WO2017011886A1

WO2017011886A1 - Photopolymerisable resin composite and use thereof

Info

Publication number: WO2017011886A1
Application number: PCT/BR2016/000071
Authority: WO
Inventors: Dayane Carvalho Ramos Salles DE OLIVEIRA; Mateus Garcia ROCHA; Mario Alexandre Coelho S!NHORETI; Américo Bortolazzo CORRER; Ivo Carlos CORREA
Original assignee: Universidade Estadual De Campinas - Unicamp; Universidade Federal Do Rio De Janeiro - Ufrj
Priority date: 2015-07-20
Filing date: 2016-07-19
Publication date: 2017-01-26
Also published as: BR102015017232A2

Abstract

The present invention relates to a photopolimerisable resin composite with a higher filler particle content and a resin matrix of dimethacrylate monomers which are polymerised by free radical reaction initiated by the synergy of photoinitiator systems based on camphorquinone (CQ) and (2,4,6-trimethylbenzoyl)diphenylphosphine oxide (TPO or MAPO). In addition, the invention relates to the use of this photopolymerisable resin composite to manufacture odontological resin materials, such as sealants, composite resins of low or high viscosity and photoactivated or dual curing resin cements. The photopolymerisable resin composite of this invention makes it easier to imitate the colouring of natural teeth, since it achieves a wider range of brighter colours for odontological restoration materials.

Description

PHOTO-POLYMERIZABLE RESINOSOTE COMPOSITE AND ITS USE

Field of the Invention:

[001] The present invention is applicable in the field of medical science, more specifically: in the field of dentistry, and refers to a light-curable resin composite.

[002] The composite of this invention has a high charge particle content and a free radical reaction monomer eros diacryate resin matrix, initiated by the synergism of camphorquinone (CQ) and oxide (2,4) photoinitiating systems. , 6-trimethylbenzoyl diphenyl} phosphine (TPO or MAPO).

Additionally, the invention relates to the use of the photopolymerizable resin composite described in the manufacture of dental resinous materials, such as seeding, low or high viscosity composite resins, and photoactive or dual setting resin cements.

Background of the Invention:

[004] In recent decades, the demand for restorations with a color similar to natural teeth has increased among clinicians and patients ...

[005] For the clinical success of restorations, photoactivated composite resins are widely used and have good clinical performance, being able to: form an effective union with the dental substrate, improving tooth resistance and reducing its susceptibility to fracture.

[006] The polymerization reaction of composite resins depends directly on the photosensitization of the component called photoinitiator. Currently, camphorquinone (QC) associated with tertiary amine is the photoinitiator system of Type II most often found in most light-curing resin composites.

The concentration of camphorquinone as an isolated system ranges from 0.2% to 5.0% by weight of the total formulation. However, although the CQ-Amine system provides adequate material polymerization up to 2mm, technical disadvantages related to the optical properties of the material are still factors that reduce the longevity of aesthetic dental restorations.

[008] Some questions about the aesthetics of materials formulated with this photoliquing system began to be managed by increasing the aesthetic appeal of the dental public and the popularization of dental ciareation. This is due to the fact that camphorquinone is a bright yellow colored molecule and therefore makes it impossible to make very light colored materials to mimic lightened patients, for example.

Another issue raised is the color change during healing. Due to its strong coloration, the reduction of the yellow degree after the reaction causes a great color change in the material after the polymerization. In spite of. This seems a plus, as the material becomes less yellow, not all camphorquinone is consumed, leaving the material still yellowish. Still, this makes it difficult to choose the right color of restorative material with. relation to the tooth to be restored, since ^: the color of the unpolymerized material to be chosen will be quite different from the material after polymerization.

[010] Therefore, in order to enable the manufacture of lighter color formulations without affecting the Conversion grade, the present invention proposes a light-curable resin composite whose polymerization is initiated by the synergism of two photoinitiator systems.

Some prior art documents describe dental formulations comprising the complete replacement of the CQ-amine system with a phosphenic oxide (TPO) or the association of type I and II photoinitiating systems, however, these are formulations of adhesive systems.

