WO2023000996A1 - 一种用于牙科修复的聚合性单体组合物及其制备方法和应用 - Google Patents

一种用于牙科修复的聚合性单体组合物及其制备方法和应用 Download PDF

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Publication number
WO2023000996A1
WO2023000996A1 PCT/CN2022/104534 CN2022104534W WO2023000996A1 WO 2023000996 A1 WO2023000996 A1 WO 2023000996A1 CN 2022104534 W CN2022104534 W CN 2022104534W WO 2023000996 A1 WO2023000996 A1 WO 2023000996A1
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Prior art keywords
polymerizable monomer
monomer composition
resin
weight
methacrylate
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PCT/CN2022/104534
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English (en)
French (fr)
Inventor
李洪文
刘乾乾
乔春梅
王伟刚
许文冬
魏嘉欣
Original Assignee
爱迪特（秦皇岛）科技股份有限公司
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Priority to KR1020227035776A priority Critical patent/KR20230015317A/ko
Priority to JP2022550800A priority patent/JP2023537441A/ja
Publication of WO2023000996A1 publication Critical patent/WO2023000996A1/zh

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
    • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/10—Esters
    • C08F220/34—Esters containing nitrogen, e.g. N,N-dimethylaminoethyl (meth)acrylate
    • C08F220/343—Esters containing nitrogen, e.g. N,N-dimethylaminoethyl (meth)acrylate in the form of urethane links
    • 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
    • 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
    • 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
    • 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
    • A61K6/73—Fillers comprising sulfur-containing compounds
    • 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
    • A61K6/74—Fillers comprising phosphorus-containing compounds
    • A61K6/75—Apatite
    • 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
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K6/00—Preparations for dentistry
    • A61K6/70—Preparations for dentistry comprising inorganic additives
    • A61K6/71—Fillers
    • A61K6/77—Glass
    • 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
    • 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
    • A61K6/891—Compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F222/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a carboxyl radical and containing at least one other carboxyl radical in the molecule; Salts, anhydrides, esters, amides, imides, or nitriles thereof
    • C08F222/10—Esters
    • C08F222/1006—Esters of polyhydric alcohols or polyhydric phenols
    • C08F222/104—Esters of polyhydric alcohols or polyhydric phenols of tetraalcohols, e.g. pentaerythritol tetra(meth)acrylate
    • C08F222/1045—Esters of polyhydric alcohols or polyhydric phenols of tetraalcohols, e.g. pentaerythritol tetra(meth)acrylate of aromatic tetraalcohols

Definitions

  • the invention belongs to the technical field of composite materials, and in particular relates to a polymerizable monomer composition for dental restoration and its preparation method and application.
  • resin-ceramic restoration materials combine the characteristics of high strength of ceramic materials and good toughness of resin materials, there are still two problems: (1) Although resin-ceramic restoration materials inherit the biocompatibility of ceramic materials to a certain extent , avoiding the shortcomings of ceramic materials such as high strength, easy wear and tear on the opposing teeth, and brittle fracture, and compared with resin materials, the mechanical properties have also been greatly improved, but in actual dental restorations, the mechanical performance of resin-ceramic composite materials is poor. It cannot be fully satisfied.
  • CN106132383A discloses a polymerizable monomer composition for dental materials with a cured product that simultaneously achieves high toughness and rigidity, a composition for dental materials containing the polymerizable monomer composition for dental materials, and a composition with high mechanical properties of its cured product.
  • the polymerizable monomer composition for dental materials contains a urethane acrylate compound obtained by reacting a specific hydroxy acrylate with a diisocyanate, and a polymerizable compound
  • the diisocyanate is a divalent aromatic hydrocarbon group with 6 to 9 carbons or a divalent bridged ring hydrocarbon group with 6 to 9 carbons bonded to two isocyanate groups through a methylene group that can be substituted by a hydrogen atom
  • the polymerizable compound contains at least one polymerizable group selected from a methacryloyl group and an acryloyl group.
  • CN105310889A discloses a dental curable composition, wherein a resin monomer and a filler are contained in a weight ratio of 10:90 to 70:30, and 0.01 to 10 parts by weight are contained relative to 100 parts by weight of a resin monomer A polymerization initiator, 0.001-1 part by weight of a terpenoid compound.
  • a terpenoid compound as a chain transfer agent, among the components contained in the dental curable composition, the thermal polymerization rate of the resin monomer that has high thermal conductivity and starts to polymerize rapidly due to heat is slowed down, thereby performing uniform heating. Polymerization, thereby suppressing the generation of microscopic and macroscopic strains, and can suppress the occurrence of cracks and debris.
  • the addition of the chain transfer agent can also suppress the foaming of the resin monomer having a low boiling point, so that the incorporation of air bubbles can also be suppressed.
  • the addition of chain transfer agents and the design of polymerizable monomers cannot improve the mechanical properties such as bending strength and hardness of the final ceramic resin material, and thus cannot effectively improve the service life of the material.
  • CN102665605A discloses a thermosetting composite resin block, which consists of a polymerizable resin containing ethylenically unsaturated groups, an initiator dissolved in the resin and activated at a temperature of about 100°C to about 150°C and Composed of inorganic fillers mixed with the resin; the flexural strength, abrasion resistance and aesthetic properties of the resin block are significantly improved.
  • the improved mechanical strength is only 200MPa, which cannot fully meet the needs of patients.
  • the object of the present invention is to provide a polymerizable monomer composition for dental restoration and its preparation method and application
  • the polymerizable monomer composition includes a specific number of polymerizable monomers , the combination of initiator and crosslinking agent; by adding a crosslinking agent, the double bond conversion rate of the polymerizable monomer composition is improved, the residual rate of the polymerizable monomer is reduced, and the crosslinking density of the system after polymerization is increased , which in turn can enhance the flexural strength and hardness of the polymer, reduce the water absorption value and dissolution value, so that when it is applied to the resin ceramic repair material, it can effectively improve the mechanical properties and biocompatibility of the resin ceramic repair material.
  • the present invention provides a polymerizable monomer composition for dental restoration, the polymerizable monomer composition includes the following components in parts by weight: 20-100 parts by weight of a polymerizable monomer, 0.01 parts by weight of an initiator ⁇ 10 parts by weight and 0.01 ⁇ 10 parts by weight of crosslinking agent.
  • the polymerizable monomer is preferably 25 parts by weight, 30 parts by weight, 35 parts by weight, 40 parts by weight, 45 parts by weight, 50 parts by weight, 55 parts by weight, 60 parts by weight, 65 parts by weight, 70 parts by weight Parts by weight, 75 parts by weight, 80 parts by weight, 85 parts by weight, 90 parts by weight or 95 parts by weight.
  • the weight part of the polymerizable monomer is preferably all other point values between the above point values. Due to space limitation and for the sake of simplicity, the present invention will not exhaustively list the specific point values included in the range. .
  • the initiator is preferably 0.2 parts by weight, 0.5 parts by weight, 1 parts by weight, 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.
  • the weight part of the polymerizable monomer is preferably all other point values between the above point values. Due to space limitation and for the sake of simplicity, the present invention will not exhaustively list the specific point values included in the range. .
  • the crosslinking agent is preferably 0.2 parts by weight, 0.5 parts by weight, 1 parts by weight, 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 parts or 9 parts by weight.
  • the weight part of the polymerizable monomer is preferably any other point value between the above-mentioned point values. Due to space limitation and for the sake of brevity, the present invention will not exhaustively list the specific points included in the range. value.
  • the polymerizable monomer composition for dental restoration provided by the present invention increases the double bond conversion rate of the polymerizable monomer by adding a crosslinking agent, reduces the residue of the polymerizable monomer in the dental restoration material, and makes the polymerization system
  • the cross-linking density increases, which in turn can enhance the flexural strength and hardness of the polymer, and reduce its water absorption and dissolution values.
  • the crosslinking agent includes ethylene glycol dimethacrylate, 1,6-hexanediol dimethacrylate, trimethylpropane trimethacrylate, trimethylolpropane triacrylate, Any one or at least two of divinylbenzene, acrylic acid, hydroxyethyl acrylate, hydroxypropyl acrylate, methacrylic acid, hydroxyethyl methacrylate, hydroxypropyl methacrylate or N-methylolacrylamide combination of species.
  • the polymerizable monomers include methyl methacrylate, ethyl methacrylate, isobutyl methacrylate, tert-butyl methacrylate, isopentyl methacrylate, benzyl methacrylate, Glycidyl methacrylate, lauryl methacrylate, tetrahydrofurfuryl methacrylate, 2-(N,N-dimethylamino)ethyl methacrylate, 2,3-methacrylate Dibromopropyl, 2-Hydroxyethyl Methacrylate, 2-Hydroxypropyl Methacrylate, 6-Hydroxyhexyl Methacrylate, 10-Hydroxydecyl Methacrylate, Triethylene Glycol Monomethacrylate , triethylene glycol dimethacrylate, propylene glycol monomethacrylate, ethylene glycol methacrylate, diethylene glycol methacrylate, methoxydi
  • the polymerizable monomer has a refractive index after polymerization of 1.52 ⁇ 1.58, preferably 1.525, 1.53, 1.535, 1.54, 1.545, 1.55, 1.555, 1.56, 1.565, 1.57 or 1.575.
  • the refractive index of the polymerizable monomer after polymerization is preferably all other specific point values between the above-mentioned point values. Due to space limitations and for the sake of simplicity, the present invention will not exhaustively list the ranges included. specific point value.
