WO2014204289A1 - ADHESIVOS ORTODÓNCICOS LIBRES DE BisGMA - Google Patents
ADHESIVOS ORTODÓNCICOS LIBRES DE BisGMA Download PDFInfo
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- WO2014204289A1 WO2014204289A1 PCT/MX2014/000092 MX2014000092W WO2014204289A1 WO 2014204289 A1 WO2014204289 A1 WO 2014204289A1 MX 2014000092 W MX2014000092 W MX 2014000092W WO 2014204289 A1 WO2014204289 A1 WO 2014204289A1
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- WIPO (PCT)
- Prior art keywords
- adhesive
- orthodontic
- enamel
- adhesives
- silicon dioxide
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Classifications
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- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
- A61L24/00—Surgical adhesives or cements; Adhesives for colostomy devices
- A61L24/02—Surgical adhesives or cements; Adhesives for colostomy devices containing inorganic materials
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- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K6/00—Preparations for dentistry
- A61K6/15—Compositions characterised by their physical properties
- A61K6/17—Particle size
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K6/00—Preparations for dentistry
- A61K6/30—Compositions for temporarily or permanently fixing teeth or palates, e.g. primers for dental adhesives
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K6/00—Preparations for dentistry
- A61K6/40—Primers
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- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K6/00—Preparations for dentistry
- A61K6/70—Preparations for dentistry comprising inorganic additives
- A61K6/71—Fillers
- A61K6/76—Fillers comprising silicon-containing compounds
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
- A61L24/00—Surgical adhesives or cements; Adhesives for colostomy devices
- A61L24/04—Surgical adhesives or cements; Adhesives for colostomy devices containing macromolecular materials
- A61L24/06—Surgical adhesives or cements; Adhesives for colostomy devices containing macromolecular materials obtained by reactions only involving carbon-to-carbon unsaturated bonds
Definitions
- the present invention is in the field of attachments and reagents used for orthodontics, specifically orthodontic adhesives for example for brackets.
- Bisphenol A plays an important role in almost all composites and sealants, and is the integral part of the BisGMA molecule;
- Bisphenol A found in the mouth can originate from dental materials either when used as a direct ingredient, as a degradation product of other ingredients, such is the case of the use of bisphenol dimethacrylate A (BisDMA) since it is exposed in the oral cavity to degradation of saliva stearases);
- Bisphenol A found in the mouth can originate from being present as trace material derived from the manufacture of other ingredients, such is the case of products containing BisGMA in sealant and adhesive composites, since Bisphenol A is the precursor of BisGMA, Therefore, residues may be present in the final product, this is very common if reactions during manufacturing are not adequately controlled 3 .
- BisGMA is a monomer that has a high molecular weight, and due to its stereotactic structure and its high viscosity it presents a phenomenon of steric hindrance during polymerization and as a result a rigid material with little flexibility is obtained to move in the space, this makes handling difficult, so that another monomer such as triethylene glycol dimethacrylate (TEGDMA) must be incorporated to dilute its hard consistency and provide better performance 8 .
- TEGDMA triethylene glycol dimethacrylate
- US 6,090,867 refers to a dental adhesive system that allows the easy removal of ceramic brackets from the acrylate-based adhesive enamel surface comprising a plasticizer that gives it ductility, and where the plasticizer has poor solubility in water or saliva , it does not evaporate at the temperature of the oral cavity and is not toxic at the doses used.
- US Patent 5,575,645 refers to an orthodontic apparatus placed in a container and containing a stable adhesive for storage that comprises EBDA and is free of TEGDMA.
- the EBDA may contain EBDMA, and after polymerization it has a bond strength of 25 to 54 kg / cm 2 , it has a consistency of 12 to 24.5 mm.
- US Patent 5,295,824 refers to a plastic (polycarbonate) bracket with a Primer layer (of monomeric acrylic adhesive) adhered to the surface that makes contact with the tooth and its function is to increase the bond strength between the bracket and the adhesive dental; to obtain this type of self-adhesive bracket, it is necessary to apply a solvation mixture to the bracket and heat it to a temperature of 60 to 100 ° C so that the solvents are volatilized and that the monomers and with the solvation mixture conform to the first, and require 2 to 30 minutes to spread to the surface of the bracket that will make contact with the tooth, you can only guarantee the stability of the first in the bracket for a few weeks, so this method in addition to being laborious is inefficient.
- US patent 5810584 refers to a bracket that carries the adhesive previously applied to the bonding surface, and is characterized by not being sticky, mention formulations of these adhesives, all these adhesives are based on BisGMA.
- Self-etching adhesives are an alternative for orthodontic cementation, these substances are a weak acid incorporated into the first one, so they call it one step, and the number of procedures is reduced.
- These products combine the enamel conditioner together with the hydrophilic adhesive system in a single bottle, making it possible to simplify the first 2 steps of the cementation of brackets (the etched with orthophosphoric acid followed by the application of the bonding resin) and transforming them into a unique gesture, the bond strength of these adhesives should be optimal but no results are provided or data from other parameters expected for good performance in others are reported. aspects of its functions 9 .
- etching acid is rubbed which has to be washed and dried; then a first is applied which is light cured for 5 to 10 seconds depending on the manufacturer; The adhesive is then applied to the bracket, positioned on the enamel and polymerized for 10 to 15 seconds.
- the step that is eliminated is the application of the first; that is, the etching acid (37% phosphoric acid) is rubbed on the tooth, washed and dried; The adhesive is placed on the bracket and this on the tooth and polymerized for 10 seconds.