[012] The technical justification for replacing the CQ-Amine system in adhesive systems is mainly due to the higher reactivity of type I photoinitiators, such as phosphinic oxide 2,4,6-trimethyl-diphenyl (TPO or ftPO ^' }, bis-2,4,6-trimethylbenzoyl diphenylphosphinic oxide (BAPG), phenylpropanedione (PPD). Among these, TPO and BAPO stand out for generating 2 and 2 to 4 free radicals, respectively, while the CQ system Amine generates only 1 free radical, yet this system is totally dependent on the random combination of the QC and amine components which in some cases may not occur and thus generate no free radical.

[013] The amount of free radicals is fundamental for the polymerization of the material and, consequently, for the physical, chemical and biological properties. Thus, the higher the radical generation, the higher the degree of conversion and the greater the biocompatibility of the adhesive system.

In view of these advantages, US3022114 and US2011 / 0275Q35 refer to "seif-etc" dental adhesive systems containing camphorquinone and TPO as a photoinitiating system.

[015] Unlike these documents, this invention: proposed resinous dental composites with high load content- ^• compared to adhesive systems (which have low or no filler particles content).

[016] The article "Can CQ If Completeiy Replaced by Alternative Initiators in Dental Adhesives?" of ILTE, Micoleta et al (200-7 ·), refers to dental adhesive systems containing camphorquinone or TPO as the photoinitiated system. In addition to the fact that this document differs from the present invention in that it relates to adhesive systems, it also differs in using photoinitiator systems in isolation.

[017] In the present invention, the replacement of the conventional initiator system by the association of camphorquinone and TPO made it possible to maintain the chemical-physical properties of the material, with aesthetic gains and polymerization depth gain.

In US8821157, a formulation in orthodontic adhesive systems containing camphorquinone as a photoinitiating system and some unspecified phosphoric oxide is also described. Because it is an adhesive system, the formulation has no or low concentration of filler particles and still has the exclusive indication of fixing brackets and orthodontic bands.

[019] The presence and quantity of charge particles is the key factor in establishing the optimal concentration of the photoinitiator system so as not to impair the chemical-physical properties and indications of the material for its use, such as the composite in question.

[020 j The technology described in the article "SAPO as an alternative photoinltíator for the radical polymerization of Dental Zesins ", by Meereís et al (2014),. refers to dental adhesive systems containing a BAPO-type phosphinic oxide as an alternative photoinitiating system. The proposed invention differs from this article in that it is high content dental composite resins. by using another phosphinic oxide photoinitiator system, the PO.

[021] It is noteworthy that, regardless of the advantage of the use of type 1 photoinitiators in dental adhesive systems, the advantages are not evident when these are used indistinctly in restorative composites, either in their pure use or in association with the CQ-Araina system. This occurs for two reasons: higher polymerization shrinkage stress and lower cure depth.

[022] The highest polymerization shrinkage stress occurs because, for restorative materials, the degree of conversion is directly related to the polymerization shrinkage.

[023] Materials with greater polymerization shrinkage can generate gaps between the tooth interface and restoration, which may affect the longevity of the restoration in the mouth.

[024] Despite not being directly applied, it may seem simple to use the same photoinitiation system as adhesive systems ^' with. low load content in. high load content restorative materials.

However, as can be seen from Figure 1, constructed on the basis of the present invention, it can be seen that the load directly influences the conversion rate of the resinous material. Thus, when no charge particle content is added to the material, the The degree of conversion is much higher with the same amount (concentration) of photoinitiator system compared to materials with charge particle inclusion.

[026] This is because, when there is no addition of charge particles, the refractive index of the matrix is the same to allow light to pass through for homogeneous photoactivation throughout the material. On the other hand, with the addition of oarga particles, there is a difference between the refractive index of the resin matrix and the charge particle in order to cause light scattering, attenuating the amount of light that passes completely through the material, such as schematic illustrated in Figure 2.

[027] Therefore, the higher the load content, the lower the degree of conversion. Thus, it is evident that in order to obtain an adequate degree of conversion, with the addition of high concentration charged particles, different concentrations of the photoinitiator system must be tested for application in composites.

[028] Therefore, in view of the absence of prior art documents and the need to obtain a dental composite which has no change in the degree of conversion or polymerization depth and enables the manufacture of a wider range of lighter colors. For dental restorative materials, the present invention relates to a light-curable resin composite comprising high filler content and a resin matrix of dimethacrylate monomers that polymerize by free radical reaction initiated by the synergism of photoinitiator systems.

