57 C. (Source: A comparison of thermal properties between gutta-percha and a synthetic polymer based root canal filling material (Resilon). Journal of Endodontics, 2006 Jul; 32(7): 683-6. Miner MR, Berzins DW, Bahcall JK ·). From the comparison results, when the weight ratio of the polyhydric alcohol to the diisocyanate is equal to 0.8 (weight ratio 1:1·6〇), the polyurethane formed by the fjexamethylene Di isocyanate (HDI) as the diisocyanate material is compounded. The material has a melting point of 54.1 C; and Isophorone Diisocyanate (IPDI) as a diisocyanate material is 48·6 t:. Further, when the above weight ratio is increased (> 0.8), the melting point of the formed polyurethane composite material does not change significantly, but the temperature is maintained below 55. Hey. _More temperature range and commercial 12 200840831

The melting points of Guta-Percha and Resil〇n provide a lower melting point for the polyurethane composites provided in this example. Since the clinician needs to pre-heat and soften the sealing material in order to perform the root surgery, the melting point of the sealing material should not be too high. From the above results, it can be seen that the polyurethane composite material provided by the present invention is in compliance with industrial needs. Second Example Polyurethane Composites Winter Mechanical Properties Comparison This example compares the effects of different weight ratios of polyol, bismuth diisocyanate and chain extender on the mechanical properties of the resulting polyurethane composite. The weight ratio of the thermoplastic polyurethane and the filler contained in the polyurethane composite material is less than 〇·5; the polyalcohol used in the fight is

Poly(butylene-adipate) glyc〇l (PBA) and the chain extender is 1,4-Butanediol (1, 4, BD). The comparison results are shown in Table #2: Table 2 Comparison of Mechanical Properties of Polyurethane Composites ΐTPU Composition Mechanical Properties L/esigiiaiions Polyol / Diisocyanate / Chain extender Tensile Strength (Mpa) Yang's Modulus ( Mpa) Composite HI 1/1.60/0.5 Not-available Not-available Composite H2 1/1.36/0.3 Not-available Not-available 13 200840831

Composite H3 1/L12/0.1 21.8+2.6 130.0118.3 Composite IP1 1/1.60/0.5 Not-available Not-available Composite IP2 1/136/0.3 0.8±0.3 32·1±13.4 Composite BP3 1/1.12/ 0.1 15i8± 1.9 96.2±17.7 Gutta-percha — 5·98±1·15 (8) 78.71±23.41(a) Resilon 8.09i2.30(a) 86.58142.23(a) As can be seen from the table, commercial Gutta-percha; and Resi Ion materials The tensile strength is less than 10 MPa and its Young's Modulus is less than 90 MPa. In the polyurethane composite provided by the present invention, when the weight ratio of the polyhydric alcohol to the diisocyanate is greater than 〇·88 (weight ratio: 1:1·12), IPDI is used as the diisocyanate material. The urethane composite has a tensile strength greater than that of the dish Pa (IP3; π. _pa) and its coefficient of increase is greater than 90 MPa (IP3; 96·2 MPa:); the polyurethane formed using HDI as the bisisocyanate material The tensile strength of the compound material is greater than 2〇MPa (H3; 21.8MPa) and its Young's coefficient is greater than 1〇嶋(10); 130·〇MPa). Since the mechanical properties of the root canal filling material will directly affect the firmness and chewing ability of the postoperative teeth (4), it can be seen from the above results that the polyaminopyrene composite material provided by the present invention does have a _ root canal sealing material. The potential for application. 200840831 A cone material in a root canal filling material is disclosed in a second embodiment of the invention. The above-mentioned cone is intended to contain a polyurethane composite as described in the first embodiment, and an antibacterial material may be mixed to enhance the applicability of the material. Obviously, the invention may be modified and varied in accordance with the description of the implementation. Therefore, f is to be understood purely within the scope of the Galilee claim, and the present invention can be widely practiced in other embodiments in addition to the above detailed description. The above are only the preferred embodiments of the present invention, and are not intended to limit the "reduction" of the present invention; all equivalent modifications and modifications made by the other embodiments of the present invention should be applied to the following applications. Within the patent. 15

Claims (1)