- a further object of the present invention is to provide an orthodontic adhesive with an elastic module that allows the adequate transmission of forces generated by the orthodontic appliances to the dental part. It is a further object of the present invention, to provide an orthodontic adhesive with adhesion both to the base of the attachments and to the enamel so that it does not damage the enamel. It is a further object of the present invention to provide an orthodontic adhesive with minimal sorption and solubility.
- a further object of the invention is to provide an adhesive with a film thickness of 39 ⁇ 2 ⁇ that is suitable to enable a better performance of movement of the brackets on the teeth.
- Figure 1 shows a photograph of the Acid etching, strong acid that can be 35% orthophosphoric or phosphoric acid to exert the demineralizing action on tooth enamel.
- Figure 2 shows a photograph of the First Transbond.
- Figure 3 shows a photograph of the first self-etching Transbond, this being a kit that consists of a weak acid that can be acrylic or citric and separately a first that is mixed until it is used.
- Figure 4 shows a photograph of Adhesive A, Transbond Paste Adhesive
- Figure 5 shows a photograph of Adhesive C, Transbond Paste Adhesive
- Figure 6 shows a photograph of the recommended kit that includes: a recording acid (strong acid), a primer and a paste adhesive.
- a recording acid strong acid
- a primer and a paste adhesive.
- Figure 7 shows a photograph of the acid etching in liquid (strong acid)
- Figure 8 shows a photograph of the First Ortho Solo.
- Figure 9 shows a photograph of Adhesive B, Enlight Paste Adhesive.
- Figure 10 is a scheme describing the procedure for determining hardening time.
- Figure 11 is a graph showing the average time of hardening of orthodontic adhesives (in paste).
- Figure 12 is a graph showing the average total hardening time of orthodontic adhesives (adhesive systems).
- Figure 13 shows a photograph of a PVC mold.
- Figure 14 is a scheme describing the sequence of steps to assess resistance to shedding.
- Figure 15 is a graph showing the average adhesion stress of orthodontic adhesives.
- Figure 16 is a graph showing the average elastic modulus of orthodontic adhesives.
- Figure 17 shows a photograph of a typical type 2 fault image.
- Figure 18 shows a photograph of a typical image of the tooth and bracket after having performed adhesion strength test, with adhesive of the invention or experimental.
- Figure 19 shows a photograph of a typical image of the tooth and bracket after having performed adhesion strength test, with adhesive system of the invention (experimental).
- Figure 20 shows a photograph of a typical image of the tooth and bracket after having performed adhesion strength test, with Adhesive A.
- Figure 21 shows a photograph of a typical image of the tooth and bracket after having performed adhesion strength test, with Adhesive C.
- Figure 22 shows a photograph of a typical image of the tooth and bracket after having performed adhesion strength test, with Adhesive B.
- Figure 23 shows a photograph of a mold for sorption and solubility.
- Figure 24 is a scheme describing the method for calculating sorption and solubility
- Figure 25 is a graph showing the averages of sorption and solubility of pastes at different pH.
- Figure 26 is a graph showing Sorption and solubility of primers at different pH (Primers).
- Figure 27 is a scheme describing the method of measuring fluency.
- Figure 28 is a graph showing the average fluidity of orthodontic adhesives (Paste).
- Figure 29 is a graph showing the average fluidity of orthodontic adhesives (First).
- Figure 30 is a scheme describing the procedure for determining film thickness.
- Figure 31 is a graph showing the average thickness of orthodontic adhesive film
- Figure 32 is a graph showing the average contact angle of primers of adhesive systems.
- Figure 33 is a graph showing the average surface tension averages of the adhesive systems.
- Figure 34 A shows a photograph of the initial image of the adhesive at the time of photopolymerization immediately after mixing in the month of April, in December, corresponds to the polymerization of the adhesive after 8 months of mixing He explains that the color of the adhesive has not undergone changes since its preparation, that is, it maintains color stability.
- Figure 34 B shows a photograph of the image of the adhesive at rest during the 8 months of its mixture where it is observed that there is no phase separation.
- Figure 34 C shows a photograph of the initial image of the paste of the adhesive system at the time of photopolymerization immediately after mixing in the month of April, in December, corresponds to the polymerization of the adhesive after 8 months of mixing which explains why the color of the adhesive has not undergone changes since its preparation, that is, it maintains color stability.
- Figure 34 D shows a photograph of the image of the adhesive at rest during the 8 months of its mixture where it is observed that there is no phase separation.
- Figure 35 is a table showing the percentage loss of mass of orthodontic adhesives subjected to thermogravimetry.
- Figure 36 is a graph showing the thermogravimetric behavior of the single pass adhesive of the invention.
- Figure 37 is a graph showing the thermogravimetric behavior of the adhesive of the adhesive system of the invention. DETAILED DESCRIPTION OF THE INVENTION
- the present invention provides to the field of orthodontics of adhesives and adhesive systems for appliances or attachments that adhere to dental pieces, it is therefore the formulation of a dental adhesive to cement attachments such as brackets , buttons and tubes either metallic or plastic to tooth enamel for orthodontic treatments and also includes the formulation of a primer and a fluid paste that work as a system.
- a dental adhesive to cement attachments such as brackets , buttons and tubes either metallic or plastic to tooth enamel for orthodontic treatments
- the present invention was derived from the development of an adhesive material with orthodontic application by replacing Bisphenol glycidyl methacrylate (BisGMA) with a multifunctional methacrylate, Tnmethylolpropane Trimethacrylate (TMPTMA); also known as: 1, 1, -Tnmethylolpropane trimethacrylate; 1,3-Propanediol, 2-ethyl-2- (hydroxymethyl) -, trimethacrylate; 2-Ethyl-2 (hydroxymethyl) -1, 3-propanediol trimethacrylate; ATM 11; TMP Acriester; Blemmer PTT; Methacrylic acid, 1,1,1-trihydroxymethyl propane triester; TMPT (crosslinking agent); 2- propenoic acid, 2-methyl-, 1, 1 '- (2-ethyl-2 - (((2-methyl-1-oxo-2-propen-1- yl) oxy) methyl) -1, 3- propanediil) ester; 2- propenoic
- the adhesives of the invention have been tested experimentally and it has been concluded that they are capable of withstanding orthodontic biomechanics, that is, that they support the tractional and torsional forces with low elastic modulus.