Brief Description of the Invention: The present intent refers to a photopolymerizable resin composite, which has a high filler content and a resinous matrix of dimethacrylate monomers.

Additionally, the invention relates to the use of said photopolymerizable resin composite in the manufacture of dental resinous materials such as sealants, low or high viscosity composite resins, and photoactive or dual set resin cements.

Brief Description of the Figures:

[031] For a complete and complete view of the object of this invention, reference figures are given as follows.

[032] Figure 1 graphs the indirect linear correlation of the degree of conversion as a function of the percentage of charge particles.

[033] Figure 2 schematically illustrates the difference in light passing through the material according to the content of the charge particles.

[034] Figures 3A-E graph the depth conversion degree map according to exposure at each wavelength (blue and violet) for the photoinitiator systems tested, where (A) is only QC, ( B) is only the TFO, (C) is the 3GQ: 1TP0 association, (D) is the ICQrlTPO association and (E) is the 1CQ: 3TP0 association, respectively.

Figures 4A-B graphically depict light passing through the composite according to each; of the photoinitiator systems tested where (A) is at a thickness of 1mm and (B) is at a thickness of 3mm. Figures 5A-B graphically represent the light irradiation at each wavelength within the composite according to the tested photocellular systems, where (A) is in Imm thickness and (3) at 3mm thickness,

[637] Figure 6 graphs the degree of yellow before and after polymerization of each of the photoinitiator systems tested.

Figure 7 graphically represents the degree of color change after polymerization of each of the photoinitiator systems tested.

[039] Figure 8 graphs the absorbance according to. the wavelength of different photoinitiators: QC _(blue): fvermelho TPO) and Ivocenn ⁵⁵ (Green 5.

[040] Figure 9 graphically represents the monomeric conversion capability of each photoliquer system.

Detailed Description of. Invention:

[041] The present invention describes a compound! light-curable resinous resin for dental use, which may comprise low to high viscosities according to the lower or higher filler content such that: larger fillers are added to lower percentages of organic matrix and photoinitiator system for formulation of higher viscosity; and lower amounts of filler are added to higher percentages of organic matrix and photoinitiating system for formulation of lower viscosity composites and may comprise of;

- 50 to 90% filler particles;

- 9.8 to 45% of mono-erosion resin matrix base climetacrylates;

- 0.2 to 5.0% of the QC-based photoinitiator system associated with tertiary araina in a ratio equal to or multiplied by two in relation to the percentage of QC and TPO with ratios of 3: 1 to 1: 1 was in relation to the roolar amount. of CQ.

In a preferred embodiment, the resin matrix exhibits associations of high molecular weight diraethacrylate monomers such as Bisphenol A Glycyl Dimethacrylate (Bis-GMA), Bisphenol A Ethoxylated Glycidyl Dimethacrylate (Bis-EMA), Urethane Dimethacrylate (UDMA) , polyethylene glycol dimethacrylate (PEGDMA), triethylene glycol dimethacrylate

(TEGDMA) and its mixtures and low molecular weights as: Bis (glyceryl dimetacrialto) pyromellitate chloride

(P GDM), Hydroxyethyl Methacrylate (HEMA), Hydroxyethyl Methacrylate Phosphate (HEMA-P), 10-Methacryl Ioxideell Dihydrogen Phosphate (1Q-MDP), 4 Methacryloxymethyltrimethacrylate

(- ΞΤ), 4 methacryloxy-trimethylitate anhydride (4- META), Eenyl-P, glycerol dimethacrylate dihydrogen phosphate

(GDMP), 11-methacryloyloxy, 1-decanedicarboxylic acid

(MAC-10) and mixtures thereof.

The charge particles are selected from glass and / or inorganic silica particles. As an alternative embodiment of the invention, ceramic particles may be used.

The low or high viscosity of the resin composite depends on the differentiated association of resin matrix and the amount and type of filler particle used to produce low viscosity dental materials { ^. flow) at high viscosities, such as composite resins. W

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[045] Photoinitiating systems are the QC and TPO components in combinations ranging from 3: 1 to 1: 1.

