RU2744746C1 - Light-cured dental material based on polymers - Google Patents

Abstract

FIELD: medicine.

SUBSTANCE: present invention relates to medicine, namely to a light-curing dental material based on polymers containing urethane dimethacrylate, polyethylene glycol dimethacrylate, 2-hydroxyethyl methacrylate and diphenyl (2,4,6-trimethylbenzoyl) phosphine oxide, in the following ratio of components, wt.%: urethane dimethacrylate - 50-68, polyethylene glycol dimethacrylate - 30-48, 2-hydroxyethyl methacrylate - 1-5, diphenyl (2,4,6-trimethylbenzoyl) phosphine oxide - 1-3.

EFFECT: development of a light-curing composition with a reduced odor intensity, low toxicity and no irritating effect, ensuring stable printing results and increasing mechanical properties.

1 cl, 10 ex

Description

The invention relates to the field of dentistry, namely to a light-cured dental material based on polymers, intended for modeling and use in the process of manufacturing dental restorations. The material is used in specialized rooms equipped with a 3D printer using stereolithography technology.

The following solutions are known from the prior art.

Known light-curing material based on polymers (US patent No. 4267133, published 05/12/1981), containing polymerizable methacrylate and / or acrylate with the addition of a light sensitizer and / or filler, where benzyl benzoin methyl ether, ethyl benzoin ether, propyl ether can be used as a light sensitizer benzoin, benzoin butyl ester, which can be used alone or in combination. Although the amount of photosensitizer is determined by the type of base material, curing rate, the ratio of other additives (pigment, etc.), it is usually used in an amount of 0.2 to 10% by weight of the material, preferably 0.5-8 wt. %. In this case, the procedure for light curing is carried out using actinic radiation with a wavelength of 3400 Å or more.

The disadvantage of the known material is that it is not intended for use in 3D printing.

Also known is a light-curing material based on polymers (US patent No. 6506815, published 05/30/2002), containing polymerizable monomer of methacrylate or acrylate in an amount from 15 to 95 wt. %; organic filler and / or organo-inorganic composite filler in an amount from 1 to 75 wt% used to improve flexural strength, to provide impact resistance and to bring the polymer composition to a pasty state, as well as an initiator system, which consists of a heat-type polymerization initiator benzoyl peroxide and / or camphorquinone photoinitiator. Their amount is from 0.05 to 5.0 mass%, and to them can be added from 1 to 60 mass% of filler surface treated with vinyl trichlorosilane.

The disadvantage of the known material is that it is not intended for use in 3D printing.

The closest analogue of the patented solution is a light-curing material based on polymers containing an organic matrix, which consists of urethane dimethacrylate (15.0-29.0 wt.%) As a high-molecular oligomer participating in the light polymerization reaction and increasing the elasticity of the material; an elastomer (8.0-16.0 wt%) and triethylene glycol dimethacrylate (2.0-3.8 wt%) (hereinafter TGM-3) as a crosslinking agent and a monomer-diluent that reduces the viscosity of high molecular weight oligomers; organic-inorganic filler, which includes an organic filler modified by an oligomeric mixture polymethyl methacrylate and a cluster consisting of an organic filler modified with an oligomeric mixture CS-400 polyurethane and a pre-silanized inorganic filler of finely dispersed silicon oxide. The oligomeric mixture includes the following components: urethane dimethacrylate, triethylene glycol dimethacrylate, elastomer, camphoroquinone, ethyl 4-dimethylaminobenzoate; an initiating system, which consists of photoinitiators (camphorquinone and dimethylketalbenzyl) with a wavelength of 340-400 nm in the UV spectrum and 400-500 nm in the visible part of the spectrum and a thermal initiator that promotes the formation of radicals under the action of infrared thermal radiation with a wavelength of 750-1500 nm , each of which can be introduced into the composition in a minimum amount of 0.005 mass. %

The disadvantage of the known material is that it is not intended for use in 3D printing.