- the adhesives of the invention are low viscosity adhesives that penetrate both the retention of the bracket and those made by acid etching on the enamel surface. They have adhesion both to the base of the attachments and to the enamel.
- the adhesives of the invention are photopolymerizable which means that the operator will have enough time to place the apparatus in proper position and are easily handled adhesives. They have the minimum film thickness so as not to alter the prescription of the system.
- the adhesives of the invention have minimal or no sorption, also have minimal or no solubility to avoid premature detachments, to avoid white lesions under the apparatus and to avoid microfiltration, therefore, when removing the apparatus at the end of the treatment they do not cause damage structural enamel.
- the adhesives of the invention can remain in the mouth for the necessary time of current straight arch orthodontic treatments, which has been estimated to be an average of 24 months.
- the adhesives of the invention are 2 different formulations:
- the first of the adhesives will be hereafter referred to as "one-step” because it is formed by a fluid paste (fluid paste 1) consisting of two phases:
- A. organic phase (Monomer: Trimethylolpropane trimethacrylate 40.67% w / w (TMPTMA), Photoinitiator: Camforoquinone 0.3%, Accelerator: Dimethyl p-toluidine 0.03%) and
- B. inorganic phase Silanized silicon dioxide of nanometric particle size (16 nm) 2% and 57% w / w of silanized silicon dioxide of micrometric particle size (325 pm).
- this adhesive called “one-step” one step is eliminated in the procedures for adhering brackets and also a single adhesive phase is being provided and not two polymerized layers as in the case of self-etching primers and In conventional systems, the latter is of particular importance since having an adhesive layer with low elastic modulus allows that after the bracket is detached, the fault occurs in the adhesive, that is, the adhesive that polymerized inside of the retentions there remain and the fracture is in the body of the adhesive; so that the remaining adhesive on the surface of the enamel will have to be removed with a rotating instrument to ensure the integrity of the enamel prisms; commercial adhesives such as Transbond LV and Enlight after having detached the brackets, do not show adhesive residue on the enamel but this may be can lead to the release of enamel prisms resulting in pain for the patient and the need for surface repair Dental to achieve aesthetics again.
- the second of the adhesives will be hereafter referred to as an adhesive system because two adhesives act together and for its use the application of a first layer called "Primer” is required followed by a layer of a fluid paste (Fluid Paste 2).
- the first consists of two phases:
- Organic phase Monomer: Trimethylolpropane trimethacrylate 83.67% w / w, Solvent: 10% isopropyl alcohol, Photoinitiator: 0.3% Camforoquinone, Accelerator: 0.03% Dimethyl p-toluidine.
- Inorganic phase Silanized silicon dioxide of nanometric particle size (16 nm) 6%.
- the fluid paste 2 is formed by two phases:
- Organic phase onomer: Trimethylolpropane trimethacrylate 40.67% w / w, Photoinitiator: Camforoquinone 0.3%, Accelerator: Dimethyl p-toluidine 0.03%.
- Inorganic phase Silanized silicon dioxide of nanometric particle size (16 nm) 3% and 56% of silanized silicon dioxide of micrometric particle size (325 pm).
- the mixture used to perform the entire experimental part was prepared by a single operator (to minimize errors due to handling) and was stored under controlled humidity and temperature conditions (65 ⁇ 2%, 21 ⁇ 2 ° C). Reagents were maintained for 24 hours at 65 ⁇ 2% RH. and 21 ⁇ 2 ° C before use.
- TMPT A is a monomer of high reactivity and low viscosity (45 mPas at 25 ° C), gives the adhesive of the invention, its characteristics, as it could be demonstrated during the experimental development and finally two competitive products were obtained in the market, since the one-step adhesive exhibits better performance than any of the three commercial adhesives prepared with Bis glycidyl methacrylate (BisGMA), with which it was compared and the second shows the performance suggested by parameters proposed by Reynolds 10 , for orthodontic adhesives to avoid causing damage to the dental structure and also better physical properties than the commercial ones with which it was compared.
- BisGMA Bis glycidyl methacrylate
- the procedure to use it involves: applying the first Transbond self-etching (figure 3) and 2) applying the Transbond XT paste (figure 4), or: 1) applying the etching acid (Figural) to the tooth, 2) applying the First Transbond (figure 2) and apply Transbond XT paste (figure 4).
- adhesive B consisting of a first "Ortho Solo” and a paste “Enlight”
- the procedure for using it involves 1) applying an etching acid (figure 7), 2) applying the first of the brand name Orto alone (figure 8) and 3) applying the paste of the Enlight trademark (figure 9).
- Figure 6 shows the ORMCO trademark kit that includes the elements of Figures 7, 8 and 9.
- the procedure for using it involves: 1) applying the first Transbond autogravure (figure 3) and 2) applying the Transbond LV paste (figure 5), or: 1) applying the etching acid (Figural) to the toothpiece, 2) apply the first Transbond (figure 2) and apply the Transbond LV paste (figure 5).
- the one-step adhesive of the invention unlike commercial ones ( Figures 1-9), does not require the prior application of a primary reagent that will be referred to as First; The latter is applied immediately after acid etching on the enamel surface.