200840831 X. Patent application scope: 1. A polyurethane composite material comprising: a thermoplastic polyurethane, the thermoplastic poly-urethane comprising a polyurethane The ester backbone, the polyurethane backbone comprising a hard segment and a superior bond segment. The hard bond segment is reacted with a chain extender by a pair of isocyanate (Diisocyanate) Forming, the soft segment is formed by a polyol, wherein the read polyol is selected from one of the following groups or any combination thereof: a poly-ester polyol, a poly An ether-type poly-ether polyol; and a filler. The polyurethane blending material according to claim 1, wherein the above-mentioned bisisocyanate comprises one of the following groups or any combination thereof: (1) aromatic polyisocyanates: tolylene diisocyanate ( TDI)(2,4- : or 2,6-TDI), diphenylmethane diisocyanate: (MDI)(4, 4, - or 2,4,-MDI), polymeric MDI, xylylene diisocyanate (XDI), naphthylene di isocyanate ( NDI) (usually 1,5-NDI), paraphenylene diisocyanate (PPDI), tetramethylxyly1ene di isocyanate (TMXDI), tolidine di isocyanate (TODI), 16 200840831 3, 3, —dimethoxy-4, 4'-biphenylene diisocyanate 〇(2 ) alicyclic polyisocyanates: dicyclohexylmethane diisocyanate (HMDI) (4,4?-or 2,4'-HMDI), isophorone diisocyanate (IPDI), isopropylidene-bis-(4-cyclohexyl isocyanate) (I PC ), hydrogenated xylylene di isocyanate (hydrogenated XDI), cyclohexylene diisocyanate (CHPI) (usually 1,5-tetrahydonaphthaiene diisocyanate o (3) aliphatic diisocyanate g (a 1 iphatic polyisocyanates): hexamethylene di isocyanate di isocyanate o diisocyanate [ (LDI), (HDI), lysine tetramethylene The polyurethane g-recovery material according to claim i, wherein the above-mentioned diisocyanate is selected from one of the following groups or any combination thereof: a cyclic diisocyanate, an aliphatic diisocyanate . The polyaminophthalate composite according to claim 1, wherein the above-mentioned bis-oxyacid vinegar is Hexamethylene diisocyariate (HDI). The polyurethane composite according to claim 1, wherein the above-mentioned 17 200840831 ί j polyester polyol comprises one of the following groups or any combination thereof: Polycaprolactone (PCL), Poly (butylene- Adipate) - glycol (PBA) - Poly(ethylene-adipate) glycol (PEA)-Poly(ethylene-butylene-adipate) glytol (PEBA), : Poly(hexylene-adipate) glycol (PhX) 〇6·Claim claims The polyurethane adhesive material according to 1, wherein the above-mentioned m polyether polyalcohol comprises one of the following groups or a combination thereof: Polyethylene Glycol (PEG), Polypropylene Glycol (PPG), Polytetramethylene Glycol ( The polyaminophthalate composite material according to claim 1, wherein the above-mentioned polyalcohol is Poly(butylene_adipate) glyc〇i (pba). The polyaminophthalate composite according to claim 1, wherein the above filler comprises one of the following groups or any combination thereof: zinc hydride, fluoroaluminosilicate glass. The weight ratio of the polyisocyanate to the bis-isocyanate is greater than 0.8. The polyaminophthalic acid vinegar composite according to claim 1, wherein the weight ratio of the thermoplastic polyurethane to the filler is less than 0.5. 11. The polyaminophthalate composite of claim 1 wherein: the polyaminophthalate composite has a melting point below 60 °C. The polyurethane sound-bonding material according to claim 1, wherein the polyaminophthalic acid ester composite has a melting point of less than 55.0. The polyurethane composite according to claim 1, wherein the polyaminophthalic acid S composite has a tensile strength of more than 10 MPa. a polyamino phthalate composite material, wherein the above-mentioned polyamino phthalate composite material has a tensile strength (tei^si le strength) of more than 20 MPa 〇 15 · a polyurethane rim as described in the claims a material, wherein the Young's Modulus of the above-mentioned water urethane composite material is greater than 90 MPa. 200819 200840831 1β• The polyaminomethyl-based chelating material according to claim 1, wherein the amino group is The Young's modulus of the composite material 乂Y〇ung, s M〇dulus) is greater than 100 MPa. - The cone material of the scooping material, the cone material, such as the weight of the material The polyaminomethyl group described in 1 is a composite material. The cone material according to claim 17, wherein the crucible is blended with an antibacterial material.