The technical problem solved by the claimed invention consists in the development of a light-curing composition with a decrease in odor intensity, low toxicity and no irritating effect, ensuring stable printing results and increasing mechanical properties.

The problem is solved due to the composition of a light-curing dental material based on polymers containing urethane dimethacrylate, polyethylene glycol dimethacrylate, 2-hydroxyethyl methacrylate and diphenyl (2,4,6-trimethylbenzoyl) phosphine oxide, with the following ratio of components in mass. %:

urethane dimethacrylate - 50-68,

polyethylene glycol dimethacrylate -30-48,

2-hydroxyethyl methacrylate - 1-5,

diphenyl (2,4,6-trimethylbenzoyl) phosphine oxide or Phenylbis (2,4,6-trimethylbenzoyl) phosphine oxide - 1-3.

In addition, in particular cases of implementation of the invention, the following are used:

- pigments:

- white titanium dioxide in a concentration of 0.1-1 wt. % or 0-0.9 wt. % depending on the version:

- iron oxide red at a concentration of 0.1-1 wt. % depending on the version,

- iron oxide brown at a concentration of 0.1 - 1 wt. % depending on the version;

- barium sulfate at a concentration of 20-30% as a radiopaque agent.

Urethane dimethacrylate is used in the composition as a high molecular weight oligomer, which is the main component that determines the properties of the initial mixture in liquid form and the finished product obtained as a result of 3D printing. Due to its structure and molecular weight, it provides optimal values of the physical and mechanical characteristics of the material. When used in a composition of less than 50% or more than 70%, there is a deterioration in physical and mechanical properties, as well as a decrease in print quality.

Polyethylene glycol dimethacrylate is used in the composition as a bifunctional monomer. Due to its structure and molecular weight, it provides reactivity and optimal viscosity of the system, as well as optimal physical and mechanical characteristics of the finished product obtained as a result of 3D printing. When used in a composition of less than 30% or more than 50% polyethylene glycol dimethacrylate, the required physical and mechanical parameters deteriorate and the print quality decreases.

2-hydroxyethyl methacrylate in the composition plays the role of a monofunctional monomer, due to the structure and molecular weight, provides the optimal viscosity of the finished system. When 2-hydroxyethyl methacrylate is used in a composition of less than 1% and more than 5%, the optimal viscosity of the system changes, which, in turn, leads to a deterioration in print quality.

Diphenyl (2,4,6-trimethylbenzoyl) phosphine oxide in the composition of the material plays the role of a photoinitiator for the polymerization of free radical photopolymerizable compositions when irradiated with light in the range from 350 nm to 405 nm. This photoinitiator is most suitable for initiating the polymerization of the system when it is added in a concentration of 1-3%, while ensuring optimal print quality, as well as the physical and mechanical characteristics of the product. In the case of using in the composition of a concentration of less than 1% or more than 3%, the speed and quality of printing deteriorate, as well as the physical and mechanical characteristics of the printed product.

Phenylbis (2,4,6-trimethylbenzoyl) phosphine oxide in the composition of the material plays the role of a photoinitiator for the polymerization of free radical photopolymerizable compositions when irradiated with light in the range from 380 nm to 450 nm. This photoinitiator is most suitable for initiating the polymerization of the system when it is added in a concentration of 1-3%, while ensuring the optimal print quality, as well as the physical and mechanical characteristics of the product. In the case of using in the composition of a concentration of less than 1% or more than 3%, the speed and quality of printing deteriorate, as well as the physical and mechanical characteristics of the printed product.

The claimed material is obtained by vigorous stirring on a dissolver while heating a mixture of oligomer and monomers to at least 60 ° C with the addition of a photoinitiator until uniformity is achieved. After that, to obtain a material with certain organoleptic properties, pigments and fillers are added to the system and the mixture is again subjected to intensive mixing.