- First a primary reagent that will be referred to as First
- the absence of this step results in characterizing the adhesive of the invention as a "one-step" adhesive, although this feature refers to the procedure when used to adhere orthodontic appliances.
- the possibility of reducing in time and form the manipulation in the placement of the brackets is being provided since conventional methods require application of two products after the required acid etching.
- the one-step adhesive of the invention has a hardening time of 10 seconds that is the lowest achieved so far and is similar to that of commercial ones: A and C that also require 10 seconds to harden and is less than the adhesive commercial B, which needs 15 seconds.
- a and C that also require 10 seconds to harden and is less than the adhesive commercial B, which needs 15 seconds.
- the great advantage lies in the total time since the application of the Primer to culminate with light curing, since while commercials need 15 and 20 seconds in total, it is necessary to apply first (5 seconds) and light curing for an additional 10 seconds, the The adhesive of the invention needs only 10 seconds in total because it does not require Primer.
- Example 2 explains how the hardening time consumed in each tooth was measured (figure 10), in graph 1 (figure 11) the hardening time of the adhesives of the invention is shown.
- Graph 2 ( Figure 12) shows the total time it would take to use each of the adhesives on average: adhesive B (Enlight) needs 20 seconds to apply its entire system that includes Primer (5 s) and paste (15 s); both Transbond LV (adhesive C) and Transbond XT (adhesive A) need 15 seconds for their entire system: Primer (5 s) and paste (10 s);
- the one-step adhesive object of this patent needs only 10 seconds to be applied and it is an adhesive system that requires 15 seconds in total as adhesives A and C. It can be considered that in medical practice the time consumed in the preparation and placement of instruments and devices turns out to be an aspect that adds value to the products that are used.
- the one-step adhesive of the invention was tested and compared with commercials A, B and C regarding the adhesion strength parameter, considering international standards, 14 with human dental enamel substrate and metal attachments (brackets) and presented 9.5 ⁇ 1.5 MPa without placing a Primer.
- This resistance is similar to that presented by commercial adhesives: Adhesive A: (9.4 ⁇ 0.8MPa)
- Adhesive B (10.0 ⁇ 2.4MPa) that need the Primer to achieve accession.
- the elastic modulus presented by the adhesive of the invention was 30 MPa, this is significantly lower than the commercial ones: A (44 MPa), C (45 MPa) and B (52 MPa).
- the advantage of a low elastic module is that since it is a more elastic material, it will allow that when the bracket receives a force, the adhesive dissipates it and transmits it to the tooth to achieve dental movement without failure.
- the results on the site and type of failure of the adhesives 15 it was found that at the time of the detachment of the bracket, both the adhesive object of this application and the adhesive A remain adhered to the enamel. This fact guarantees the integrity of the enamel prisms by avoiding detachment when the devices are lowered at the end of the treatment.
- Adhesive C less than 50% of adhesive in the enamel and Adhesive B presented more than 50% of adhesive in the tooth.
- the fluidity of the adhesive of the invention 16.17 was 330mm 2 , which allows it to easily penetrate both the micro-retentions created in the enamel by the effect of acid etching and at the base of the attachments. While commercials do not exceed 300mm 2 , that is, they are more viscous either because of the ingredients they carry or because they are prepared with inorganic fillers in a greater percentage than the adhesive of the invention (experimental).
- Adhesive A and Adhesive C were similar to two commercial (Adhesive A and Adhesive C) and less than Adhesive B EXP (300 pg / mm 3 , 300 g / mm 3 ), Adhesive A (300 pg / mm 3 , 300 pg / mm 3 ), Adhesive C (289 pg / mm 3 , 3 8 g / mm 3 ) and Adhesive B (330 pg / mm 3 , 389pg / mm 3 ) .
- the adhesive of the invention presented lower sorption than commercial ones: (294 g / mm 3 , 294 g / mm 3 ), adhesive A (300 g / mm 3 , 391 g / mm 3 ), adhesive C (318 ⁇ g / mm 3 , 311 g / mm 3 ) and adhesive B (389 g / mm 3 , 402 pg / mm 3 ), whereby it can be inferred that the adhesive of the invention is more resistant to the acidic environment and in patients presenting salivary pH more acidic (with high caries index) the adhesive of the invention is more stable than commercial ones, which have higher sorption and greater solubility.
- the adhesive of the invention had a film thickness of 39 ⁇ 2 pm less than the behavior of Adhesive C (47 ⁇ 2 ⁇ ) and with respect to the other commercial adhesives A and B, they presented film thicknesses with differences of film thickness much more marked: Adhesive A (69 ⁇ 1 ⁇ ) and Adhesive B (124 ⁇ 1 ⁇ ); so it is inferred that using them could compromise the treatment because there is no necessary control of dental movement.
- the shelf life is another parameter that was measured.
- the experimental adhesive or of the invention has shown to be stable at rest at 21 ⁇ 1 ° C, has not presented phase separation or apparent color change.
- Stability in oral temperatures is another parameter that was measured: the oral cavity is subject to temperature changes due to the intake of food and beverages, this temperature fluctuates from 5 to 55 ° C.
- the experimental adhesive or of the invention like the three commercial adhesives tested, showed stability when they were heated from room temperature (25 ° C) to 60 ° C since none showed a loss of mass.
- the adhesive system that includes a first and a fluid paste, these are two different formulations that give completely different values, not greater than commercial ones.
