CN113181059A - Oral cavity repairing material and preparation method and application thereof - Google Patents
Oral cavity repairing material and preparation method and application thereof Download PDFInfo
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- CN113181059A CN113181059A CN202110649567.1A CN202110649567A CN113181059A CN 113181059 A CN113181059 A CN 113181059A CN 202110649567 A CN202110649567 A CN 202110649567A CN 113181059 A CN113181059 A CN 113181059A
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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
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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
- A61K6/60—Preparations for dentistry comprising organic or organo-metallic additives
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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
- A61K6/78—Pigments
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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
- A61K6/80—Preparations for artificial teeth, for filling teeth or for capping teeth
- A61K6/884—Preparations for artificial teeth, for filling teeth or for capping teeth comprising natural or synthetic resins
- A61K6/887—Compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
Abstract
The invention provides an oral cavity repairing material and a preparation method and application thereof, wherein the oral cavity repairing material comprises a combination of a first polymethyl methacrylate resin, a second polymethyl methacrylate resin, a pigment, a dispersing agent, a coating agent and a compatilizer; the oral cavity repairing material is prepared by adding the first polymethyl methacrylate resin, the second polymethyl methacrylate resin, the coating agent, the dispersing agent and the compatilizer, so that the prepared oral cavity repairing material is uniformly dispersed, the agglomeration of the pigment can be effectively avoided, the problem that crystal points appear on the surface and inside of the product due to the agglomeration and nonuniform dispersion of the pigment is further avoided, the oral cavity repairing material with stable color is successfully prepared, and the oral cavity repairing material has important research value.
Description
Technical Field
The invention belongs to the technical field of composite materials, and particularly relates to an oral repair material, and a preparation method and application thereof.
Background
With the progress of science and technology, electronic information technology is rapidly developing. The introduction of the combination of computer system intelligent design (CAM) and computer precision machining (CNC) and other technologies has led to pioneering development and application in the field of bioremediation materials. The introduction of the CAM/CNC technology enables the product to have the characteristics of short production period, high product precision, good aesthetic effect and the like, and the comprehensive performance of the product is integrally improved. Meanwhile, the product has flexible designability, shorter design period and quality stability control.
In the oral cavity repair materials science, polymethyl methacrylate (PMMA) resin matrix composite material is the most common repair material, and has the outstanding characteristics of excellent plasticity, good mechanical property, corrosion resistance, durability, biocompatibility and the like. PMMA has great application in the field of biological repair materials, is a common oral repair material, has the characteristics of short product forming period, simple and convenient grinding and polishing, good physical and chemical properties, biocompatibility and the like, and simultaneously has the characteristics of flexible designability, color gradient comparable to that of natural teeth and stable controllability of products.
Many PMMA dental composites are commercially available. CN103273713A discloses a four-layer color synthetic resin block and a preparation method thereof, wherein the four-layer color synthetic resin block is composed of four layers of structures in sequence, and each layer of structure comprises the following components: polymethyl methacrylate, iron oxide red, iron oxide black, iron oxide yellow, titanium white, methyl methacrylate and ethylene glycol dimethacrylate. The preparation method comprises the following steps: drying the polymethyl methacrylate powder at 80-90 ℃; preparing four layers of materials according to the proportion, uniformly mixing the materials of each layer, and kneading the materials until the dough period to form a plastic dough material; hot-pressing four layers of plastic dough materials in a mould in sequence, wherein the hot-pressing temperature is 110-130 ℃, and the hot-pressing time is 10-20 min; and (3) carrying out heat treatment on the four-layer-color synthetic resin block subjected to hot press molding at the temperature of 80-90 ℃ for 10-12 h to obtain a four-layer-color synthetic resin block finished product, wherein the dental model or the temporary crown bridge processed by the method has natural and vivid color development. However, the color gradient change of the product prepared by the method is obvious and can not be compared with that of the protoplasm dental material, the requirement of people on beauty can not be met, the process is complex, and the control on the stability of the product is difficult.