[046] Additionally, the invention relates to the use of composite resin fotopolimeri Zavel in manufacturing dental resin materials such as sealants, composite resins of low or high viscosity: photocured resin or ^cement: Dual attached.

Tests:

Determination of the choice of the ideal phosphinic oxide for synergistic association with the CQ-amine photoinitiator system.

[047] The choice of the ideal phosphinic oxide for synergistic association with the CQ-amine photoinitiated system was based on the pilot study of the analysis of the degree of monomeric conversion with equimolar concentrations of the phosphoric oxides TPO and BABO relative to the CQ-amine system. with a minimum concentration of 0,2% by weight.

[043] Initial tests have shown that even at equimolar concentrations relative to the CQ-amine system, BAPO has a higher degree of conversion than the CQ-amine system, while TPO has a similar degree of conversion to the CQ-amine system for Iram specimens. . thick, as observed in Figure 1.

Determination of optimal concentration of synergistic association between QC and TPO:

Choosing the ideal phosphine oxide for synergistic association with the CQ-amine system so as not to change the degree of conversion, the optimal concentration of each photoinitiator system, CQ and TPO, was initially tested by analyzing the degree of monomeric conversion in different depths and different test proportions, totaling the total concentration of 0,2% by weight.

The analysis of the degree of depth conversion (Figures 3A-E) showed that the proportions between 3: 1 and 1: 1 of QC and TPO, respectively, showed similar degree of monomero conversion to the QC-C system. up to 2mm, as specified by ISO4049: 2009, specifies for dental materials.

The similarity in the degree of depth conversion of the 3: 1 to 1: 1 ratio of QC and TPO can be explained by the results of light passing through the composite, which was similar (3: 1) or higher ( 1: 1) compared to the CQ-amine system, as is apparent from Figures 4A-B and 5Ά-Β. Thus, the addition of up to 50 µl TPO to the CQ-amine photoinitiator system did not influence the light passage through the composite or the degree of depth conversion: up to 2 mm.

Other tests performed:

{052] Other tests were performed to evaluate the improvements provided by the synergistic association of TPO and QC, such as the evaluation of the initial color and color stability after photoactivation by spectrophotometry.

As can be seen from Figure 6, the addition of 100% camphorquinone (QC) makes the resinous material more yellowish (dark blue) compared to formulations containing bisphenyl (2,4,6-trimethylbenzoyl) phosphinic oxide ( TPO). Thus, the formulation comprising 50% QC and 50% TPO (1: 1) showed a lower degree of yellow before and after polyserization.

[054] Such a result ensures that resinous materials Containing 50% QC and 50 TPO (1: 1) make it possible to manufacture a wider range of lighter colors compared to conventional formulations of ...

In relation to color stability, shown in Figure 7, the ratio of 1: 1 QC and TPO also showed less color change after photoactivation compared to the QC-amine system, although higher than that of TPO without Association .

[056] Thus, this result ensures greater reliability in choosing the definitive color of the resinous material as it undergoes less color change after curing.

Comparative Tests

[057] The only commercially available restorative composite that does not have camphorquinone as its exclusive photoinitiator system is the company's Ivocerin ^® . Ivoclar Vívadent, who presents his own photoinitiator.

[058] The material of this company proved to be capable of providing adequate degree of conversion as compared to conventional camphorquinone based resins.

However, such a photoinitiator only partially replaces the camphorquinone concentration with a slightly less yellowish photoinitiator because its absorption is not exclusively within the blue wavelength (such as camphorquinone), but partly within the wavelength. violet wave (see Figure 9).

Each photoinitiator is capable of absorbing a certain wavelength: camphorquinone absorbs within the blue wavelength (440nm to 85nm); the TPO, exclusively the violet wavelength (380nm to 440nm). W

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and BAPO, in wavelengths partially in blue to violet.

[061] This fact further reduces the applicability of photoinitiators such as BAPO and TPO for composites, as longer wavelengths (such as blue; tend to penetrate more than shorter wavelengths (such as violet).

Thus, the invention proposes a phosphinic oxide photoinitiator to obtain less initial yellowing of the material as well as less alteration of. color after polymerization without affecting the degree of material conversion. The choice of TPO was made by producing a smaller amount of free radicals in relation to the other phosphine oxides.