- the adhesion system presents less adhesion effort than commercial ones, but within the parameters mentioned by Reynolds 10 to support orthodontic biomechanics but without damaging the enamel prisms and with different characteristics in terms of sorption, solubility, fluidity, film thickness ( Figure 15)
- the adhesive system of the invention as well as commercial systems (Fig. 1-9), requires the prior application of a primer called first; The latter is applied immediately after acid etching on the enamel surface.
- the adhesive system of the invention has a hardening time similar to the commercial ones: Transbond XT and Transbond LV, require 10 seconds to harden and less than Enlight, which needs 15 seconds.
- the total time since the application of the first to finish with the light curing, is the same as the commercials Transbond XT and Transbond LV (15 s), Enlight requires 20 seconds.
- the adhesive system of the invention when tested with human dental enamel substrate and metal attachments (brackets) presented 6.5 ⁇ 1 MPa of resistance, this resistance is lower than that presented by commercial adhesives: Transbond XT: (9.4 ⁇ 0.8MPa) , Transbond LV: (9.5 ⁇ 1.5MPa) and Enlight: (9.5 ⁇ 1.5MPa).
- the advantage of the experimental adhesive system is that by presenting sufficient adhesion to withstand orthodontic biomechanics but not too much like commercial ones, it reduces the risk of causing enamel prisms to be removed when the appliance is removed.
- the elastic modulus presented by the adhesive system of the invention was significantly lower than the commercial ones, 34 MPa; Transbond XT (44 MPa), Transbond LV (45 MPa) and Enlight (55 MPa).
- the advantage of a low elastic module is that since it is a more elastic material, it will allow when the bracket receives a force, the adhesive dissipates it and transmits it to the tooth to achieve dental movement without it failing ( Figure 16).
- both the adhesive system of the invention and Transbond XT remain attached to the enamel. This fact guarantees the integrity of the enamel prisms by avoiding detachment at the time of lowering the apparatus at the end of the treatment.
- the other adhesives left debris on the enamel and on the bracket mesh indicating that there could be damage to the enamel, so the treatment is compromised as it will now be necessary to restore the enamel.
- Transbond LV less than 50% of adhesive in the enamel and Enlight presented more than 50% of adhesive in the tooth.
- the Primer has a fluidity of 330mm 2 , this allows it to easily penetrate the microretentions created in the enamel due to the effect of acid etching. While the commercial Transbond XT presented 353mm 2 , being more fluid it can have greater penetration capacity, and in case of trying to use this first in dentin it can be more irritating to the pulp: Ortho only present 207mm 2 means that it is more viscous already either because of the ingredients it carries or because they are prepared with inorganic fillers in greater percentage than the first experimental.
- the fluid paste has a fluidity of 348mm 2 , this allows it to easily penetrate the base of the attachments. While commercials do not exceed 300mm 2 , that is, they are more viscous either because of the ingredients they carry or because they are prepared with inorganic fillers in a greater percentage than the experimental adhesive.
- the experimental adhesive (0.06 pg / mm 3 , 0.06 pg / mm 3 ) exhibited greater sorption than the commercial one: Transbond XT (0.03 pg / mm 3 , 0.04 pg / mm 3 ) and less than the commercial Ortho Solo (0.03 pg / mm 3 , 0.1 pg / mm 3 ), which can be inferred that the experimental adhesive is more resistant to the acidic environment and in patients with salivary pH more acidic (with high caries index) .
- the experimental adhesive (300 pg / mm 3 , 288 pg / mm 3 ) presented less sorption than commercial ones: Transbond XT (300 pg / mm 3 , 391 pg / mm 3 ), Transbond LV (318 pg / mm 3 , 311 pg / mm 3 ) and Enlight (389 pg / mm 3 , 402 pg / mm 3 ), which can be inferred that the experimental adhesive is more resistant to the acidic environment and in patients who present salivary pH more acidic (with high caries index), the experimental one is more stable than commercial ones, who present greater sorption and greater solubility.
- the adhesive system of the invention had a film thickness of 26 ⁇ 1 pm much lower than Transbond LV (47 ⁇ 2 pm), Transbond XT (69 ⁇ 1 pm) and Enlight (124 ⁇ 1 m) so it is inferred that using them could compromise the treatment as there is not so much control of dental movement.
- the first one has a greater area of wetting with the substrate and better penetration in the micro-retentions created by acid etching.
- the first of the system of the invention had the same contact angle value as the commercial Transbond XT (40 ⁇ 0.1 degrees); slightly lower than the one presented by the Ortho Solo commercial included in the Enlight commercial adhesion system (41 ⁇ 0.8 degrees); ( Figure 32).
- the surface tension 33 allows the first one with smaller values together with the contact angle and fluidity to have a greater area of adhesion and to penetrate better in the micro-retentions created in the enamel surface by the action of acid etching.
- the objective of the invention is to offer the technical field an adhesive whose organic phase is basically constituted by the TMPTMA monomer (40.00-50.00% w / w), and has Camforoquinone (from 0.10 to 0.50%, preferably 0.3% (w / w ) as a photoinitiator; and Dimethyl p-toluidine (0.01-0.05%, preferably 0.03%) as an accelerator, and whose inorganic phase is constituted by silanized silicon dioxide of nanometric particle size (16 nm) (at 1.00 to 2.00% , preferably 2%) and silicon dioxide Silanized micrometric particle size (325 ⁇ ) (from 50.00 to 60.00%, preferably 57%, with respect to the total weight.
- the objective of the invention is to offer the technical field an adhesive which, being able to be used in a single step, improves the procedure for placing orthodontic appliances, making it an adhesive that offers a competitive advantage in the market, which reduces the chair cost and time with the patient, additionally it is a relevant feature that does not contain in its BisGMA formulation.