  • the initiator includes dicumyl peroxide, tert-butyl peroxide, benzoyl peroxide, lauroyl peroxide, tert-butyl peroxyacetate, tert-butyl peroxybenzoate, peroxide Any one of tert-butyl t-valerate, potassium persulfate, sodium persulfate, ammonium persulfate, azobisisobutyronitrile or azobisisoheptanonitrile or dimethyl azobisisobutyrate or at least A combination of the two.
  • the present invention provides a method for preparing the polymerizable monomer composition as described in the first aspect, the preparation method comprising: mixing a polymerizable monomer, an initiator and a crosslinking agent to obtain the polymerizable monomer composition.
  • the mixing time is not less than 1h, preferably 1.1h, 1.2h, 1.3h, 1.4h, 1.5h, 1.6h, 1.7h, 1.8h, 1.9h or 2h; the mixing time is preferably All other specific point values between the above-mentioned point values are limited in space and for the sake of brevity, the present invention does not exhaustively list the specific point values included in the range.
  • the mixing is carried out under stirring conditions, more preferably under stirring conditions with a rotation speed not less than 20r/min; the rotation speed is preferably 30r/min, 40r/min, 50r/min, 60r/min, 70r/min, 80r/min, 90r/min or 100r/min.
  • the mixing temperature is not greater than 50°C, and the mixing temperature is preferably 45°C, 40°C, 35°C, 30°C, 25°C, 20°C, 15°C, 10°C or 5°C; the mixing The temperature is preferably all other specific point values between the above-mentioned point values. Due to space limitation and for the sake of brevity, the present invention does not exhaustively list the specific point values included in the range.
  • the present invention provides a resin ceramic repair material, which includes the polymerizable monomer composition as described in the first aspect and an inorganic filler.
  • the resin ceramic restoration material provided by the present invention through the addition of a polymerizable monomer composition with a crosslinking agent, makes the obtained resin ceramic restoration material improve the properties of bending strength, water absorption value and dissolution value on the basis of maintaining aesthetics
  • the obtained resin ceramic restoration material has high strength and toughness, so that when the material is applied to tooth restoration, it can maintain a good shape no matter in the process of processing, or in the process of wearing and using by the patient, and will not appear. chipping, fracture and other phenomena; and due to the reduction of water absorption value and dissolution value and the improvement of mechanical strength, its service life is increased, and it can be used for permanent restoration, so that this material can be more widely used in tooth restoration to meet the needs of the market. demand.
  • the resin ceramic restoration material includes the following components in parts by weight: 10-90 parts by weight of the polymerizable monomer composition as described in the first aspect and 10-90 parts by weight of inorganic filler.
  • the mass parts of the polymerizable monomer composition is preferably 20 parts by weight, 30 parts by weight, 40 parts by weight, 50 parts by weight, 60 parts by weight, 70 parts by weight or 80 parts by weight;
  • the mass fraction of the permanent monomer composition is preferably all other specific point values between the above point values. Due to space limitation and for the sake of brevity, the present invention does not exhaustively list the specific point values included in the range.
  • the mass parts of the inorganic filler is preferably 20 parts by weight, 30 parts by weight, 40 parts by weight, 50 parts by weight, 60 parts by weight, 70 parts by weight or 80 parts by weight; the mass parts of the inorganic filler
  • the numbers are preferably all other specific point values between the above-mentioned point values, and due to space limitation and for the sake of brevity, the present invention does not exhaustively list the specific point values included in the range.
  • the inorganic fillers include silica, aluminum silicate, alumina, calcium fluoride, strontium fluoride, calcium carbonate, kaolin, clay, mica, aluminum sulfate, calcium sulfate, barium sulfate, titanium oxide, calcium phosphate , hydroxyapatite, calcium hydroxide, strontium hydroxide, zeolite, titanium dioxide or zirconium oxide, or any one or a combination of at least two.
  • the inorganic fillers also include glass-based inorganic fillers.
  • the glass-based inorganic filler includes any one of fluorine glass, borosilicate glass, soda glass, barium glass, barium aluminosilicate glass, strontium-containing glass, zirconium-containing glass, glass ceramics or fluoroaluminosilicate glass Or just a combination of at least two.
  • the refractive index of the inorganic filler is 1.52 to 1.58, preferably 1.525, 1.53, 1.535, 1.54, 1.545, 1.55, 1.555, 1.56, 1.565, 1.57 or 1.575; the refractive index of the inorganic filler is preferably the above point
  • the present invention will not exhaustively list the specific point values included in the range.
  • the inorganic filler is a coupling agent modified inorganic filler.
  • the inorganic filler provided by the present invention is a coupling agent-modified inorganic filler, and the affinity between the coupling agent-modified inorganic filler and the polymerizable monomer composition is better, thereby improving the performance of resin ceramics.
  • the mechanical strength of the cured restorative material is better.
  • the coupling agent includes ⁇ -methacryloxypropyltrimethoxysilane, ⁇ -methacryloxypropyltriethoxysilane or ⁇ -aminopropyltrimethoxysilane Any one or a combination of at least two, and more preferably ⁇ -methacryloxypropyltrimethoxysilane.
  • the resin-ceramic restoration material further includes additives.
  • the content of additives in the resin ceramic restoration material is 0-5 parts by weight and not 0, preferably 0.1 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, 3.5 parts by weight, 4 parts by weight or 4.5 parts by weight;
  • the mass parts of additives in the resin-ceramic repair material are preferably all other specific point values between the above-mentioned point values, limited by space and for the sake of simplicity , the present invention will not exhaustively enumerate the specific point values included in the range.
  • the additive includes any one or a combination of at least two of colorants, fluorescent agents, indicators, viscosity regulators, wetting agents, antioxidants, stabilizers or diluents.
  • the present invention provides a method for preparing a resin ceramic repair material as described in the third aspect, the preparation method comprising: reacting a polymerizable monomer composition, an inorganic filler and an optional additive to obtain the Resin ceramic restorative material.
  • the reaction time is not less than 1h, preferably 1.1h, 1.2h, 1.3h, 1.4h, 1.5h, 1.6h, 1.7h, 1.8h, 1.9h or 2h; the reaction time is preferably All other specific point values between the above-mentioned point values are limited in space and for the sake of brevity, the present invention does not exhaustively list the specific point values included in the range.
  • the pressure of the reaction is not less than 1Mpa, preferably 2Mpa, 3Mpa, 4Mpa, 5Mpa, 6Mpa, 7Mpa, 8Mpa or 9Mpa; the pressure of the reaction is preferably all other specific point values between the above point values, limited to For the sake of space and brevity, the present invention does not exhaustively enumerate the specific points included in the range.
  • the temperature of the reaction is not less than 80°C, preferably 85°C, 90°C, 95°C, 100°C, 105°C, 110°C, 115°C or 120°C; the temperature of the reaction is preferably one of the above points
  • the present invention does not exhaustively enumerate the specific point values included in the range due to space limitation and for the sake of brevity.
  • the resin ceramic restorative material provided by the invention is filled in a mould, polymerized and solidified under heat and pressure to form.
  • the fifth aspect of the present invention is an application of the resin-ceramic restorative material as described in the third aspect in dental restorative materials.
  • the present invention has the following beneficial effects:
  • the polymerizable monomer composition used for dental restoration increases the double bond conversion rate of the polymerizable monomer by adding a crosslinking agent, reduces the residue of the polymerizable monomer, and makes the crosslinking of the polymerization system
  • the joint density increases, thereby enhancing the flexural strength and hardness of the polymer, and reducing its water absorption value and dissolution value.
  • the resin ceramic restoration material provided by the present invention by adding a polymerizable monomer composition with a crosslinking agent, makes the obtained resin ceramic restoration material improve the bending strength, water absorption value, dissolution value performance.
  • the bending strength of the resin ceramic restoration material provided by the present invention is 225-274MPa
  • the elastic modulus is 10.3-11.5GPa
  • the Vickers hardness is 102-131HV2.0
  • the abrasion resistance is 12.1-16.6 mm 3
  • the water absorption value is 11-15 ⁇ g/mm 3
  • the dissolution value is 0.8-1.2 ⁇ g/mm 3 .
  • the resin ceramic restorative material provided by the present invention has both high strength and toughness, so that when the material is applied to tooth restoration, it can maintain a good shape no matter in the process of processing, or in the process of wearing and using by the patient.
  • a polymerizable monomer composition for dental restoration comprising the following components in parts by weight:
  • the preparation method comprises: uniformly mixing urethane dimethacrylate, triethylene glycol dimethacrylate and trimethylpropane trimethacrylate at 40° C. and a stirring condition of 300 r/min, Then add benzoyl peroxide and continue mixing under stirring condition for 2h to obtain the polymerizable monomer composition.
  • a polymerizable monomer composition for dental restoration comprising the following components in parts by weight:
  • Its preparation method includes: 2,2-bis(4-(3-(meth)acryloyloxy-2-hydroxypropoxy)phenyl)propane under stirring conditions of 45°C and a rotation speed of 200r/min , triethylene glycol dimethacrylate and trimethylpropane trimethacrylate were uniformly mixed, and then added benzoyl peroxide and continued to mix for 1 h under stirring conditions to obtain the polymerizable monomer composition.
  • a polymerizable monomer composition for dental restoration comprising the following components in parts by weight:
  • Its preparation method includes: 2,2-bis(4-(3-(meth)acryloyloxy-2-hydroxypropoxy)phenyl)propane , triethylene glycol dimethacrylate and ethylene glycol dimethacrylate were uniformly mixed, and then added benzoyl peroxide and continued to mix for 1.5 h under stirring conditions to obtain the polymerizable monomer composition.