CN108078789A discloses a preparation method of a multicolor integrated dental repair material, which comprises the following steps: adding the components into a plurality of containers, controlling the temperature to be 10-25 ℃, stirring for 3-5 min, uniformly mixing, and standing for 10-20 min to enable the components to become viscous colloid, so as to obtain mixtures with different colors; step two, placing the mixture with different colors in an environment with the temperature below 15 ℃ for cooling to obtain semi-solidified mixtures with different colors; and step three, taking out and stacking a plurality of semi-cured mixtures with different colors into a mold with openings at two ends, enabling an upper mold and a lower mold to move oppositely to seal the mold, heating to 40-80 ℃, carrying out pressure polymerization, curing and forming, and demolding to obtain the multicolor integrated dental repair material. The prepared gradient dental restoration material has high interface strength, high material consistency, good impact resistance and high manufacturing precision. CN112206170A discloses a gradient resin and a preparation method and application thereof. The gradual-change resin is formed by fusing different layers with color transition change, wherein the color transition change range between the two adjacent layers is 0.1-20%, and the gradual-change resin consists of 98-99.99% of resin powder and 0.01-2% of pigment by mass percentage. The light transmittance of the prepared gradient resin product is more than or equal to 50 percent, the product has no interlayer layering, natural color transition, mutual fusion between layers and no interlayer transition boundary, and has excellent aesthetic effect when being used for dental materials. However, the two methods only use simple physical mixing to carry out high-temperature compression molding with the colored filler and other additives, but it is difficult to ensure that the filler is fully dispersed in the resin matrix, and the color stability of the prepared product is difficult to ensure.
Therefore, the development of an oral cavity repairing material with uniformly dispersed components, stable color and simple preparation method is a technical problem which needs to be solved urgently in the field.
Disclosure of Invention
Aiming at the defects of the prior art, the invention aims to provide an oral repair material and a preparation method and application thereof; the oral cavity repairing material comprises a combination of a first polymethyl methacrylate resin, a second polymethyl methacrylate resin, a pigment, a dispersing agent, a coating agent and a compatilizer, all components of the prepared oral cavity repairing material are uniformly dispersed through reasonable proportioning of all the components, the problem that crystal points appear on the surface and inside of a product due to agglomeration and nonuniform dispersion of the pigment is avoided, the oral cavity repairing material with stable color is successfully prepared, and the oral cavity repairing material has important research value.
In order to achieve the purpose, the invention adopts the following technical scheme:
in a first aspect, the invention provides an oral cavity repairing material, which is characterized by comprising the following components in parts by weight: 58-80 parts of first-class polymethyl methacrylate resin, 0.001-4 parts of pigment, 0.1-4 parts of dispersing agent, 0.1-40 parts of coating agent and 2-10 parts of compatilizer.
The first type of polymethylmethacrylate resin may be 60 parts by weight, 62 parts by weight, 64 parts by weight, 66 parts by weight, 68 parts by weight, 70 parts by weight, 72 parts by weight, 74 parts by weight, 76 parts by weight or 78 parts by weight, and specific values therebetween, which are not exhaustive and included in the ranges for brevity and conciseness.
The second poly (methyl methacrylate) resin may be 2 parts by weight, 3 parts by weight, 4 parts by weight, 5 parts by weight, 6 parts by weight, 7 parts by weight, 8 parts by weight, or 9 parts by weight, and specific points therebetween, which are not exhaustive and included in the range for brevity.
The colorant may be 0.002 parts by weight, 0.005 parts by weight, 0.009 parts by weight, 0.02 parts by weight, 0.05 parts by weight, 0.09 parts by weight, 0.2 parts by weight, 0.5 parts by weight, 0.9 parts by weight, 1 part by weight, 2 parts by weight, or 3 parts by weight, and specific points therebetween, and the invention is not exhaustive and for the sake of brevity.
The dispersant may be present in an amount of 0.3 parts by weight, 0.5 parts by weight, 1 part by weight, 1.5 parts by weight, 2 parts by weight, 2.5 parts by weight, 3 parts by weight, or 3.5 parts by weight, and specific values therebetween, not exhaustive of the specific values included in the ranges, limited to space and for brevity.
The coating agent may be 3 parts by weight, 6 parts by weight, 9 parts by weight, 10 parts by weight, 13 parts by weight, 16 parts by weight, 19 parts by weight, 23 parts by weight, 26 parts by weight, 29 parts by weight, 33 parts by weight, 36 parts by weight or 39 parts by weight, and specific points therebetween are not exhaustive for the purpose of brevity and conciseness, and the invention is not intended to be exhaustive of the specific points included in the ranges.
The compatibilizer comprises 3, 4, 5, 6, 7, 8, or 9 parts by weight, and the particular points between the above points are not exhaustive for the invention and are not intended to limit the scope of the invention to the particular points included in the recited ranges for brevity and conciseness.
Firstly, the oral cavity repairing material provided by the invention adopts two kinds of polymethyl methacrylate resin, the dispersing agent, the coating agent and the compatilizer are added, and the dosage of each component is adjusted, so that the components are coordinated and matched, the pigment obtains the optimal dispersion effect in a polymer matrix, and the problem that crystal points appear on the surface and inside of the product due to pigment agglomeration and uneven dispersion is further avoided.