- Another object of the invention is to provide an adhesive for orthodontic use and for dental use in general, which has numerous characteristics not only desirable in an adhesive of its kind but exceeds several of the characteristics, is composed of a single monomer, so which does not have copolymerization and where said monomer is a methacrylate with three functional groups, which by the type of polymerization it presents allows for a lower elastic modulus than those of known adhesives, which translates into optimum performance for orthodontics, especially of the functions of the brackets; It presents minimal sorption and solubility this helps its stability under different pH conditions, so that it will be stable regardless of the salivary pH of the patient.
- a further objective of the invention is to provide an acid-resistant adhesive, suitable for patients who even have a more acidic salivary pH (due to the high caries index), the adhesive of the invention is finally more stable than commercial ones, which have a higher sorption. and greater solubility.
- An embodiment of the invention independently involves providing a fluid paste 1, whose organic phase is formed by: a Monomer: Trimethylolpropane trimethacrylate 40.67% w / w, Photoinitiator: Camforoquinone 0.3%, Accelerator: Dimethyl p -toluidine 0.03%, the inorganic phase of The fluid paste 1 consists of: Silanized silicon dioxide of nanometric particle size (16 nm) 2% and 56% of silanized silicon dioxide of micrometric particle size (325 ⁇ ).
- One embodiment of the invention independently involves providing first orthodontic characterized by having two phases: An organic phase consisting of: the trimethylolpropane trimethacrylate monomer 83.67% w / w Solvent: 0% isopropyl alcohol, Photoinitiator: 0.3% Camforoquinone, Accelerator: Dimethyl p-toluidine 0.03%
- the inorganic phase of the first consists of silanized silicon dioxide of nanometer particle size (16 nm) 6%.
- An additional advantage is that due to its fluidity of 330 mm 2 , the adhesive penetrates more easily to the micro-retentions generated by acid etching.
- One embodiment of the invention is to provide the adhesive of the invention formulated within a glassy amber syringe with disposable dosing tips since acid etching can be performed with any etching acid available to the orthodontist.
- Another embodiment of the invention is to provide a kit or kit comprising the liquid etching acid in a dropper bottle; adhesive of the invention formulated within a vitreous amber syringe with disposable dosing tips.
- kits or kit comprising the liquid etching acid; the first in an amber vitreous bottle with dropper dispenser and the fluid adhesive paste of the invention in amber vitreous syringe with dosing tips for application.
- Another embodiment of the invention consists in providing a kit comprising the fluid paste of the invention and a first of the invention both packaged independently and protected from light.
- a further embodiment of the invention consists in providing a method of aesthetic orthodontic treatment which consists in applying the first and the fluid paste of the invention for the adjustment of orthodontic devices, including brackets.
- a further embodiment of the invention is to provide an aesthetic orthodontic treatment method that consists of applying the adhesive in a single step of the invention for the adjustment of orthodontic appliances, including brackets.
- Example 1 Process for obtaining adhesives:
- TMPTMA trimethylolpropane trimethacrylate monomer
- Fluid paste The monomer was mixed with the accelerator (Dimethyl p-toluidine 0.03%). When displaying a homogeneous mixture, the photo-activator was added
- micrometric silicon dioxide (Camforoquinone 0.3%). Then the micrometric silicon dioxide (56%) was incorporated to finish with the nanometric silicon dioxide (2%). Once a homogeneous mixture was obtained, it was stored in an amber bottle, labeled with the mixture number and date of preparation. The use of less than 56% of micrometric silicon dioxide does not work.
- the hardening time of the adhesive was determined by placing a drop of adhesive inside a stainless steel mold 4 mm in diameter and 1 mm thick with a Teflon spatula until scratched; it was irradiated with a light source (previously assessed for irradiation: 600 mW / cm 2 ) for 5 seconds. Subsequently, a perpendicular force was applied to penetrate the adhesive using a micrometric screw with a sharp attachment. If the adhesive still did not harden, another drop of adhesive was placed in the mold and light cured for 10 seconds, the indentation procedure was performed. The total procedure is repeated until hardening of the material immersed in the mold.
- Figure 10 shows the sequence of the test. The hardening time of each adhesive mixture is shown in the graph of Figure 11 and its averages in the graph of Figure 12.
- Example 3 Determination of resistance to detachment:
- the teeth were cut 5mm apical from the cement enamel junction line (below the anatomical crown) to be able to locate the center of the anatomical crown to the center of the cylinder (sample holder).
- Prophylaxis was performed on the vestibular face of the teeth with rubber cup and fluoride-free prophylactic paste, washed with pressurized water and dried with oil-free pressure air.
- the teeth that carried the adhesives of the invention were rubbed with phosphoric acid diluted in 37% water, with a micro-brush over the adhesion area for 15 seconds; washed and dried for 20 seconds, the adhesive was applied on the base of the bracket and on the surface of the enamel treated with etching acid and using a bracket holder clamp, it was placed at the center of the anatomical crown of the tooth exerting pressure to the center of the bracket to remove excess adhesive with a scanner, to immediately light cure.
- the manufacturer's instructions were followed for commercial adhesives.
- the teeth of the adhesive system of the invention and commercial AY B were rubbed with 37% phosphoric acid, with a micro-brush on the adhesion area for 15 seconds; washed and dried for 20 seconds; washed and dried for 20 seconds, a homogeneous layer of primer was applied and polymerized 5 seconds.
- a homogeneous layer of primer was applied according to the manufacturer's instructions, after applying the first one, oil-free air was blown for 5 seconds and light curing with the light of the lamp being affected for 10 seconds.