As a result, the material has a liquid consistency with organoleptic properties determined by fillers and pigments. In this case, the liquid has a mild odor.

For the manufacture of dental products from this material, such as mouthguards, crowns, etc. the resulting material is loaded into a 3D printer using stereolithography technology, in which the material is cured under the influence of radiation of a certain wavelength.

Water absorption of products made from the declared material, no more than 40 μg / mm³. The solubility of products made from the declared material is not more than 7.5 μg / mm³.

The solution is further illustrated by examples.

Example 1.

The type of material claimed is Dental Yellow Clear, and is used to make surgical templates. It is a transparent yellow liquid with a mild odor. To obtain the specified type of material, the components are mixed in the following proportions:

urethane dimethacrylate - 58%,

polyethylene glycol dimethacrylate -37%,

2-hydroxyethyl methacrylate - 3%,

Phenylbis (2,4,6-trimethylbenzoyl) phosphine oxide - 2%.

In this case, the material is obtained by intensive mixing on a dissolver while heating a mixture of all components until uniform.

Flexural strength of a product made from the material obtained is not less than 70 MPa. For this type of material, there is a restriction on contact with the patient's body tissues for no more than 24 hours, since products made from Dental Yellow Clear are short-term contact products according to the classification given in GOST R ISO 7405, clause 4.2.

Example 2.

The type of material claimed is Dental Clear, used for making surgical templates and aligners. It is a clear, colorless liquid with a mild odor. To obtain the specified type of material, the components are mixed in the following proportions:

urethane dimethacrylate - 58%,

polyethylene glycol dimethacrylate -37%,

2-hydroxyethyl methacrylate - 3%,

diphenyl (2,4,6-trimethylbenzoyl) phosphine oxide - 2%.

In this case, the material is obtained by intensive mixing on a dissolver while heating a mixture of all components until uniform. Flexural strength of a product made from the material obtained is not less than 70 MPa.

For this type of material, a limitation is imposed on contact with the patient's body tissues for no more than 30 days, since products made from Dental Clear material are long-term contact products according to the classification given in GOST R ISO 7405, clause 4.2.

Example 3.

The type of material claimed is Dental Peach, used for the production of demonstration models and master models for thermoforming. It is an opaque peach-colored liquid with a mild odor. To obtain the specified type of material, the components are mixed in the following proportions:

urethane dimethacrylate - 58%,

polyethylene glycol dimethacrylate -37%,

2-hydroxyethyl methacrylate - 3%,

phenylbis (2,4,6-trimethylbenzoyl) phosphine oxide - 2%.

The claimed material is obtained by vigorous stirring on a dissolver while heating a mixture of oligomer and monomers with the addition of a photoinitiator until uniform. After that, to obtain a material with certain organoleptic properties, the following pigments are added to the system:

iron oxide red pigment - 0.1-1% in relation to the resulting mass, depending on the desired shade,

pigment white titanium dioxide - 0.1-1% in relation to the resulting mass, depending on the desired shade,

and again subject the mixture to vigorous stirring.

Flexural strength of a product made from the material obtained is not less than 70 MPa. For this type of material, there is a limitation on contact with the patient's body tissues for no more than 24 hours, since products made from Dental Peach material are short-term contact products according to the classification given in GOST R ISO 7405, clause 4.2.

Example 4.

The type of material claimed is Dental Bleach, which is used to make temporary crowns and bridges in white. It is a translucent white liquid with a mild odor. To obtain the specified type of material, the components are mixed in the following proportions:

urethane dimethacrylate - 58%,

polyethylene glycol dimethacrylate -37%,

2-hydroxyethyl methacrylate - 3%,

diphenyl (2,4,6-trimethylbenzoyl) phosphine oxide - 2%.