Secondly, the best self-lubricating effect of various fillers in matrix resin is realized by introducing a coating agent and a dispersing agent, the appearance of the finally obtained oral cavity repairing material crystal points is avoided by combining a special processing technology and a special method, the 'zero' crystal points of a polymer matrix are realized, and the product quality is greatly upgraded; and the components have good dispersion fluidity, so that the filler can be well dispersed in a resin matrix, the problems of unstable color of product batches and the like caused by nonuniform dispersion of the filler are solved, and the method has important research value.
Finally, through the compounding of two kinds of polymethyl methacrylate resin, when guaranteeing that the material has good mobility, promoted its mechanical properties simultaneously, the reduction product softening temperature of great limit guarantees that the product mills the process and can not produce deckle edge and glue the bonding machine needle phenomenon.
Preferably, the colorant comprises a combination of white, black, red and yellow fillers.
Preferably, the content of the white filler in the dental restorative material is 0.001 to 1 part by weight, such as 0.003, 0.006, 0.009, 0.03, 0.06, 0.09, 0.3, 0.6, or 0.9 parts by weight, and specific points therebetween, which are limited by space and for the sake of brevity, are not exhaustive, and the specific points included in the range are not included.
Preferably, the white filler comprises titanium dioxide.
Preferably, the content of the black filler in the dental restorative material is 0.001 to 1 part by weight, for example, 0.003, 0.006, 0.009, 0.03, 0.06, 0.09, 0.3, 0.6, or 0.9 parts by weight, and specific points therebetween are limited by space and for the sake of brevity, and the present invention is not exhaustive of the specific points included in the range.
Preferably, the black filler comprises any one of iron black, carbon black, ultra-fine graphite, or graphene, or a combination of at least two thereof.
Preferably, the content of the red filler in the dental restorative material is 0.001 to 1 part by weight, such as 0.003, 0.006, 0.009, 0.03, 0.06, 0.09, 0.3, 0.6, or 0.9 parts by weight, and specific points therebetween, which are limited by space and for the sake of brevity, are not exhaustive, and the specific points included in the range are not included.
Preferably, the red filler comprises chrome aluminum red and/or zirconium iron red.
Preferably, the content of the yellow filler in the dental restorative material is 0.001-1 part by weight, 0.003 part by weight, 0.006 part by weight, 0.009 part by weight, 0.03 part by weight, 0.06 part by weight, 0.09 part by weight, 0.3 part by weight, 0.6 part by weight or 0.9 part by weight, and specific points therebetween are limited by space and for the sake of brevity, and the invention is not exhaustive of the specific points included in the range.
Preferably, the yellow filler comprises zirconium vanadium yellow and/or iron yellow.
Preferably, the molecular weight of the first type of polymethylmethacrylate resin is greater than the molecular weight of the second type of polymethylmethacrylate resin.
Preferably, the molecular weight of the first type of polymethylmethacrylate resin and the second type of polymethylmethacrylate resin is 15000 to 1000000Da, such as 20000Da, 30000Da, 50000Da, 90000Da, 150000Da, 350000Da, 550000Da, 850000Da or 950000Da, independently, and the specific point values therebetween are limited in space and for the sake of brevity, and the present invention is not exhaustive enumeration of the specific point values included in the ranges.
Preferably, the first type of polymethylmethacrylate resin has a melt index less than the melt index of the second type of polymethylmethacrylate resin.
Preferably, the first type of polymethyl methacrylate resin and the second type of polymethyl methacrylate resin each independently have a melt index of 0.8 to 16g/10min, such as 1g/10min, 2g/10min, 4g/10min, 6g/10min, 8g/10min, 10g/10min, 12g/10min or 14g/10min, and specific values therebetween are limited in space and for the sake of brevity, and the present invention does not exhaust the specific values included in the range.
As the preferred technical scheme of the invention, two kinds of methyl methacrylate resin with high/low molecular weight composition and high/low melt index are mixed, so that good dispersion fluidity can be endowed to all components, good dispersion effect of inorganic filler in a resin matrix is ensured, and the problem of uneven dispersion of the filler is solved; and the mechanical property of the material is improved while the better processability is ensured, and the softening point of the product is integrally increased.