- the adhesive was applied to the bracket and for the one-step adhesive of the invention (experimental), adhesive was also placed on the surface of the tooth and using a bracket holder clip, it was placed at the center of the anatomical crown of the To apply pressure to the center of the bracket to remove excess adhesive with a scanner, the tooth was light-cured for commercial adhesives following the manufacturer's instructions and for the experimental 10 seconds as determined in the "hardening time determination" test ( tilting the lamp to radiate on all four sides of the bracket).
- Aonginai is the area of attachment of the bracket (mesh).
- Figure 3 shows that the adhesive of the invention has similar values to the commercial ones. No adhesive showed statistically significant difference when tested with dental enamel substrates and metal brackets.
- Figure 4 shows that the adhesive of the invention has the lowest elastic modulus, which represents the most important difference with respect to the three commercials during this evaluation stage. Being a less rigid material, it will have a better behavior in its clinical use, allowing the forces applied to the bracket to be dissipated, the adhesive absorbed and slightly flexed to dissipate them towards the tooth without breaking.
- the three commercials being more rigid (higher value) run the risk of failing when thicker arc changes are applied:
- Example 4 Identification of the type and site of ARI failure: 14
- Adhesive A (figures 18 to 20) ARI 3 A: who allowed 100% of the adhesive to remain on the enamel surface, guaranteeing the integrity of the enamel prisms avoiding releasing them at the time of lowering the apparatus at the end of the treatment.
- Adhesive C (figure 21) presented ARI 1
- Adhesive less than 50% of adhesive in enamel and Adhesive B (figure 22) ARI 2
- Adhesive presented more than 50% of adhesive in the tooth.
- Specimens from each group were prepared using a stainless steel mold 4.43 mm in diameter and 1.5 mm thick (Figure 23). A drop of adhesive was placed in the center of the mold.
- a photo-polymerized lamp was used, previously assessing its operation in terms of irradiance (600mW / cm 2 ).
- the light curing lamp tip was placed over the center of the adhesive for 10 seconds except for Adhesive B who required 15 seconds.
- Adhesive B who required 15 seconds.
- they were placed inside the desiccator with silica and this in the temperature controlled chamber at 37 ⁇ 1 ° C.
- the silica was previously dehydrated for 5 hours at 130 ° C. After 24 hours, the samples were weighed in a analytical balance with an accuracy of +/- 0.2 mg, repeating this cycle until a constant mass was obtained, that is until the lost mass of each sample was not greater than 0.2 mg in a 24-hour period. This measurement was reported as Mi.
- the specimens were individually submerged in hermetically sealed containers, in two types of water: group 1) demineralized water (pH 7.7) and group 2) double-distilled water (pH 6.8). 8 28
- the containers were stored at 37 ° C for 7 days inside the temperature controlled chamber. After this time, the specimens were removed, dried with paper, stirred in the air for 15 seconds and after one minute of having removed them from the water, weighed to obtain (M 2 ).
- V specimen volume
- M 2 It is the weight of the sample after 7 days of immersion in water.
- the experimental adhesive is expected to perform better than commercial ones when they are clinically tested since they can be used in any type of patient (regardless of salivary pH).
- a sheet of millimeter paper was placed under a glass plate (30 mm wide x 30 mm long and 5 mm thick); 0.5 ml of adhesive was deposited on the glass plate; immediately after, the adhesive was covered with another glass plate of the same dimensions, placing two weights on them and in the center so that it gives a total weight of 120 g on the adhesive. They were placed inside the filter chamber in the light for 1 minute because the mixtures and commercial adhesives are light-cured; After this time, it was measured on the millimeter paper, the smallest diameter and the largest diameter of each sample.
- Figure 27 shows the sequence of steps to measure fluency. The average of the two diameter measurements was reported to calculate the area of each sample using the formula.
- the test was performed inside an orange chamber to filter the light and avoid photopolymerization of the adhesives.
- Two square glass plates were used, placing one on top of the other, measured with the micrometer screw; reporting this as reading A.
- the upper glass was removed, 0.2g of adhesive was placed in the center of the plate, the upper glass was placed again in the same position as the first measurement was made. They were placed centered under the pre-calibrated loading device and 150 N (15 Kg) were applied. After 10 minutes, the load was removed and measured again, recording this measurement as reading B.
- Figure 30 shows the procedure followed.
- New mixtures were manufactured, light-cured and compared to those made 8 months ago (light-cured immediately after the mixture was obtained in April 2012), to determine if the adhesives had changed color.
- Figure 29 A shows that there has been no apparent color change.
- Figure 29 B shows no separation after being kept at rest for 8 months.
- Example 9 Determination of thermal stability: Thermogravimetric analysis.
- thermogravimetry studies were performed. Stainless steel molds (1 mm thick x 4 mm in diameter) previously washed with acetone were used. To obtain the specimens, the molds were filled with each adhesive, they were light cured by previously assessing the lamp for irradiance (600mW / cm 2 ) using a curing radiometer.
- the light was affected on the samples of the experimental adhesives or of the invention for 10 seconds (time previously determined in the hardening time test); for commercial adhesives it was polymerized according to the manufacturer's instructions: Adhesive A and Adhesive C for 10 seconds and Adhesive B for 15 seconds. Once the material was light cured, they were demoulded ( Figure 34A to 34C). Once the material was demolished, an agate mortar and pistil was used to fragment the material. Each sample was weighed in 70 L alumina cells (open). The test was carried out in an ambient atmosphere, at intervals of 25 to 60 ° C, with a heating ramp of 5 o C / min. The percentage of mass loss at different temperatures was determined.