  • a polymerizable monomer composition for dental restoration comprising the following components in parts by weight:
  • a polymerizable monomer composition for dental restoration comprising the following components in parts by weight:
  • a polymerizable monomer composition for dental restoration comprising the following components in parts by weight:
  • a polymerizable monomer composition for dental restoration the only difference from Example 1 is that trimethylpropane trimethacrylate is not added, and other components, dosage and preparation method are the same as Example 1 .
  • a polymerizable monomer composition for dental restoration the only difference from Example 2 is that trimethylpropane trimethacrylate is not added, and other components, dosage and preparation method are the same as Example 1 .
  • a polymerizable monomer composition for dental restoration the only difference from Example 6 is that trimethylpropane trimethacrylate is not added, and other components, dosage and preparation method are the same as Example 6 .
  • a resin ceramic restorative material comprises the following components in parts by weight:
  • the polymerizable monomer composition is the polymerizable monomer composition obtained in Example 1;
  • the inorganic filler 1 is amorphous barium boroaluminosilicate modified by ⁇ -methacryloxypropyltrimethoxysilane Glass powder (GM27884), particle size D50 is 1.5 ⁇ m;
  • inorganic filler 2 is amorphous barium boroaluminosilicate glass powder (GM27884) modified by ⁇ -methacryloxypropyl trimethoxysilane, particle size
  • the diameter D50 is 0.7 ⁇ m;
  • the inorganic filler 3 is fumed silica (OX-50) modified by ⁇ -methacryloxypropyltrimethoxysilane, and the particle diameter D50 is 40nm;
  • the preparation method of the resin ceramic restoration material provided in this application example includes: reacting the polymerizable monomer composition, inorganic filler 1, inorganic filler 2 and inorganic filler 3 at 15 MPa and 120°C for 2 hours to obtain the resin ceramic restoration material.
  • a resin ceramic restorative material comprises the following components in parts by weight:
  • Polymerizable monomer composition 20 parts by weight;
  • Inorganic filler 2 80 parts by weight
  • the polymerizable monomer composition is the polymerizable monomer composition obtained in Example 1;
  • the inorganic filler 2 is amorphous barium boroaluminosilicate modified by ⁇ -methacryloxypropyltrimethoxysilane Glass powder (GM27884), the particle size D50 is 0.7 ⁇ m;
  • the preparation method of the resin ceramic restoration material provided in this application example includes: reacting the polymerizable monomer composition and the inorganic filler 2 at 15 MPa and 120° C. for 2 hours to obtain the resin ceramic restoration material.
  • a resin ceramic restorative material comprises the following components in parts by weight:
  • Polymerizable monomer composition 25 parts by weight;
  • the polymerizable monomer composition is the polymerizable monomer composition obtained in Example 1;
  • the inorganic filler 4 is amorphous barium boroaluminosilicate modified by ⁇ -methacryloxypropyltrimethoxysilane Glass powder (GM27884), particle size D50 is 0.18 ⁇ m;
  • the preparation method of the resin ceramic restoration material provided in this application example includes: reacting the polymerizable monomer composition and the inorganic filler 4 at 15 MPa and 120° C. for 2 hours to obtain the resin ceramic restoration material.
  • a resin ceramic restorative material comprises the following components in parts by weight:
  • the polymerizable monomer composition is the polymerizable monomer composition obtained in Example 2;
  • the inorganic filler 1 is amorphous barium boroaluminosilicate modified by ⁇ -methacryloxypropyltrimethoxysilane Glass powder (GM27884), particle size D50 is 1.5 ⁇ m;
  • inorganic filler 2 is amorphous barium boroaluminosilicate glass powder (GM27884) modified by ⁇ -methacryloxypropyl trimethoxysilane, particle size
  • the diameter D50 is 0.7 ⁇ m;
  • the inorganic filler 4 is amorphous barium boroaluminosilicate glass powder (GM27884) modified by ⁇ -methacryloxypropyltrimethoxysilane, and the particle diameter D50 is 0.18 ⁇ m;
  • the preparation method of the resin ceramic restoration material provided in this application example includes: reacting the polymerizable monomer composition, the inorganic filler 1, the inorganic filler 2 and the inorganic filler 4 at 15 MPa and 120° C. for 2 hours to obtain the resin ceramic restoration material.
  • a resin ceramic restorative material comprises the following components in parts by weight:
  • Polymerizable monomer composition 22 parts by weight;
  • the polymerizable monomer composition is the polymerizable monomer composition obtained in Example 2;
  • the inorganic filler 4 is amorphous barium boroaluminosilicate modified by ⁇ -methacryloxypropyltrimethoxysilane Glass powder (GM27884), particle size D50 is 0.18 ⁇ m;
  • the preparation method of the resin ceramic restoration material provided in this application example includes: reacting the polymerizable monomer composition and the inorganic filler 4 at 15 MPa and 120° C. for 2 hours to obtain the resin ceramic restoration material.
  • a resin ceramic restorative material comprises the following components in parts by weight:
  • the polymerizable monomer composition is the polymerizable monomer composition obtained in Example 3;
  • the inorganic filler 2 is amorphous barium boroaluminosilicate modified by ⁇ -methacryloxypropyltrimethoxysilane Glass powder (GM27884), particle size D 50 is 0.7 ⁇ m;
  • inorganic filler 3 is fumed silica (OX-50) modified by ⁇ -methacryloxypropyltrimethoxysilane, particle size D 50 is 40nm;
  • Inorganic filler 4 is amorphous barium boroaluminosilicate glass powder (GM27884) modified by ⁇ -methacryloxypropyltrimethoxysilane, and the particle diameter D50 is 0.18 ⁇ m;
  • the preparation method of the resin ceramic restoration material provided in this application example includes: reacting the polymerizable monomer composition, the inorganic filler 2, the inorganic filler 3 and the inorganic filler 4 at 15 MPa and 120° C. for 2 hours to obtain the resin ceramic restoration material.
  • a resin ceramic restorative material comprises the following components in parts by weight:
  • Polymerizable monomer composition 35 parts by weight
  • the polymerizable monomer composition is the polymerizable monomer composition obtained in Example 4;
  • the inorganic filler 3 is fumed silica modified by ⁇ -methacryloxypropyltrimethoxysilane (OX-50 ), the particle size D 50 is 40nm;
  • the inorganic filler 4 is amorphous barium boroaluminosilicate glass powder (GM27884) modified by ⁇ -methacryloxypropyltrimethoxysilane, and the particle size D 50 is 0.18 ⁇ m;
  • the preparation method of the resin ceramic restoration material provided in this application example includes: reacting the polymerizable monomer composition, the inorganic filler 3 and the inorganic filler 4 at 15 MPa and 120° C. for 2 hours to obtain the resin ceramic restoration material.
  • a resin ceramic restorative material comprises the following components in parts by weight:
  • the polymerizable monomer composition is the polymerizable monomer composition obtained in Example 4;
  • the inorganic filler 2 is amorphous barium boroaluminosilicate modified by ⁇ -methacryloxypropyltrimethoxysilane Glass powder (GM27884), particle size D 50 is 0.7 ⁇ m;
  • inorganic filler 3 is fumed silica (OX-50) modified by ⁇ -methacryloxypropyltrimethoxysilane, particle size D 50 is 40nm;
  • Inorganic filler 4 is amorphous barium boroaluminosilicate glass powder (GM27884) modified by ⁇ -methacryloxypropyltrimethoxysilane, and the particle diameter D50 is 0.18 ⁇ m;
  • the preparation method of the resin ceramic restoration material provided in this application example includes: reacting the polymerizable monomer composition, the inorganic filler 2, the inorganic filler 3 and the inorganic filler 4 at 15 MPa and 120° C. for 2 hours to obtain the resin ceramic restoration material.
  • a resin ceramic restorative material comprises the following components in parts by weight:
  • the polymerizable monomer composition is the polymerizable monomer composition obtained in Example 5;
  • the inorganic filler 1 is amorphous barium boroaluminosilicate modified by ⁇ -methacryloxypropyltrimethoxysilane Glass powder (GM27884), particle size D50 is 1.5 ⁇ m;
  • inorganic filler 2 is amorphous barium boroaluminosilicate glass powder (GM27884) modified by ⁇ -methacryloxypropyl trimethoxysilane, particle size The diameter D50 is 0.7 ⁇ m;
  • the inorganic filler 3 is fumed silica (OX-50) modified by ⁇ -methacryloxypropyltrimethoxysilane, and the particle diameter D50 is 40nm;
  • the preparation method of the resin ceramic restoration material provided in this application example includes: reacting the polymerizable monomer composition, inorganic filler 1, inorganic filler 2 and inorganic filler 3 at 15 MPa and 120°C for 2 hours to obtain the resin ceramic restoration material.
  • a resin ceramic restorative material comprises the following components in parts by weight:
  • Polymerizable monomer composition 25 parts by weight;
  • Inorganic filler 1 70 parts by weight
  • Inorganic filler 2 5 parts by weight
  • the polymerizable monomer composition is the polymerizable monomer composition obtained in Example 6;
  • the inorganic filler 1 is amorphous barium boroaluminosilicate modified by ⁇ -methacryloxypropyltrimethoxysilane Glass powder (GM27884), particle size D 50 is 0.7 ⁇ m;
  • inorganic filler 2 is fumed silica (OX-50) modified by ⁇ -methacryloxypropyltrimethoxysilane, particle size D 50 is 40nm;
  • the preparation method of the resin ceramic restoration material provided in this application example includes: reacting the polymerizable monomer composition, the inorganic filler 1 and the inorganic filler 2 at 15Mpa and 120°C for 2 hours to obtain the resin ceramic restoration material.