Preferably, the particle size of the first type of polymethylmethacrylate resin and the particle size of the second type of polymethylmethacrylate resin are each independently 40 to 150 μm, such as 45 μm, 50 μm, 55 μm, 60 μm, 65 μm, 70 μm, 75 μm, 80 μm, 85 μm, 90 μm, 100 μm, 110 μm, 120 μm, 130 μm or 140 μm, and specific point values therebetween are limited in space and for simplicity, and the invention is not exhaustive of the specific point values included in the ranges.
Preferably, the coating agent comprises any one of methyl methacrylate, ethylene glycol dimethacrylate, hydroxyethyl methacrylate or triethylene glycol dimethacrylate or a combination of at least two thereof.
Preferably, the dispersant comprises pentaerythritol stearate and/or N, N' -ethylene bis stearamide.
Preferably, the dispersant further comprises any one of or a combination of at least two of polyethylene homopolymer, ethylene-vinyl acetate copolymer or polymethyl methacrylate.
Preferably, the compatibilizer comprises any one or a combination of at least two of ethylene propylene diene monomer, butadiene rubber, isobutylene rubber, nitrile rubber, ethylene-butyl acrylate-glycidyl methacrylate copolymer, ethylene-methyl acrylate-glycidyl methacrylate copolymer, styrene-butadiene thermoplastic elastomer, hydrogenated styrene-butadiene block copolymer, chlorinated polyethylene, acrylonitrile-butadiene-styrene copolymer, or methyl acrylate-butadiene-styrene copolymer.
Preferably, the oral cavity restoration material further comprises an antioxidant.
Preferably, the antioxidant is present in the oral cavity restoration material in an amount of 0.01 to 1 part by weight, for example, 0.05, 0.08, 0.2, 0.4, 0.6, 0.8 or 0.9 parts by weight, and specific values therebetween are not exhaustive, and for brevity, the invention is not intended to be limited to the specific values included in the ranges.
Preferably, the antioxidant comprises any one of or a combination of at least two of hindered phenolic antioxidants, phosphite antioxidants or hindered amine/hydroxylamine antioxidants.
In a second aspect, the present invention provides a method for preparing an oral cavity restoration material according to the first aspect, wherein the method comprises the following steps:
(1) dispersing and mixing a second type of methyl methacrylate, a pigment, a dispersant and an optional antioxidant to obtain a mixed material; coating and mixing a second methyl methacrylate, a compatilizer and a coating agent to obtain a wetting material;
(2) and (2) mixing the mixed material obtained in the step (1) with a wetting material, and forming to obtain the oral cavity repairing material.
Preferably, the dispersion mixing in step (1) is carried out by any one or at least two of a paddle stirrer, a rotary mixer, a planetary ball mill, a stirred ball mill, a high-speed shear mixer or a jet mill.
Preferably, the mesh size of the mixed material in the step (1) is 100-200 mesh, such as 110 mesh, 120 mesh, 130 mesh, 140 mesh, 150 mesh, 160 mesh, 170 mesh, 180 mesh or 190 mesh, and the specific point values between the above-mentioned point values are limited by space and for the sake of brevity, and the invention is not exhaustive.
Preferably, the molding in step (2) includes any one of extrusion molding, compression molding or injection molding or a combination of at least two of them.
Preferably, the extrusion temperature is 140-230 ℃, for example, 150 ℃, 160 ℃, 170 ℃, 180 ℃, 190 ℃, 200 ℃, 210 ℃ or 220 ℃, and the specific values therebetween are not exhaustive for brevity and conciseness, and the specific values included in the range are not intended to be exhaustive.
Preferably, the extrusion speed is 300-600 rpm, such as 330rpm, 360rpm, 390rpm, 430rpm, 460rpm or 490rpm, and the specific values therebetween are limited for space and simplicity, and the invention is not exhaustive.
Preferably, the thickness of the extrusion-molded extruder nip is 0.1-2 mm, such as 0.5mm, 1.2mm, 1.4mm, 1.6mm or 1.8mm, and the specific values therebetween are not exhaustive, and for brevity and clarity, the invention is not intended to be limited to the specific values included in the ranges.
Preferably, the temperature of the press forming is 140-200 ℃, for example 145 ℃, 150 ℃, 155 ℃, 160 ℃, 165 ℃, 170 ℃, 175 ℃, 180 ℃, 185 ℃ or 190 ℃, and the specific values therebetween are limited by space and for the sake of brevity, and the invention is not exhaustive of the specific values included in the range.
Preferably, the pressure of the press forming is 2 to 10Mpa, such as 3Mpa, 4Mpa, 5Mpa, 6Mpa, 7Mpa, 8Mpa or 9Mpa, and the specific values therebetween are limited by space and for the sake of brevity, and the invention is not exhaustive.