The claimed material is obtained by vigorous stirring on a dissolver while heating a mixture of oligomer and monomers with the addition of a photoinitiator until uniform. Then, to obtain a material with certain organoleptic properties, white titanium dioxide pigment is added to the mixture - 0.1-1%, in relation to the resulting mass, depending on the desired shade, and the mixture is again subjected to intensive mixing.

Flexural strength of a product made from the material obtained is not less than 100 MPa. For this type of material, a limitation is imposed on contact with the patient's body tissues for no more than 30 days, since products made from Dental Bleach material are long-term contact products according to the classification given in GOST R ISO 7405, clause 4.2.

Example 5.

The type of material claimed is Dental Cast, used to make models suitable for casting metals and pressing ceramics. It is a transparent liquid of red / cherry color with a mild odor. To obtain the specified type of material, the components are mixed in the following proportions:

urethane dimethacrylate - 58%,

polyethylene glycol dimethacrylate - 37%,

2-hydroxyethyl methacrylate - 3%,

phenylbis (2,4,6-trimethylbenzoyl) phosphine oxide - 2%.

Cherry dye is added - 0.01% in relation to the resulting mass of the mixture.

In this case, the material is obtained by intensive mixing on a dissolver while heating a mixture of all components until homogeneous.

Flexural strength of a product made from the material obtained is not less than 30 MPa. The specified type of material does not come into contact with the patient's tissues.

Example 6.

The type of material declared is Dental RO, which is used to make X-ray contrast aligners and templates. It is an opaque gray liquid with a mild odor. To obtain the specified type of material, the components are mixed in the following proportions:

urethane dimethacrylate - 58%,

polyethylene glycol dimethacrylate -37%,

2-hydroxyethyl methacrylate - 3%,

phenylbis (2,4,6-trimethylbenzoyl) phosphine oxide - 2%.

The claimed material is obtained by vigorous stirring on a dissolver while heating a mixture of oligomer and monomers with the addition of a photoinitiator until uniform. Then, to obtain a material with certain organoleptic properties, barium sulfate is added to the system - 20-30% by weight in relation to the resulting mass, and the mixture is again subjected to intensive mixing.

Flexural strength of a product made from the material obtained is not less than 50 MPa. For this type of material, a limitation is imposed on contact with the patient's body tissues for no more than 24 hours due to the fact that products made from Dental RO material are short-term contact products according to the classification given in GOST R ISO 7405, clause 4.2.

Example 7.

The type of material claimed is Dental Pink, used for the manufacture of a temporary denture base and individual trays. It is a translucent pink liquid with a mild odor. To obtain the specified type of material, the components are mixed in the following proportions:

urethane dimethacrylate - 58%,

polyethylene glycol dimethacrylate -37%,

2-hydroxyethyl methacrylate - 3%,

phenylbis (2,4,6-trimethylbenzoyl) phosphine oxide - 2%.

The claimed material is obtained by vigorous stirring on a dissolver while heating a mixture of oligomer and monomers with the addition of a photoinitiator until uniform. After that, to obtain a material with certain organoleptic properties, the following pigments are added to the system:

iron oxide red pigment - 0.1-1% wt in relation to the resulting mass, depending on the desired shade,

pigment white titanium dioxide - 0.1-1% wt in relation to the resulting mass, depending on the desired shade,

and again subject the mixture to vigorous stirring.

Flexural strength of a product made from the material obtained is not less than 70 MPa. For this type of material, there is a restriction on contact with the patient's body tissues for no more than 30 days, since products made from Dental Pink material are long-term contact products according to the classification given in GOST R ISO 7405, clause 4.2.

Example 8.

The type of material claimed is Dental Pink Soft, used to make elastic gingival masks. It is a translucent pink liquid with a mild odor. To obtain the specified type of material, the components are mixed in the following proportions:

urethane dimethacrylate - 58%,

polyethylene glycol dimethacrylate - 37%,

2-hydroxyethyl methacrylate - 3%,

phenylbis (2,4,6-trimethylbenzoyl) phosphine oxide - 2%.