  • a resin ceramic restorative material comprises the following components in parts by weight:
  • the polymerizable monomer composition is the polymerizable monomer composition obtained in Example 1;
  • the inorganic filler 5 is amorphous barium boroaluminosilicate glass powder (GM27884), and the particle diameter D50 is 1.5 ⁇ m;
  • the inorganic filler 6 It is amorphous barium boroaluminosilicate glass powder (GM27884), particle size D 50 is 0.7 ⁇ m;
  • inorganic filler 7 is fumed silica (OX-50), particle size D 50 is 40nm;
  • the preparation method of the ceramic restoration material comprises: reacting the polymerizable monomer composition, the inorganic filler 1, the inorganic filler 2 and the inorganic filler 3 at 15 MPa and 120° C. for 2 hours to obtain the resin ceramic restoration material.
  • a resin-ceramic restoration material the only difference from Application Example 1 is that the polymerizable monomer composition obtained in Comparative Example 1 is used to replace the polymerizable monomer composition obtained in Example 1, other components, dosage and preparation method All are the same as Application Example 1.
  • a resin-ceramic restoration material the only difference from Application Example 4 is that the polymerizable monomer composition obtained in Comparative Example 2 is used to replace the polymerizable monomer composition obtained in Example 2, other components, dosage and preparation method All are the same as Application Example 1.
  • a resin ceramic restorative material the only difference from Application Example 10 is that the polymerizable monomer composition obtained in Comparative Example 3 is used to replace the polymerizable monomer composition obtained in Example 6, other components, dosage and preparation method All are the same as Application Example 10.
  • Performance test (1) Bending strength and elastic modulus: Cut the cured resin ceramic repair material into a test piece of 1.2mm ⁇ 4.0mm ⁇ 18mm, and then wet-grind the surface of the test piece with 2000-grit sandpaper, and use a tensile force Testing machine, under the conditions of fulcrum spacing of 12mm and crosshead speed of 1.0mm/min, three-point bending test is carried out, and the average value of ten samples is used for evaluation;
  • Vickers hardness Use 2000-mesh sandpaper to grind and polish the test surface of the cured resin ceramic repair material to ensure that the surface of the sample is smooth; then use a Vickers hardness tester to test: select "2" for the test force value; measure resin ceramics 3 different positions of the repair material, and calculate the average value;
  • the bending strength of the resin-ceramic restoration materials obtained in the application examples 1-10 with the addition of cross-linking agent is 225-274MPa
  • the elastic modulus is 10.3-11.5GPa
  • the Vickers hardness is 102-131HV2 .0
  • the wear resistance is 12.1-16.6mm 3
  • the bending strength of the resin-ceramic repair material obtained in Comparative Application Examples 1-3 is only 190-212MPa
  • the elastic modulus is 7.5-8.2GPa
  • the Vickers hardness is 75-87HV2.0, wear resistance of 19.6-22.7mm 3 ; indicating that the mechanical properties of the resin ceramic repair material provided by the present invention are more excellent.
  • the water absorption value of the resin-ceramic restoration materials obtained in Application Examples 1-10 is 11-15 ⁇ g/mm 3
  • the dissolution value is 0.8-1.2 ⁇ g/mm 3 , which are obviously lower than those of the resin-ceramic restoration materials obtained in Comparative Application Examples 1 and 2.
  • Water absorption value and dissolution value it shows that the resin ceramic restorative material obtained by the present invention has little residual resin monomer.
  • the resin ceramic repair material provided by the present invention has excellent mechanical properties, biocompatibility, safety and long service life.