[.063] In the prior evaluation of formulations equal to similar resin composite formulations containing the different photoinitiators (see Figure 10), it is noteworthy that when BAPO is used as a photoinitiator system, the composite exhibits a higher degree of conversion to the surface of compared to when camphorquinone is used. On the other hand, for TPO there is no statistical difference in the degree of conversion compared to camphorquinone.

Of course, total substitution of camphorquinone for TPO would be impossible because of all the physical issues that could affect the depth of polymerization exposed so far.

Camphorquinone, although causing yellowing of the material, exhibits better light absorption at depth as it absorbs the blue wavelength.

[066] On the other hand, TPO has a more aesthetic and potential white color of similar or superior generation of radicals ^: free compared to camphorquinone.

[ ^Q 67] As shown in Figure 6, the increase in TPO caused yellowing reduction in relation to higher QC concentrations and the 1: 1 QC and ?? Q association showed less yellowish coloration and similar to TPO isolated as photoinitiated system. .r compared to camphorquinone alone and even less color change after polymerization compared to isolated QC, as shown in Figure 7.

[068] Thus, this association favors the production of. composites in lighter colors and even facilitates the correct choice of color due to the smaller color change after polymerization.

[069] On the other hand, as observed in Figures A-3 and S¾H3, a. The reduction in QC caused a drastic loss of light passage for the formulation with higher concentration of TPO compared to the formulation of CO and TPO alone compared to isolated QC. However, the 1: 1 formulation showed light passage higher than isolated QC.

[070] Although this fact did not have a greater influence on the polymerization of the 1: 1 formulation compared to the isolated QC, observing Figures 3A-E, it is noticeable that the cure depths of both were statistically equal up to 2mm. and concentrations above 50% of TPO relative to QC, as they caused a reduction in light passage and loss of cure depth.

Claims

1. A photopolymer resizable composite comprising:

- resin matrix base of dimethacrylate monomers;

- charge particles;

- photoinitiator system based. of QC and TPO in ratios from 3: 1 to 1: 1.

Composite according to Claim 1, comprising 9.8 to 45% resin matrix base.

Composite according to Claim 1, characterized in that it comprises 50 to 90% of carbon particles.

Composite according to Claim 1, characterized in that it comprises 0.2 to 5.0% of photoinitiated system.

Composite according to Claim 1, characterized in that the resinous matrix preferably has combinations of high molecular weight dimethacrylate monomers such as Bisphenoyl Glycyl Dimethacrylate (Bis-GMA), Bisphenoyl Ethoxylated Glycidyl Dimethacrylate (Bis-EMA), Urethane Dimethacrylate (UDMA), polyethylene glycol dimethacrylate (PEGDMA), triethylene glycol dimethacrylate (TEGDMA) and their mixtures and low molecular weights such as bis (glycerii dimethacrialto) pyromellitate (PMGDM), hydroxyethyl methacrylate (HEMA), hydroxyethyl methacrylate (HEMA), HEMA-P), 10-methacryloyloxydecyl dihydrogen phosphate (10-MDP), 4-methacryloxytrimethylacetate (4-MET), 4 methacryloxy-ethyl trimellitate anhydride (4-SEA), Phenyl-P, glycerol dimethacrylate dihydrogen phosphate (GDMP), 11-methacryloyloxy, 1-decaroxydicarfooxylic acid (MAC-10) and mixtures thereof.

Composite according to Claim 1, characterized in that the filler particles are separated from the group consisting of glass particles and / or. pyrogenic silica.

7. Composite according to King Indication 3, characterized in that the particles of charge are also ceramic particles.

Composite according to Claim 1, characterized in that the viscosity of the resin composite varies according to the association of resin matrix and the amount and type of the loading particle.

Composite according to Claim 1, characterized in that it further comprises a reducing agent in the ratio equal to or multiplied by two at. relative to the percentage of QC, wherein preferably the reducing agent is a tertiary amine .:

Use of the light-curable resin composite as defined in claims 1 to 9, characterized in that it is in the manufacture of dental resinous materials such as sealants, low or high viscosity composite resins, and photoactive or dual-set resin cements.