Preferably, the dwell time of the press forming is 40-80 min, such as 43min, 46min, 48min, 53min, 56min, 59min, 66min, 63min, 69min, 73min, 76min or 79min, and the specific values therebetween are limited by space and for the sake of brevity, and the invention is not exhaustive.
Preferably, the injection molding temperature is 105-200 ℃, for example 115 ℃, 125 ℃, 135 ℃, 145 ℃, 155 ℃, 165 ℃, 175 ℃, 185 ℃ or 195 ℃, and the specific values therebetween are limited by space and for the sake of brevity, and the invention is not intended to be exhaustive of the specific values included in the range.
Preferably, the injection molding pressure is 2 to 12Mpa, such as 3Mpa, 4Mpa, 5Mpa, 6Mpa, 7Mpa, 8Mpa, 9Mpa, 10Mpa or 11Mpa, and the specific values therebetween are limited by the space and for the sake of brevity, and the invention is not exhaustive.
Preferably, the grinding temperature of the injection molding is 0 to 50 ℃, for example, 5 ℃, 10 ℃, 15 ℃, 20 ℃, 25 ℃, 30 ℃, 34 ℃, 40 ℃ or 45 ℃, and the specific values therebetween are limited by space and for the sake of brevity, and the invention is not exhaustive of the specific values included in the range.
In a third aspect, the invention provides a gradual-change oral cavity repair material, which is formed by fusing the oral cavity repair material with transitional color change as described in the first aspect.
The color stability of the oral cavity repairing material with the color transition change in the gradual-change oral cavity repairing material is good, so that the color deviation of the gradual-change oral cavity repairing material is small, and the color is stable.
In a fourth aspect, the present invention provides a method for preparing the gradual-change oral cavity repair material according to the third aspect, wherein the method for preparing the gradual-change oral cavity repair material comprises the following steps: and (3) pressing and molding the oral cavity repairing material with the transitional color change as described in the first aspect to obtain the gradual-change oral cavity repairing material.
The preparation method of the gradual change oral cavity repairing material provided by the invention is a multi-element composite molding mode, and the oral cavity repairing materials with various colors gradually changed and prepared by the first aspect of the invention are fused together, so that the color system of each specification of the product has natural gradual change, no layering, stable color and consistent aesthetic effect with the protoplasm dental material.
Preferably, the color gradient between two adjacent oral cavity restoration materials is 1-5%, such as 1.5%, 2%, 2.5%, 3%, 3.5%, 4% or 4.5%, and the specific values therebetween are not exhaustive for the sake of brevity and clarity.
In a fifth aspect, the present invention provides the use of a graded oral restoration material as described in the fourth aspect in a dental graded restoration.
Compared with the prior art, the invention has the following beneficial effects:
according to the oral cavity repairing material provided by the invention, the first polymethyl methacrylate resin with a specific part is added, the second polymethyl methacrylate resin with a specific part is matched, and the coating agent, the dispersing agent and the compatilizer are added, so that the prepared oral cavity repairing material is uniformly dispersed, the agglomeration of the pigment can be effectively avoided, the problem that crystal points appear on the surface and inside of the product due to the agglomeration and nonuniform dispersion of the pigment is further avoided, and the oral cavity repairing material with stable color is successfully prepared.
Detailed Description
The technical solution of the present invention is further explained by the following embodiments. It should be understood by those skilled in the art that the examples are only for the understanding of the present invention and should not be construed as the specific limitations of the present invention.
Examples 1 to 3
An oral cavity repairing material comprises the following specific components in parts by weight as shown in Table 1;
TABLE 1
| Example 1 | Example 2 | Example 3 | |
| Polymethyl methacrylate resin of the first type | 80 | 58 | 70 |
| Second poly (methyl methacrylate)Resin composition | 10 | 1 | 5 |
| Titanium dioxide | 0.002 | 0.01 | 1 |
| Iron oxide black | 0.001 | 0.01 | 1 |
| Iron oxide red | 0.001 | 0.01 | 1 |
| Iron oxide yellow | 0.004 | 0.02 | 1 |
| Pentaerythritol stearate | 0.08 | 0.1 | 4 |
| Ethylene propylene diene monomer | 4 | 2 | 10 |
| Methacrylic acid methyl ester | 5.712 | 0.1 | 10 |
| Hindered phenol antioxidants | 0.2 | 1 | 0.01 |
The preparation method of the oral cavity restoration material provided in the embodiment 1 to 3 comprises the following steps:
(1) dispersing and mixing a second poly-methyl methacrylate (with the molecular weight of 100000-500000 Da) and the melt index of 4.8g/10min), titanium dioxide filler, iron oxide red, iron oxide black, iron oxide yellow, pentaerythritol stearate (Wuhan Ke Mike) and a hindered phenol antioxidant (following the City's republic chemical industry) by a paddle stirrer to obtain a mixed material with the mesh number of 150; coating and mixing a first type of polymethyl methacrylate (with the molecular weight of 500000-1000000 Da and the melt index of 3.3g/10min), ethylene propylene diene monomer (superior chemical engineering) and methyl methacrylate (Jilin petrochemical, superior products) to obtain a wetting material;
(2) and (2) mixing the mixture material obtained in the step (1) with a wetting material, and performing compression molding at 150 ℃, the dwell time of 50min and the pressure of 5Mpa to obtain the oral cavity repairing material.