  • the present invention illustrates a polymerizable monomer composition for dental restoration and its preparation method and application through the above examples, but the present invention is not limited to the above examples, that is, it does not mean that the present invention must Rely on the above-mentioned embodiment to implement.
  • Those skilled in the art should understand that any improvement of the present invention, the equivalent replacement of each raw material of the product of the present invention, the addition of auxiliary components, the selection of specific methods, etc., all fall within the scope of protection and disclosure of the present invention.

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Abstract

本发明提供一种用于牙科修复的聚合性单体组合物及其制备方法和应用，所述聚合性单体组合物包括聚合性单体、引发剂和交联剂的组合；通过添加交联剂，提高了所述聚合性单体的双键转化率，降低了其残余率；将其添加到树脂陶瓷修复材料中可以使得制备得到的树脂陶瓷修复材料具有较高的强度、韧性，进而应用于牙齿修复时，不论在加工过程中，还是在患者佩戴、使用过程中都可以保持良好的形态；且由于所述树脂陶瓷修复材料的吸水值和溶解值的降低以及机械强度的提高，增加了其使用寿命，满足市场的需求。

Description

一种用于牙科修复的聚合性单体组合物及其制备方法和应用
本申请要求于2021年07月21日提交中国专利局、申请号为202110826681.7、发明名称为“一种用于牙科修复的聚合性单体组合物及其制备方法和应用”的中国专利申请的优先权，其全部内容通过引用结合在本申请中。
技术领域
本发明属于复合材料技术领域，具体涉及一种用于牙科修复的聚合性单体组合物及其制备方法和应用。
背景技术
目前，基于CAD/CAM技术的数字化修复已经成为口腔修复学的重要发展方向。多种口腔修复体已经可以通过数字化手段加工制作。CAD/CAM切削的牙科修复材料中，陶瓷材料因其力学性能、光学性能和生物相容性更好，是CAD/CAM技术应用最多的材料。但是，陶瓷材料脆性大，易发生瓷裂现象，对切削钻头的磨损较大，且因其硬度大对对颌牙的磨损很严重。树脂材料因价格低、韧性好、易加工切削、修复周期短，不磨损对颌牙，在CAD/CAM切削中占有较大比例。但是，树脂材料强度低、耐磨性较差，使用寿命短等，不能用作永久修复材料。
树脂陶瓷修复材料虽然结合了陶瓷材料强度高的特点和树脂材料韧性好的特点，但是仍然存在以下两点问题：(1)虽然树脂陶瓷修复材料在一定程度上继承了陶瓷材料的生物相容性，避免了陶瓷材料强度高易磨损对颌牙，易脆性断裂等缺点，并且与树脂材料相比力学性能也有不小的提升，但在实际的齿科修复中，树脂陶瓷复合材料的力学表现却并不能达到让人完全满意的程度。(2)树脂陶瓷修复材料的吸水值太高会使得该材料的机械性能降低，产生微渗漏、使材料的热稳定性降低，导致材料的未反应单体析出乃至造成聚合物链段的水解，最终使得材料的使用寿命降低。
CN106132383A公开了一种具有同时实现高韧性和刚性的固化物的 牙科材料用聚合性单体组合物、及含有该牙科材料用聚合性单体组合物的牙科材料用组合物、及具有高机械物性的其固化物。该发明中牙科材料用聚合性单体组合物含有氨基甲酸酯丙烯酸酯化合物和聚合性化合物，所述氨基甲酸酯丙烯酸酯化合物是通过使特定的羟基丙烯酸酯与二异氰酸酯反应而得到的，所述二异氰酸酯是二价的碳数6～9的芳香族烃基或二价的碳数6～9的桥环式烃基介由氢原子可被烃基取代的亚甲基与2个异氰酸酯基键合而成的，所述聚合性化合物含有选自甲基丙烯酰基及丙烯酰基中的至少1种聚合性基团。CN105310889A公开了一种牙科用固化性组合物，其中，以重量比10:90～70:30的比率含有树脂单体和填充材料，并且相对于100重量份树脂单体，含有0.01～10重量份聚合引发剂、0.001～1重量份类萜系化合物。通过添加类萜系化合物作为链转移剂，使牙科用固化性组合物所含的成分中导热性高且基于热而开始急剧聚合的树脂单体的热聚合速度变得迟缓，从而进行均匀的热聚合，进而抑制微观、宏观应变的产生，且能够抑制裂纹、碎屑的发生。此外，添加该链转移剂，还能够抑制沸点低的树脂单体的发泡，因此也能够抑制气泡的混入。但是，添加链转移剂以及对聚合性单体的设计并不能提高最终得到的陶瓷树脂材料的弯曲强度、硬度等机械性能，进而不能有效提高材料的使用寿命。
CN102665605A公开了一种热固化复合树脂块，该树脂块由含有烯键式不饱和基团的可聚合树脂，溶解在该树脂中在约100℃至约150℃的温度下活化的引发剂和与该树脂混合的无机填料组成；该树脂块的弯曲强度、耐磨耗性能和美学特性均得到显著改善。此外，由于引发剂的分解温度较高，在正常的处理条件下不会过早地分解成单体，也不会因为降解过程导致坯料变色。但是，改善后的机械强度只有200MPa，并不能完全满足患者使用需求。
因此，开发一种聚合性单体组合物，进而提高树脂陶瓷修复材料的力学性能、生物相容性和寿命，是本领域技术人员亟需解决的技术问题。
发明内容
针对现有技术的不足，本发明的目的在于提供一种用于牙科修复的聚合性单体组合物及其制备方法和应用，所述聚合性单体组合物包括特定份 数的聚合性单体、引发剂和交联剂的组合；通过添加交联剂，提高了聚合性单体组合物的双键转化率，降低了聚合性单体的残余率，使得聚合后体系的交联密度增大，进而可以增强聚合物的弯曲强度和硬度，降低吸水值和溶解值，使其应用于树脂陶瓷修复材料时可有效提高树脂陶瓷修复材料的力学性能和生物相容性。
为达此目的，本发明采用以下技术方案：
第一方面，本发明提供一种用于牙科修复的聚合性单体组合物，所述聚合性单体组合物按照重量份包括如下组分：聚合性单体20～100重量份、引发剂0.01～10重量份和交联剂0.01～10重量份。
在本发明中，所述聚合性单体优选为25重量份、30重量份、35重量份、40重量份、45重量份、50重量份、55重量份、60重量份、65重量份、70重量份、75重量份、80重量份、85重量份、90重量份或95重量份。在本发明中，所述聚合性单体的重量份优选为上述点值之间的其它所有点值，限于篇幅及出于简明的考虑，本发明不再穷尽列举所述范围包括的具体点值。
在本发明中，所述引发剂优选为0.2重量份、0.5重量份、1重量份、2重量份、3重量份、4重量份、5重量份、6重量份、7重量份、8重量份或9重量份。在本发明中，所述聚合性单体的重量份优选为上述点值之间的其它所有点值，限于篇幅及出于简明的考虑，本发明不再穷尽列举所述范围包括的具体点值。
在本发明中，所述交联剂优选为0.2重量份、0.5重量份、1重量份、2重量份、3重量份、4重量份、5重量份、6重量份、7重量份、8重量份或9重量份。在本发明中，所述聚合性单体的重量份优选为上述点值之间的具其它所有点值，限于篇幅及出于简明的考虑，本发明不再穷尽列举所述范围包括的具体点值。
本发明提供的用于牙科修复的聚合性单体组合物，通过添加交联剂，提高了聚合性单体的双键转化率，降低聚合性单体在牙科修复材料中的残余，使得聚合体系的交联密度增大，进而也能增强聚合物的弯曲强度和硬度，降低其吸水值和溶解值。
优选地，所述交联剂包括乙二醇二甲基丙烯酸酯、1,6-己二醇二甲基 丙烯酸酯、三甲基丙烷三甲基丙烯酸酯、三羟甲基丙烷三丙烯酸酯、二乙烯基苯、丙烯酸、丙烯酸羟乙酯、丙烯酸羟丙酯、甲基丙烯酸、甲基丙烯酸羟乙酯、甲基丙烯酸羟丙酯或N-羟甲基丙烯酰胺中的任意一种或至少两种的组合。
优选地，所述聚合性单体包括甲基丙烯酸甲酯、甲基丙烯酸乙酯、甲基丙烯酸异丁酯、甲基丙烯酸叔丁酯、甲基丙烯酸异戊酯、甲基丙烯酸苄基酯、甲基丙烯酸缩水甘油酯、甲基丙烯酸十二烷基酯、甲基丙烯酸四氢糠基酯、甲基丙烯酸2-(N,N-二甲基氨基)乙酯、甲基丙烯酸2,3-二溴丙酯、甲基丙烯酸2-羟基乙酯、甲基丙烯酸2-羟基丙酯、甲基丙烯酸6-羟基己酯、甲基丙烯酸10-羟基癸酯、三乙二醇单甲基丙烯酸酯、三乙二醇二甲基丙烯酸酯、单甲基丙烯酸丙二醇酯、乙二醇甲基丙烯酸酯、二乙二醇甲基丙烯酸酯、甲氧基二乙二醇甲基丙烯酸酯、聚乙二醇甲基丙烯酸酯、N-羟甲基(甲基)丙烯酰胺、N-琥珀基(甲基)丙烯酰胺、10-(甲基)丙烯酰氧基癸基磷酸二氢酯、二(甲基)乙二醇丙烯酸酯、二(甲基)丙二醇丙烯酸酯、二(甲基)丙烯酸新戊二醇酯、二(甲基)丁二醇丙烯酸酯、二(甲基)己二醇丙烯酸酯、二(甲基)丙烯酸聚乙二醇酯、二甲基丙烯酸氨基甲酸酯、双酚A甲基丙烯酸乙酯、(甲基)丙烯酸双酚A缩水甘油酯(2,2-双[4-[3-(甲基)丙烯酰氧基-2-羟基丙氧基]苯基]丙烷)、2,2-双[4-(甲基)丙烯酰氧基乙氧基苯基]丙烷、2,2-双(4-(甲基)丙烯酰氧基二乙氧基苯基)丙烷、2,2-双[4-(甲基)丙烯酰氧基聚乙氧基苯基]丙烷、三羟甲基丙烷三(甲基)丙烯酸酯、三羟甲基乙烷三(甲基)丙烯酸酯、三羟甲基丙烷三(甲基)丙烯酸酯、四羟甲基甲烷三(甲基)丙烯酸酯、四(甲基)季戊四醇丙烯酸酯、双三羟甲基丙烷四(甲基)丙烯酸酯、双季戊四醇四(甲基)丙烯酸酯、双季戊四醇六(甲基)丙烯酸酯或N,N’-(2,2,4-三甲基六亚甲基)双[2-(氨基羧基)丙烷-1,3-二醇]四甲基丙烯酸酯中的任意一种或至少两种的组合。