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- Health & Medical Sciences (AREA)
- Epidemiology (AREA)
- Life Sciences & Earth Sciences (AREA)
- Animal Behavior & Ethology (AREA)
- General Health & Medical Sciences (AREA)
- Public Health (AREA)
- Veterinary Medicine (AREA)
- Oral & Maxillofacial Surgery (AREA)
- Chemical & Material Sciences (AREA)
- Surgery (AREA)
- Inorganic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Dental Preparations (AREA)
- Adhesives Or Adhesive Processes (AREA)
- Dental Tools And Instruments Or Auxiliary Dental Instruments (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
Abstract
Description
Claims
Priority Applications (4)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CA2915586A CA2915586A1 (en) | 2013-06-17 | 2014-06-17 | Bisgma-free orthodontic adhesives |
JP2016521238A JP2016523249A (ja) | 2013-06-17 | 2014-06-17 | BisGMA非含有の歯列矯正用接着剤 |
BR112015031365A BR112015031365A8 (pt) | 2013-06-17 | 2014-06-17 | adesivos ortodônticos livres de bisgma |
US14/898,808 US9707159B2 (en) | 2013-06-17 | 2014-06-17 | BisGMA-free orthodontic adhesives |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
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MXMX/A/2013/006893 | 2013-06-17 | ||
MX2013006893A MX354347B (es) | 2013-06-17 | 2013-06-17 | Adhesivos ortodóncicos libres de bisgma. |
Publications (1)
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WO2014204289A1 true WO2014204289A1 (es) | 2014-12-24 |
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ID=52104936
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PCT/MX2014/000092 WO2014204289A1 (es) | 2013-06-17 | 2014-06-17 | ADHESIVOS ORTODÓNCICOS LIBRES DE BisGMA |
Country Status (6)
Country | Link |
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US (1) | US9707159B2 (es) |
JP (1) | JP2016523249A (es) |
BR (1) | BR112015031365A8 (es) |
CA (1) | CA2915586A1 (es) |
MX (1) | MX354347B (es) |
WO (1) | WO2014204289A1 (es) |
Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US5426134A (en) * | 1992-06-25 | 1995-06-20 | Ivoclar Ag | Dental material |
US20020082315A1 (en) * | 1998-01-28 | 2002-06-27 | Norbert Moszner | Urethane di(meth)acrylate derivatives of 1,3-bis(1-isocyanato-1-methylethyl)benzene |
WO2007079070A1 (en) * | 2005-12-29 | 2007-07-12 | 3M Innovative Properties Company | Dental compositions and initiator systems with polycyclic aromatic component |
US7963769B2 (en) * | 2007-10-08 | 2011-06-21 | Kerr Corporation | Dental adhesive and method of use |
Family Cites Families (8)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US5354199A (en) | 1991-08-02 | 1994-10-11 | Minnesota Mining And Manufacturing Company | Adhesive for packaged orthodontic appliance |
US5295824A (en) | 1992-09-04 | 1994-03-22 | Ormco Corporation | Plastic bracket with adhesive primer layer and methods of making |
US6090867A (en) | 1993-02-19 | 2000-07-18 | Georgia Tech Research Corporation | Orthodontic adhesive |
US5810584A (en) | 1997-04-04 | 1998-09-22 | Ormco Corporation | Orthodontic appliances (brackets) having pre-applied adhesive |
DE19803979C2 (de) * | 1998-01-28 | 2001-06-28 | Ivoclar Ag Schaan | Zusammensetzungen enthaltend Urethandi(meth)acrylat-Derivate von 1,3-Bis (1-isocyanato-1-methylethyl)benzol |
JP4417623B2 (ja) * | 2000-12-04 | 2010-02-17 | 株式会社トクヤマ | 歯科用硬化性組成物 |
ATE542517T1 (de) * | 2006-12-28 | 2012-02-15 | 3M Innovative Properties Co | Haftzusammensetzung für hartes gewebe |
JP2010046266A (ja) * | 2008-08-21 | 2010-03-04 | Tokuyama Dental Corp | 歯列矯正用接着材 |
-
2013
- 2013-06-17 MX MX2013006893A patent/MX354347B/es active IP Right Grant
-
2014
- 2014-06-17 US US14/898,808 patent/US9707159B2/en not_active Expired - Fee Related
- 2014-06-17 WO PCT/MX2014/000092 patent/WO2014204289A1/es active Application Filing
- 2014-06-17 CA CA2915586A patent/CA2915586A1/en not_active Abandoned
- 2014-06-17 BR BR112015031365A patent/BR112015031365A8/pt not_active IP Right Cessation
- 2014-06-17 JP JP2016521238A patent/JP2016523249A/ja not_active Ceased
Patent Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US5426134A (en) * | 1992-06-25 | 1995-06-20 | Ivoclar Ag | Dental material |
US20020082315A1 (en) * | 1998-01-28 | 2002-06-27 | Norbert Moszner | Urethane di(meth)acrylate derivatives of 1,3-bis(1-isocyanato-1-methylethyl)benzene |
WO2007079070A1 (en) * | 2005-12-29 | 2007-07-12 | 3M Innovative Properties Company | Dental compositions and initiator systems with polycyclic aromatic component |
US7963769B2 (en) * | 2007-10-08 | 2011-06-21 | Kerr Corporation | Dental adhesive and method of use |
Also Published As
Publication number | Publication date |
---|---|
US9707159B2 (en) | 2017-07-18 |
JP2016523249A (ja) | 2016-08-08 |
US20160120764A1 (en) | 2016-05-05 |
MX354347B (es) | 2018-02-21 |
BR112015031365A8 (pt) | 2018-01-23 |
CA2915586A1 (en) | 2014-12-24 |
MX2013006893A (es) | 2014-12-18 |
BR112015031365A2 (pt) | 2017-07-25 |
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