Example 4
An oral cavity restoration material is different from the oral cavity restoration material in example 1 in that the second polymethyl methacrylate resin is added in an amount of 80 parts by weight, the first polymethyl methacrylate resin is added in an amount of 10 parts by weight, and other components, the use amounts and the preparation method are the same as those of example 1.
Example 5
An oral cavity restoration material is different from the oral cavity restoration material in example 1 only in that the mixed material obtained in the step (1) and a wetting material are mixed in the step (2), and the mixture is extruded and molded under the conditions of 150 ℃, the rotating speed of 300rpm, the feeding speed of 50rpm and the outlet grinding thickness of 0.2mm to obtain the oral cavity restoration material, and other components, the using amount and the preparation method are the same as those in example 1.
Example 6
An oral cavity restoration material is different from the oral cavity restoration material in example 1 only in that the mixed material obtained in the step (1) and a wetting material are mixed in the step (2), and injection molding is carried out under the conditions that the temperature is 150 ℃, the pressure is 10Mpa and the grinding temperature of injection molding is 50 ℃ to obtain the oral cavity restoration material, and other components, the using amount and the preparation method are the same as those in example 1.
Comparative example 1
An oral cavity restoration material is different from the oral cavity restoration material in example 1 in that no first polymethyl methacrylate resin is added, the second polymethyl methacrylate resin is added in an amount of 90 parts by weight, and other components, the use amount and the preparation method are the same as those in example 1.
Comparative example 2
An oral cavity restoration material is different from the oral cavity restoration material in example 1 in that no second polymethyl methacrylate resin is added, the addition amount of the first polymethyl methacrylate resin is 90 parts by weight, and other components, the use amount and the preparation method are the same as those of example 1.
Comparative example 3
An oral cavity restorative material which is different from example 1 in that methyl methacrylate is not added, and other components, amounts and preparation methods are the same as those of example 1.
Comparative example 4
An oral cavity restoration material is different from the oral cavity restoration material in example 1 in that ethylene propylene diene monomer is not added, and other components, the using amount and the preparation method are the same as those of the oral cavity restoration material in example 1.
Comparative example 5
An oral cavity restoration material which is different from the oral cavity restoration material in example 1 in that pentaerythritol stearate is not added, and other components, the using amount and the preparation method are the same as those of example 1.
Comparative example 6
An oral cavity restorative material was distinguished from example 1 in that methyl methacrylate was added in an amount of 45 parts by weight, and other components, amounts, and preparation methods were the same as those of example 1.
Comparative example 7
An oral cavity repairing material is different from the material in the embodiment 1 in that the addition amount of the ethylene propylene diene monomer is 15 parts by weight, and other components, the using amount and the preparation method are the same as those in the embodiment 1.
Comparative example 8
An oral cavity restoration material is different from the oral cavity restoration material in example 1 in that pentaerythritol stearate is added in an amount of 5 parts by weight, and other components, the use amounts and the preparation method are the same as those in example 1.
And (3) performance testing:
(1) appearance: visually observing whether the material has non-uniformly dispersed crystal points in the appearance under a colorimetric lamp box;
(2) bending strength: performing sample preparation test according to dental standard YY0710-2009 Polymer-based crown and bridge Material;
(3) vickers hardness: and (3) carrying out sample preparation test according to the national standard GB/T4340.1-2009 part 1 test method for Vickers hardness test of metal materials.