优选地，所述聚合性单体聚合后的折射率为1.52～1.58，优选为1.525、1.53、1.535、1.54、1.545、1.55、1.555、1.56、1.565、1.57或1.575。在本发明中，所述聚合性单体聚合后的折射率优选为上述点值之间的其它所有具体点值，限于篇幅及出于简明的考虑，本发明不再穷尽列举所述范围包括的具体点值。
优选地，所述引发剂包括二枯基过氧化物、叔丁基过氧化物、过氧化苯甲酰、过氧化月桂酰、过氧乙酸叔丁酯、过氧化苯甲酸叔丁酯、过氧化叔戊酸叔丁基酯、过硫酸钾、过硫酸钠、过硫酸铵、偶氮二异丁腈或偶氮二异庚腈或偶氮二异丁酸二甲酯中的任意一种或至少两种的组合。
第二方面，本发明提供一种如第一方面所述聚合性单体组合物的制备方法，所述制备方法包括：将聚合性单体、引发剂和交联剂混合，得到所述聚合性单体组合物。
优选地，所述混合的时间不小于1h，优选为1.1h、1.2h、1.3h、1.4h、1.5h、1.6h、1.7h、1.8h、1.9h或2h；所述混合的时间优选为上述点值之间的其它所有具体点值，限于篇幅及出于简明的考虑，本发明不再穷尽列举所述范围包括的具体点值。
优选地，所述混合在搅拌的条件下进行，进一步优选为在转速不小于20r/min的搅拌条件下进行；所述转速优选为30r/min、40r/min、50r/min、60r/min、70r/min、80r/min、90r/min或100r/min。
优选地，所述混合的温度不大于50℃，所述混合的温度优选为45℃、40℃、35℃、30℃、25℃、20℃、15℃、10℃或5℃；所述混合的温度优选为上述点值之间的其它所有具体点值，限于篇幅及出于简明的考虑，本发明不再穷尽列举所述范围包括的具体点值。
第三方面，本发明提供一种树脂陶瓷修复材料，所述树脂陶瓷修复材料包括如第一方面所述的聚合性单体组合物和无机填料。
本发明提供的树脂陶瓷修复材料，通过添加有交联剂的聚合性单体组合物，使得到的树脂陶瓷修复材料在保持美观性的基础上，提高了弯曲强度、吸水值以及溶解值等性能；得到的树脂陶瓷修复材料具有较高的强度、韧性，使得该材料在应用于牙齿修复时，不论在加工过程中，还是在患者佩戴、使用过程中都可以保持良好的形态，而不至于出现崩口、断裂等现象；且由于吸水值和溶解值的降低以及机械强度的提高，增加了其使用寿命，可用于永久性修复，进而使这种材料可以更广泛地应用于牙齿修复，满足市场的需求。
优选地，所述树脂陶瓷修复材料按照重量份包括如下组分：如第一方面所述的聚合性单体组合物10～90重量份和无机填料10～90重量份。
在本发明中，所述聚合性单体组合物的质量份数优选为20重量份、30重量份、40重量份、50重量份、60重量份、70重量份或80重量份；所述聚合性单体组合物的质量份数优选为上述点值之间的其它所有具体点值，限于篇幅及出于简明的考虑，本发明不再穷尽列举所述范围包括的具体点值。
在本发明中，所述无机填料的质量份数优选为20重量份、30重量份、40重量份、50重量份、60重量份、70重量份或80重量份；所述无机填料的质量份数优选为上述点值之间的的其它所有具体点值，限于篇幅及出于简明的考虑，本发明不再穷尽列举所述范围包括的具体点值。
优选地，所述无机填料包括二氧化硅、硅酸铝、氧化铝、氟化钙、氟化锶、碳酸钙、高岭土、粘土、云母、硫酸铝、硫酸钙、硫酸钡、氧化钛、磷酸钙、羟基磷灰石、氢氧化钙、氢氧化锶、沸石、二氧化钛或氧化锆中的任意一种或至少两种的组合。
优选地，所述无机填料还包括玻璃类无机填料。
优选地，所述玻璃类无机填料包括氟玻璃、硼硅玻璃、钠玻璃、钡玻璃、钡铝硅玻璃、含锶玻璃、含锆玻璃、玻璃陶瓷或氟铝硅酸盐玻璃中的任意一种或只至少两种的组合。
优选地，所述无机填料的折射率为1.52～1.58，优选为1.525、1.53、1.535、1.54、1.545、1.55、1.555、1.56、1.565、1.57或1.575；所述无机填料的折射率优选为上述点值之间的其它所有具体点值，限于篇幅及出于简明的考虑，本发明不再穷尽列举所述范围包括的具体点值。
优选地，所述无机填料为偶联剂改性无机填料。
作为本发明的优选技术方案，本发明提供的无机填料为偶联剂改性的无机填料，偶联剂改性无机填料与聚合性单体组合物的亲和性更好，进而可以提高树脂陶瓷修复材料固化物的机械强度。
优选地，所述偶联剂包括γ-甲基丙烯酰氧基丙基三甲氧基硅烷、γ-甲基丙烯酰氧基丙基三乙氧基硅烷或γ-氨丙基三甲氧基硅烷中的任意一种或至少两种的组合，进一步优选为γ-甲基丙烯酰氧基丙基三甲氧基硅烷。
优选地，所述树脂陶瓷修复材料还包括添加剂。
优选地，所述树脂陶瓷修复材料中添加剂的含量为0～5重量份且不 为0，优选为0.1重量份、0.5重量份、1重量份、1.5重量份、2重量份、2.5重量份、3重量份、3.5重量份、4重量份或4.5重量份；所述树脂陶瓷修复材料中添加剂的质量份数优选为上述点值之间其它所有的具体点值，限于篇幅及出于简明的考虑，本发明不再穷尽列举所述范围包括的具体点值。
优选地，所述添加剂包括着色剂、荧光剂、指示剂、粘度调节剂、润湿剂、抗氧化剂、稳定剂或稀释剂中的任意一种或至少两种的组合。
第四方面，本发明提供一种如第三方面所述树脂陶瓷修复材料的制备方法，所述制备方法包括：将聚合性单体组合物、无机填料和任选地添加剂进行反应，得到所述树脂陶瓷修复材料。
优选地，所述反应的时间不小于1h，优选为1.1h、1.2h、1.3h、1.4h、1.5h、1.6h、1.7h、1.8h、1.9h或2h；所述反应的时间优选为上述点值之间的其它所有具体点值，限于篇幅及出于简明的考虑，本发明不再穷尽列举所述范围包括的具体点值。
优选地，所述反应的压力不小于1Mpa，优选为2Mpa、3Mpa、4Mpa、5Mpa、6Mpa、7Mpa、8Mpa或9Mpa；所述反应的压力优选为上述点值之间的其它所有具体点值，限于篇幅及出于简明的考虑，本发明不再穷尽列举所述范围包括的具体点值。
优选地，所述反应的温度不小于80℃，优选为85℃、90℃、95℃、100℃、105℃、110℃、115℃或120℃；所述反应的温度优选为上述点值之间的其它所有具体点值，限于篇幅及出于简明的考虑，本发明不再穷尽列举所述范围包括的具体点值。
本发明提供的树脂陶瓷修复材料填充在模具中，在加热加压的条件下进行聚合固化即可成型。
第五方面，本发明一种如第三方面所述的树脂陶瓷修复材料在牙科修复材料中的应用。
相对于现有技术，本发明具有以下有益效果：
(1)本发明提供的用于牙科修复的聚合性单体组合物，通过添加交联剂，提高了聚合性单体的双键转化率，降低聚合性单体的残余，使得聚合体系的交联密度增大，进而增强聚合物的弯曲强度和硬度，降低其吸水 值和溶解值。
(2)本发明提供的树脂陶瓷修复材料，通过添加有交联剂的聚合性单体组合物，使得到的树脂陶瓷修复材料在保持美观性的基础上，提高了弯曲强度、吸水值、溶解值等性能。
(3)具体而言，本发明提供的树脂陶瓷修复材料的弯曲强度为225～274MPa，弹性模量为10.3～11.5GPa，维氏硬度为102～131HV2.0，耐磨耗性为12.1～16.6mm 3；吸水值为11～15μg/mm 3，溶解值为0.8～1.2μg/mm 3。本发明提供的树脂陶瓷修复材料兼具较高的强度、韧性，使得该材料在应用于牙齿修复时，不论在加工过程中，还是在患者佩戴、使用过程中，都可以保持良好的形态，而不至于出现崩口、断裂等现象；且由于吸水值和溶解值的降低以及机械强度的提高，增加了其使用寿命，可用于永久性修复，进而使这种材料可以更广泛地应用于牙齿修复，满足市场的需求。
具体实施方式
下面通过具体实施方式来进一步说明本发明的技术方案。本领域技术人员应该明了，所述实施例仅仅是帮助理解本发明，不应视为对本发明的具体限制。
实施例1
一种用于牙科修复的聚合性单体组合物，按照重量份包括如下组分：
Figure PCTCN2022104534-appb-000001
其制备方法包括：在40℃、转速为300r/min的搅拌条件下将二甲基丙烯酸氨基甲酸酯、三乙二醇二甲基丙烯酸酯和三甲基丙烷三甲基丙烯酸酯混合均匀，然后再加入过氧化苯甲酰继续在搅拌条件下混合2h，得到所述聚合性单体组合物。
实施例2
一种用于牙科修复的聚合性单体组合物，按照重量份包括如下组分：
Figure PCTCN2022104534-appb-000002
其制备方法包括：在45℃、转速为200r/min的搅拌条件下将2,2-双(4-(3-(甲基)丙烯酰氧基-2-羟基丙氧基)苯基)丙烷、三乙二醇二甲基丙烯酸酯和三甲基丙烷三甲基丙烯酸酯混合均匀，然后再加入过氧化苯甲酰继续在搅拌条件下混合1h，得到所述聚合性单体组合物。
实施例3
一种用于牙科修复的聚合性单体组合物，按照重量份包括如下组分：
Figure PCTCN2022104534-appb-000003
其制备方法包括：在50℃、转速为300r/min的搅拌条件下将2,2-双(4-(3-(甲基)丙烯酰氧基-2-羟基丙氧基)苯基)丙烷、三乙二醇二甲基丙烯酸酯和乙二醇二甲基丙烯酸酯混合均匀，然后再加入过氧化苯甲酰继续在搅拌条件下混合1.5h，得到所述聚合性单体组合物。
实施例4
一种用于牙科修复的聚合性单体组合物，按照重量份包括如下组分：
Figure PCTCN2022104534-appb-000004
其制备方法与实施例1相同。
实施例5