The claimed material is obtained by vigorous stirring on a dissolver while heating a mixture of oligomer and monomers with the addition of a photoinitiator until uniform. Then, to obtain a material with certain organoleptic properties, iron oxide red pigment is added to the system - 0.1 - 1% by weight in relation to the resulting mass, depending on the desired shade, and the mixture is again subjected to intensive mixing.

The flexural strength of a product made from the resulting material is not measured, since the final product is not subjected to mechanical stress during its intended use. The defining indicator for this version of the material is its color. For this type of material, a limitation is imposed on contact with the patient's body tissues for no more than 30 days, since products made from Dental Pink Soft material are products of long-term contact according to the classification given in GOST R ISO 7405, clause 4.2.

Example 9.

The type of material claimed is Dental Sand A1-A2, used for the manufacture of temporary crowns and bridges. It is an opaque liquid of sand (A1-A2) color with a mild odor. To obtain the specified type of material, the components are mixed in the following proportions:

urethane dimethacrylate - 58%,

polyethylene glycol dimethacrylate - 37%,

2-hydroxyethyl methacrylate - 3%,

phenylbis (2,4,6-trimethylbenzoyl) phosphine oxide - 2%.

The claimed material is obtained by vigorous stirring on a dissolver while heating a mixture of oligomer and monomers with the addition of a photoinitiator until uniform. After that, to obtain a material with certain organoleptic properties, the following pigments are added to the system:

iron oxide brown pigment - 0.1-1% wt in relation to the resulting mass, depending on the desired shade.

pigment white titanium dioxide - 0.1-1 %% wt in relation to the resulting mass, depending on the desired shade,

and again subject the mixture to vigorous stirring.

Flexural strength of a product made from the material obtained is not less than 100 MPa. For this type of material, there is a limitation on contact with the patient's body tissues for no more than 30 days, since products made from Dental Sand A1-A2 material are products of long-term contact according to the classification given in GOST R ISO 7405, clause 4.2.

Example 10.

The type of material declared is Dental Sand A3, used for the manufacture of temporary crowns and bridges. It is an opaque liquid of sand (A3) color with a mild odor. To obtain the specified type of material, the components are mixed in the following proportions:

urethane dimethacrylate - 58%,

polyethylene glycol dimethacrylate - 37%,

2-hydroxyethyl methacrylate - 3%,

phenylbis (2,4,6-trimethylbenzoyl) phosphine oxide - 2%

to homogeneity.

Then add iron oxide brown pigment - 0.2-1% and white titanium dioxide pigment - 0-0.9% in relation to the resulting mass, depending on the desired shade and again vigorously stirred until a homogeneous mass of a homogeneous shade is achieved.

Flexural strength of a product made from the material obtained is not less than 100 MPa. For this type of material, a limitation is established on contact with the patient's body tissues for no more than 30 days due to the fact that products made from Dental Sand A3 material are long-term contact products according to the classification given in GOST R ISO 7405, clause 4.2.

Claims (13)

1. Light-curing dental material based on polymers containing urethane dimethacrylate, polyethylene glycol dimethacrylate, 2-hydroxyethyl methacrylate and diphenyl (2,4,6-trimethylbenzoyl) phosphine oxide, with the following ratio of components, wt. %: urethane dimethacrylate - 50-68, polyethylene glycol dimethacrylate - 30-48, 2-hydroxyethyl methacrylate - 1-5, diphenyl (2,4,6-trimethylbenzoyl) phosphine oxide - 1-3. 2. The material according to claim 1, characterized in that it additionally includes - white titanium dioxide in a concentration of 0.1-1 wt. % or 0-0.9 wt. %, and / or - iron oxide red at a concentration of 0.1-1 wt. %, and / or - iron oxide brown in a concentration of 0.1-1 wt. %, and / or - barium sulfate in a concentration of 20-30 wt.% in relation to the resulting mass of material as a radiopaque agent.