The oral cavity restoration materials provided in examples 1 to 6 and comparative examples 1 to 8 were tested according to the above test method, and the test results are shown in table 2:
TABLE 2
| Appearance of the product | Flexural Strength (MPa) | Vickers Hardness (HV) | |
| Example 1 | Crystal point free | 137 | 25.5 |
| Example 2 | Crystal point free | 137 | 24.3 |
| Example 3 | Crystal point free | 135 | 24.1 |
| Example 4 | Crystal point free | 136 | 24.7 |
| Example 5 | Crystal point free | 136.2 | 22.3 |
| Example 6 | Crystal point free | 136 | 24.7 |
| Comparative example 1 | Crystal point free | 120 | 22.7 |
| Comparative example 2 | Crystal point free | 118 | 20.1 |
| Comparative example 3 | The crystal points are obvious | 110 | 18.3 |
| Comparative example 4 | The crystal points are obvious | 131 | 23.6 |
| Comparative example 5 | The crystal points are obvious | 132 | 25 |
| Comparative example 6 | Can not be molded | / | / |
| Comparative example 7 | Can not be molded | / | / |
| Comparative example 8 | Can not be molded | / | / |
As can be seen from the data in table 2: the oral cavity repairing material provided by the invention is excellent in performance and uniform in color distribution and has no crystal points by adding the first type of polymethyl methacrylate, the second type of polymethyl methacrylate, a proper amount of coating agent, compatilizer and dispersant in specific parts; specifically, no crystal point was observed in the appearance of the dental restorative materials obtained in examples 1 to 6, the flexural strength was 135 to 137MPa, and the Vickers hardness was 22.3 to 25.5 HV.
Comparing example 1 with comparative examples 1 to 2, it was found that the mouth repair material obtained when only the first type of polymethyl methacrylate or only the second type of polymethyl methacrylate was added had amorphous spots, but both the flexural strength and the Vickers hardness were reduced.
Comparing example 1 with comparative examples 3 to 5, it was found that the dental restorative material obtained without adding any of the coating agent, the compatibilizer, or the dispersant had a remarkable crystal point and was reduced in both flexural strength and vickers hardness.
Further, by comparing example 1 with comparative examples 6 to 8, it was found that the molding could not be performed when the amounts of the coating agent, the phase solvent and the dispersant were too large.
The applicant states that the present invention is described by the above examples to describe an oral cavity repairing material and a preparation method and application thereof, but the present invention is not limited to the above examples, that is, it does not mean that the present invention must be implemented by the above examples. It should be understood by those skilled in the art that any modification of the present invention, equivalent substitutions of the raw materials of the product of the present invention, addition of auxiliary components, selection of specific modes, etc., are within the scope and disclosure of the present invention.
Claims (10)
1. The oral cavity repairing material is characterized by comprising the following components in parts by weight: 58-80 parts of first polymethyl methacrylate resin, 1-10 parts of second polymethyl methacrylate resin, 0.001-4 parts of pigment, 0.1-4 parts of dispersant, 0.1-40 parts of coating agent and 2-10 parts of compatilizer.
2. The dental restoration material of claim 1, wherein the colorant comprises a combination of a white filler, a black filler, a red filler, and a yellow filler;
preferably, the content of the white filler in the oral cavity repairing material is 0.001-1 part by weight;
preferably, the white filler comprises titanium dioxide;
preferably, the content of the black filler in the oral cavity repairing material is 0.001-1 part by weight;
preferably, the black filler comprises any one or a combination of at least two of iron black, carbon black, ultrafine graphite or graphene;
preferably, the content of the red filler in the oral cavity repairing material is 0.001-1 part by weight;
preferably, the red filler comprises chrome aluminum red and/or zirconium iron red;
preferably, the content of the yellow filler in the oral cavity repairing material is 0.001-1 part by weight;
preferably, the yellow filler comprises zirconium vanadium yellow and/or iron yellow.
3. The oral cavity restoration material according to claim 1 or 2, wherein the molecular weight of the first type of polymethylmethacrylate resin is greater than the molecular weight of the second type of polymethylmethacrylate resin;
preferably, the first polymethyl methacrylate resin and the second polymethyl methacrylate resin have molecular weights of 15000 to 1000000Da respectively and independently;
preferably, the first type of polymethylmethacrylate resin has a melt index less than the melt index of the second type of polymethylmethacrylate resin;
preferably, the first polymethyl methacrylate resin and the second polymethyl methacrylate resin have melt indexes of 0.8-16 g/10min respectively and independently;
preferably, the particle size of the first polymethyl methacrylate resin and the particle size of the second polymethyl methacrylate resin are 40 to 150 μm respectively.