一种用于牙科修复的聚合性单体组合物，按照重量份包括如下组分：
Figure PCTCN2022104534-appb-000005
Figure PCTCN2022104534-appb-000006
其制备方法与实施例1相同。
实施例6
一种用于牙科修复的聚合性单体组合物，按照重量份包括如下组分：
Figure PCTCN2022104534-appb-000007
其制备方法与实施例1相同。
对比例1
一种用于牙科修复的聚合性单体组合物，其与实施例1的区别仅在于，不添加三甲基丙烷三甲基丙烯酸酯，其他组分、用量和制备方法均与实施例1相同。
对比例2
一种用于牙科修复的聚合性单体组合物，其与实施例2的区别仅在于，不添加三甲基丙烷三甲基丙烯酸酯，其他组分、用量和制备方法均与实施例1相同。
对比例3
一种用于牙科修复的聚合性单体组合物，其与实施例6的区别仅在于，不添加三甲基丙烷三甲基丙烯酸酯，其他组分、用量和制备方法均与实施例6相同。
应用例1
一种树脂陶瓷修复材料，按照重量份包括如下组分：
Figure PCTCN2022104534-appb-000008
其中，聚合性单体组合物为实施例1得到的聚合性单体组合物；无机填料1为γ-甲基丙烯酰氧基丙基三甲氧基硅烷改性的无定型钡硼铝硅酸盐玻璃粉(GM27884)，粒径D 50为1.5μm；无机填料2为γ-甲基丙烯酰 氧基丙基三甲氧基硅烷改性的无定型钡硼铝硅酸盐玻璃粉(GM27884)，粒径D 50为0.7μm；无机填料3为γ-甲基丙烯酰氧基丙基三甲氧基硅烷改性的气相二氧化硅(OX-50)，粒径D 50为40nm；
本应用例提供的树脂陶瓷修复材料的制备方法包括：将聚合性单体组合物、无机填料1、无机填料2和无机填料3在15Mpa、120℃下反应2h，得到所述树脂陶瓷修复材料。
应用例2
一种树脂陶瓷修复材料，按照重量份包括如下组分：
聚合性单体组合物   20重量份；
无机填料2          80重量份；
其中，聚合性单体组合物为实施例1得到的聚合性单体组合物；无机填料2为γ-甲基丙烯酰氧基丙基三甲氧基硅烷改性的无定型钡硼铝硅酸盐玻璃粉(GM27884)，粒径D 50为0.7μm；
本应用例提供的树脂陶瓷修复材料的制备方法包括：将聚合性单体组合物、和无机填料2在15Mpa、120℃下反应2h，得到所述树脂陶瓷修复材料。
应用例3
一种树脂陶瓷修复材料，按照重量份包括如下组分：
聚合性单体组合物   25重量份；
无机填料4          75重量份；
其中，聚合性单体组合物为实施例1得到的聚合性单体组合物；无机填料4为γ-甲基丙烯酰氧基丙基三甲氧基硅烷改性的无定型钡硼铝硅酸盐玻璃粉(GM27884)，粒径D 50为0.18μm；
本应用例提供的树脂陶瓷修复材料的制备方法包括：将聚合性单体组合物、和无机填料4在15Mpa、120℃下反应2h，得到所述树脂陶瓷修复材料。
应用例4
一种树脂陶瓷修复材料，按照重量份包括如下组分：
Figure PCTCN2022104534-appb-000009
Figure PCTCN2022104534-appb-000010
其中，聚合性单体组合物为实施例2得到的聚合性单体组合物；无机填料1为γ-甲基丙烯酰氧基丙基三甲氧基硅烷改性的无定型钡硼铝硅酸盐玻璃粉(GM27884)，粒径D 50为1.5μm；无机填料2为γ-甲基丙烯酰氧基丙基三甲氧基硅烷改性的无定型钡硼铝硅酸盐玻璃粉(GM27884)，粒径D 50为0.7μm；无机填料4为γ-甲基丙烯酰氧基丙基三甲氧基硅烷改性的无定型钡硼铝硅酸盐玻璃粉(GM27884)，粒径D 50为0.18μm；
本应用例提供的树脂陶瓷修复材料的制备方法包括：将聚合性单体组合物、无机填料1、无机填料2和无机填料4在15Mpa、120℃下反应2h，得到所述树脂陶瓷修复材料。
应用例5
一种树脂陶瓷修复材料，按照重量份包括如下组分：
聚合性单体组合物   22重量份；
无机填料4          78重量份；
其中，聚合性单体组合物为实施例2得到的聚合性单体组合物；无机填料4为γ-甲基丙烯酰氧基丙基三甲氧基硅烷改性的无定型钡硼铝硅酸盐玻璃粉(GM27884)，粒径D 50为0.18μm；
本应用例提供的树脂陶瓷修复材料的制备方法包括：将聚合性单体组合物和无机填料4在15Mpa、120℃下反应2h，得到所述树脂陶瓷修复材料。
应用例6
一种树脂陶瓷修复材料，按照重量份包括如下组分：
Figure PCTCN2022104534-appb-000011
其中，聚合性单体组合物为实施例3得到的聚合性单体组合物；无机填料2为γ-甲基丙烯酰氧基丙基三甲氧基硅烷改性的无定型钡硼铝硅酸盐玻璃粉(GM27884)，粒径D 50为0.7μm；无机填料3为γ-甲基丙烯酰 氧基丙基三甲氧基硅烷改性的气相二氧化硅(OX-50)，粒径D 50为40nm；无机填料4为γ-甲基丙烯酰氧基丙基三甲氧基硅烷改性的无定型钡硼铝硅酸盐玻璃粉(GM27884)，粒径D 50为0.18μm；
本应用例提供的树脂陶瓷修复材料的制备方法包括：将聚合性单体组合物、无机填料2、无机填料3和无机填料4在15Mpa、120℃下反应2h，得到所述树脂陶瓷修复材料。
应用例7
一种树脂陶瓷修复材料，按照重量份包括如下组分：
聚合性单体组合物   35重量份；
无机填料3          5重量份；
无机填料4          60重量份；
其中，聚合性单体组合物为实施例4得到的聚合性单体组合物；无机填料3为γ-甲基丙烯酰氧基丙基三甲氧基硅烷改性的气相二氧化硅(OX-50)，粒径D 50为40nm；无机填料4为γ-甲基丙烯酰氧基丙基三甲氧基硅烷改性的无定型钡硼铝硅酸盐玻璃粉(GM27884)，粒径D 50为0.18μm；
本应用例提供的树脂陶瓷修复材料的制备方法包括：将聚合性单体组合物、无机填料3和无机填料4在15Mpa、120℃下反应2h，得到所述树脂陶瓷修复材料。
应用例8
一种树脂陶瓷修复材料，按照重量份包括如下组分：
Figure PCTCN2022104534-appb-000012
其中，聚合性单体组合物为实施例4得到的聚合性单体组合物；无机填料2为γ-甲基丙烯酰氧基丙基三甲氧基硅烷改性的无定型钡硼铝硅酸盐玻璃粉(GM27884)，粒径D 50为0.7μm；无机填料3为γ-甲基丙烯酰氧基丙基三甲氧基硅烷改性的气相二氧化硅(OX-50)，粒径D 50为40nm；无机填料4为γ-甲基丙烯酰氧基丙基三甲氧基硅烷改性的无定型钡硼铝 硅酸盐玻璃粉(GM27884)，粒径D 50为0.18μm；
本应用例提供的树脂陶瓷修复材料的制备方法包括：将聚合性单体组合物、无机填料2、无机填料3和无机填料4在15Mpa、120℃下反应2h，得到所述树脂陶瓷修复材料。
应用例9
一种树脂陶瓷修复材料，按照重量份包括如下组分：
Figure PCTCN2022104534-appb-000013
其中，聚合性单体组合物为实施例5得到的聚合性单体组合物；无机填料1为γ-甲基丙烯酰氧基丙基三甲氧基硅烷改性的无定型钡硼铝硅酸盐玻璃粉(GM27884)，粒径D 50为1.5μm；无机填料2为γ-甲基丙烯酰氧基丙基三甲氧基硅烷改性的无定型钡硼铝硅酸盐玻璃粉(GM27884)，粒径D 50为0.7μm；无机填料3为γ-甲基丙烯酰氧基丙基三甲氧基硅烷改性的气相二氧化硅(OX-50)，粒径D 50为40nm；
本应用例提供的树脂陶瓷修复材料的制备方法包括：将聚合性单体组合物、无机填料1、无机填料2和无机填料3在15Mpa、120℃下反应2h，得到所述树脂陶瓷修复材料。
应用例10
一种树脂陶瓷修复材料，按照重量份包括如下组分：
聚合性单体组合物    25重量份；
无机填料1           70重量份；
无机填料2           5重量份；
其中，聚合性单体组合物为实施例6得到的聚合性单体组合物；无机填料1为γ-甲基丙烯酰氧基丙基三甲氧基硅烷改性的无定型钡硼铝硅酸盐玻璃粉(GM27884)，粒径D 50为0.7μm；无机填料2为γ-甲基丙烯酰氧基丙基三甲氧基硅烷改性的气相二氧化硅(OX-50)，粒径D 50为40nm；
本应用例提供的树脂陶瓷修复材料的制备方法包括：将聚合性单体组合物、无机填料1和无机填料2在15Mpa、120℃下反应2h，得到所述 树脂陶瓷修复材料。
应用例11
一种树脂陶瓷修复材料，按照重量份包括如下组分：
Figure PCTCN2022104534-appb-000014
其中，聚合性单体组合物为实施例1得到的聚合性单体组合物；无机填料5为无定型钡硼铝硅酸盐玻璃粉(GM27884)，粒径D 50为1.5μm；无机填料6为无定型钡硼铝硅酸盐玻璃粉(GM27884)，粒径D 50为0.7μm；无机填料7为气相二氧化硅(OX-50)，粒径D 50为40nm；本应用例提供的树脂陶瓷修复材料的制备方法包括：将聚合性单体组合物、无机填料1、无机填料2和无机填料3在15Mpa、120℃下反应2h，得到所述树脂陶瓷修复材料。
对比应用例1
一种树脂陶瓷修复材料，其与应用例1的区别仅在于，采用对比例1得到的聚合性单体组合物替换实施例1得到的聚合性单体组合物，其他组分、用量和制备方法均与应用例1相同。
对比应用例2
一种树脂陶瓷修复材料，其与应用例4的区别仅在于，采用对比例2得到的聚合性单体组合物替换实施例2得到的聚合性单体组合物，其他组分、用量和制备方法均与应用例1相同。
对比应用例3
一种树脂陶瓷修复材料，其与应用例10的区别仅在于，采用对比例3得到的聚合性单体组合物替换实施例6得到的聚合性单体组合物，其他组分、用量和制备方法均与应用例10相同。