4. The oral cavity restoration material according to any one of claims 1 to 3, wherein the coating agent comprises any one or a combination of at least two of methyl methacrylate, ethylene glycol dimethacrylate, hydroxyethyl methacrylate or triethylene glycol dimethacrylate;
preferably, the dispersant comprises pentaerythritol stearate and/or N, N' -ethylene bis stearamide;
preferably, the dispersant comprises any one or a combination of at least two of polyethylene homopolymer, ethylene-vinyl acetate copolymer or polymethyl methacrylate;
preferably, the compatibilizer comprises any one or a combination of at least two of ethylene propylene diene monomer, butadiene rubber, isobutylene rubber, nitrile rubber, ethylene-butyl acrylate-glycidyl methacrylate copolymer, ethylene-methyl acrylate-glycidyl methacrylate copolymer, styrene-butadiene thermoplastic elastomer, hydrogenated styrene-butadiene block copolymer, chlorinated polyethylene, acrylonitrile-butadiene-styrene copolymer, or methyl acrylate-butadiene-styrene copolymer.
5. The dental restoration material according to any one of claims 1 to 4, further comprising an antioxidant;
preferably, the content of the antioxidant in the oral cavity repairing material is 0.01-1 part by weight;
preferably, the antioxidant comprises any one of or a combination of at least two of hindered phenolic antioxidants, phosphite antioxidants or hindered amine/hydroxylamine antioxidants.
6. A method of preparing an oral cavity restoration material according to any one of claims 1 to 5, comprising the steps of:
(1) dispersing and mixing a second type of methyl methacrylate, a pigment, a dispersant and an optional antioxidant to obtain a mixed material; coating and mixing the first methyl methacrylate, the compatilizer and the coating agent to obtain a wetting material;
(2) and (2) mixing the mixed material obtained in the step (1) with a wetting material, and forming to obtain the oral cavity repairing material.
7. The production method according to claim 6, wherein the dispersion mixing of step (1) is carried out by any one or at least two of a paddle mixer, a rotary mixer, a planetary ball mill, a stirred ball mill, a high-speed shear mixer, or a jet mill;
preferably, the mesh number of the mixed materials in the step (1) is 100-200 meshes;
preferably, the molding of step (2) comprises any one of extrusion molding, compression molding or injection molding or a combination of at least two of them;
preferably, the temperature of the extrusion molding is 140-230 ℃;
preferably, the rotation speed of the extrusion molding is 300-600 rpm;
preferably, the thickness of the ground of the extrusion molding extruder is 0.1-2 mm;
preferably, the temperature of the compression molding is 140-200 ℃;
preferably, the pressure of the compression molding is 2-10 Mpa;
preferably, the pressure maintaining time of the compression molding is 40-80 min;
preferably, the injection molding temperature is 105-200 ℃;
preferably, the pressure of the injection molding is 2-12 MPa;
preferably, the grinding temperature of the injection molding is 0-50 ℃.
8. A gradual-change oral cavity restoration material, which is characterized in that the gradual-change oral cavity restoration material is formed by fusing the oral cavity restoration material with transitional color according to any one of claims 1 to 5.
9. A method of preparing the graded oral restoration material of claim 8, the method comprising: pressing and molding the oral cavity restoration material with transitional color according to any one of claims 1 to 5 to obtain the gradual-change oral cavity restoration material;
preferably, the color gradient of two adjacent oral cavity repair materials is 1-5%.
10. Use of a graded oral restoration material according to claim 8 in a dental graded restoration.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202110649567.1A CN113181059A (en) | 2021-06-10 | 2021-06-10 | Oral cavity repairing material and preparation method and application thereof |
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| Application Number | Priority Date | Filing Date | Title |
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| CN202110649567.1A CN113181059A (en) | 2021-06-10 | 2021-06-10 | Oral cavity repairing material and preparation method and application thereof |
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| CN113181059A true CN113181059A (en) | 2021-07-30 |
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| CN202110649567.1A Withdrawn CN113181059A (en) | 2021-06-10 | 2021-06-10 | Oral cavity repairing material and preparation method and application thereof |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114316814A (en) * | 2021-12-29 | 2022-04-12 | 苏州赛伍应用技术股份有限公司 | Packaging adhesive film with color gradient effect and preparation method thereof |
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2021
- 2021-06-10 CN CN202110649567.1A patent/CN113181059A/en not_active Withdrawn
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114316814A (en) * | 2021-12-29 | 2022-04-12 | 苏州赛伍应用技术股份有限公司 | Packaging adhesive film with color gradient effect and preparation method thereof |
| CN114316814B (en) * | 2021-12-29 | 2023-09-19 | 苏州赛伍应用技术股份有限公司 | Packaging adhesive film with color gradual change effect and preparation method thereof |
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Application publication date: 20210730 |