性能测试：(1)弯曲强度和弹性模量：将固化后的树脂陶瓷修复材料切削成1.2mm×4.0mm×18mm的实验片，然后用2000目砂纸湿磨对实验片表面进行抛光，使用拉力试验机，在支点间距为12mm、十字头速度为1.0mm/min的条件下进行三点弯曲试验，以十个试样的平均值进 行评价；
(2)维氏硬度：使用2000目砂纸水磨抛光固化后的树脂陶瓷修复材料的测试面，确保试样表面光滑；然后采用维氏硬度计进行测试：测试力值选择“2”；测量树脂陶瓷修复材料的3个不同位置，求取平均值；
(3)耐磨耗性：采用机械加工设备加工固化后的树脂陶瓷修复材料，制备尺寸为
Figure PCTCN2022104534-appb-000015
的试样，每种材料制备3个试样；使用400目砂纸预磨，磨耗负荷为22N，摩擦次数为75次；取下砂纸，对料盘、对磨偶件、试样、夹具进行冲洗并擦干；使用磨料进行预磨，磨耗负荷172N，对试样摩擦150次。清洗后称量，记为试样磨前质量m 1；使用牛牙以磨耗负荷172N，对试样摩擦1500次，清洗后称量，记为试样磨后质量m 2；共磨耗3个试样，每次磨耗前更换对磨偶件和磨料；测量前测定试样密度ρ；试样体积损失量为：ΔV＝(m 1-m 2)/ρ。
(4)吸水值和溶解值：将固化后的树脂陶瓷修复材料加工成
Figure PCTCN2022104534-appb-000016
的样片，然后用2000目砂纸湿磨对样片表面进行抛光，测量试样直径及厚度计算试样体积V；将其放置一个保干器内于37℃烘箱中烘干，24h后再将试样取出，逐一用万分之一天平称重，精确至0.1mg。重复上述步骤，直至达恒重，记为m 1；将恒重的试样放置于约盛有30mL纯化水的自封袋中于37±1℃的恒温水浴锅中浸泡，浸泡7天后取出，用清水冲洗后，擦干表面水分后测试，用万分之一天平称重，记为m 2；最后将其放置于37℃烘箱中烘14～21天至恒重，用万分之一天平称重，记为m 3；吸水ρ ws＝(m 2-m 3)/V；溶解值ρ sl＝(m 1-m 3)/V。
按照上述测试方法对应用例1～11和对比应用例1～3得到的树脂陶瓷修复材料对应的树脂陶瓷修复材料进行测试，测试结果如表1所示：
表1应用例1～11和对比应用例1～3得到的树脂陶瓷修复材料的性能参数
Figure PCTCN2022104534-appb-000017
Figure PCTCN2022104534-appb-000018
根据表1的数据可以看出，添加了交联剂的应用例1～10得到的树脂陶瓷修复材料的弯曲强度为225～274MPa，弹性模量为10.3～11.5GPa，维氏硬度为102～131HV2.0，耐磨耗性为12.1～16.6mm 3；而对比应用例1～3得到的树脂陶瓷修复材料的弯曲强度为仅有190～212MPa，弹性模量为7.5～8.2GPa，维氏硬度为75～87HV2.0，耐磨耗性为19.6～22.7mm 3；说明本发明提供的树脂陶瓷修复材料的机械性能更加优异。
并且应用例1～10得到的树脂陶瓷修复材料的吸水值为11～15μg/mm 3，溶解值为0.8～1.2μg/mm 3，明显低于对比应用例1和2得到的树脂陶瓷修复材料的吸水值和溶解值；说明本发明得到的树脂陶瓷修复材料中树脂单体残余少。
且比较应用例1和应用例11可以发现，添加没有经过偶联剂改性的填料得到的树脂陶瓷修复材料的机械性能、吸水性以及溶剂性均较低。
综上可以看出：本发明提供的树脂陶瓷修复材料具有优异的机械性能、生物相容性、安全性和较长的使用寿命。
申请人声明，本发明通过上述实施例来说明一种用于牙科修复的聚合性单体组合物及其制备方法和应用，但本发明并不局限于上述实施例，即不意味着本发明必须依赖上述实施例才能实施。所属技术领域的技术人员应该明了，对本发明的任何改进，对本发明产品各原料的等效替换及辅助成分的添加、具体方式的选择等，均落在本发明的保护范围和公开范围之内。

Claims (25)

  1. 一种用于牙科修复的聚合性单体组合物，其特征在于，所述聚合性单体组合物按照重量份包括如下组分：聚合性单体20～100重量份、引发剂0.01～10重量份和交联剂0.01～10重量份。
  2. 根据权利要求1所述的聚合性单体组合物，其特征在于，所述交联剂包括乙二醇二甲基丙烯酸酯、1,6-己二醇二甲基丙烯酸酯、三甲基丙烷三甲基丙烯酸酯、三羟甲基丙烷三丙烯酸酯、二乙烯基苯、丙烯酸、丙烯酸羟乙酯、丙烯酸羟丙酯、甲基丙烯酸、甲基丙烯酸羟乙酯、甲基丙烯酸羟丙酯和N-羟甲基丙烯酰胺中的任意一种或至少两种的组合。
  3. 根据权利要求1所述的聚合性单体组合物，其特征在于，所述聚合性单体包括甲基丙烯酸甲酯、甲基丙烯酸乙酯、甲基丙烯酸异丁酯、甲基丙烯酸叔丁酯、甲基丙烯酸异戊酯、甲基丙烯酸苄基酯、甲基丙烯酸缩水甘油酯、甲基丙烯酸十二烷基酯、甲基丙烯酸四氢糠基酯、甲基丙烯酸2-(N,N-二甲基氨基)乙酯、甲基丙烯酸2,3-二溴丙酯、甲基丙烯酸2-羟基乙酯、甲基丙烯酸2-羟基丙酯、甲基丙烯酸6-羟基己酯、甲基丙烯酸10-羟基癸酯、三乙二醇单甲基丙烯酸酯、三乙二醇二甲基丙烯酸酯、单甲基丙烯酸丙二醇酯、乙二醇甲基丙烯酸酯、二乙二醇甲基丙烯酸酯、甲氧基二乙二醇甲基丙烯酸酯、聚乙二醇甲基丙烯酸酯、N-羟甲基(甲基)丙烯酰胺、N-琥珀基(甲基)丙烯酰胺、10-(甲基)丙烯酰氧基癸基磷酸二氢酯、二(甲基)乙二醇丙烯酸酯、二(甲基)丙二醇丙烯酸酯、二(甲基)丙烯酸新戊二醇酯、二(甲基)丁二醇丙烯酸酯、二(甲基)己二醇丙烯酸酯、二(甲基)丙烯酸聚乙二醇酯、二甲基丙烯酸氨基甲酸酯、双酚A甲基丙烯酸乙酯、(甲基)丙烯酸双酚A缩水甘油酯(2,2-双[4-[3-(甲基)丙烯酰氧基-2-羟基丙氧基]苯基]丙烷)、2,2-双[4-(甲基)丙烯酰氧基乙氧基苯基]丙烷、2,2-双(4-(甲基)丙烯酰氧基二乙氧基苯基)丙烷、三羟甲基丙烷三(甲基)丙烯酸酯、三羟甲基乙烷三(甲基)丙烯酸酯、三羟甲基丙烷三(甲基)丙烯酸酯、四羟甲基甲烷三(甲基)丙烯酸酯、四(甲基)季戊四醇丙烯酸酯、双三羟甲基丙烷四(甲基)丙烯酸酯、双季戊四醇四(甲基)丙烯酸酯、双季戊四醇六(甲基)丙烯酸酯和N,N’-(2,2,4-三甲基六亚甲基)双[2-(氨基羧基)丙烷-1,3-二醇]四甲基丙 烯酸酯中的任意一种或至少两种的组合。
  4. 根据权利要求1或3所述的聚合性单体组合物，其特征在于，所述聚合性单体聚合后的折射率为1.52～1.58。
  5. 根据权利要求1所述的聚合性单体组合物，其特征在于，所述引发剂包括二枯基过氧化物、叔丁基过氧化物、过氧化苯甲酰、过氧化月桂酰、过氧乙酸叔丁酯、过氧化苯甲酸叔丁酯、过氧化叔戊酸叔丁基酯、过硫酸钾、过硫酸钠、过硫酸铵、偶氮二异丁腈或偶氮二异庚腈或偶氮二异丁酸二甲酯中的任意一种或至少两种的组合。
  6. 一种如权利要求1～5任一项所述聚合性单体组合物的制备方法，其特征在于，所述制备方法包括：将聚合性单体、引发剂和交联剂混合，得到所述聚合性单体组合物。
  7. 根据权利要求6所述的制备方法，其特征在于，所述混合的时间不小于1h.
  8. 根据权利要求6或7所述的制备方法，其特征在于，所述混合在搅拌的条件下进行；
    所述混合为在转速不小于20r/min的搅拌条件下进行；
  9. 根据权利要求8所述的制备方法，其特征在于，所述混合的温度不大于50℃。
  10. 一种树脂陶瓷修复材料，其特征在于，所述树脂陶瓷修复材料包括聚合性单体组合物和无机填料的组合；
    所述聚合性单体组合物为如权利要求1～5任一项所述的聚合性单体组合物或如权利要求6～9任一项所述制备方法制备得到的聚合性单体组合物。
  11. 根据权利要求10所述的树脂陶瓷修复材料，其特征在于，所述树脂陶瓷修复材料按照重量份包括如下组分：聚合性单体组合物10～90重量份和无机填料10～90重量份。
  12. 根据权利要求10或11所述的树脂陶瓷修复材料，其特征在于，所述无机填料包括二氧化硅、硅酸铝、氧化铝、氟化钙、氟化锶、碳酸钙、高岭土、粘土、云母、硫酸铝、硫酸钙、硫酸钡、氧化钛、磷酸钙、羟基磷灰石、氢氧化钙、氢氧化锶、沸石、二氧化钛或氧化锆中的任意一种或 至少两种的组合。
  13. 根据权利要求12所述的树脂陶瓷修复材料，其特征在于，所述无机填料还包括玻璃类无机填料。
  14. 根据权利要求13所述的树脂陶瓷修复材料，其特征在于，所述玻璃类无机填料包括氟玻璃、硼硅玻璃、钠玻璃、钡玻璃、钡铝硅玻璃、含锶玻璃、含锆玻璃、玻璃陶瓷或氟铝硅酸盐玻璃中的任意一种或至少两种的组合。
  15. 根据权利要求10、11、13或14所述的树脂陶瓷修复材料，其特征在于，所述无机填料的折射率为1.52～1.58。
  16. 根据权利要求10或11所述的树脂陶瓷修复材料，其特征在于，所述无机填料为偶联剂改性无机填料。
  17. 根据权利要求16所述的树脂陶瓷修复材料，其特征在于，所述偶联剂包括γ-甲基丙烯酰氧基丙基三甲氧基硅烷、γ-甲基丙烯酰氧基丙基三乙氧基硅烷或γ-氨丙基三甲氧基硅烷中的任意一种或至少两种的组合。
  18. 根据权利要求10所述的树脂陶瓷修复材料，其特征在于，所述树脂陶瓷修复材料还包括添加剂。
  19. 根据权利要求19所述的树脂陶瓷修复材料，其特征在于，所述树脂陶瓷修复材料中添加剂的含量为0～5重量份且不为0。
  20. 根据权利要求19或20所述的树脂陶瓷修复材料，其特征在于，所述添加剂包括着色剂、荧光剂、指示剂、粘度调节剂、润湿剂、抗氧化剂、稳定剂或稀释剂中的任意一种或至少两种的组合。
  21. 一种如权利要求10～21任一项所述树脂陶瓷修复材料的制备方法，其特征在于，所述制备方法包括：将聚合性单体组合物、无机填料和任选地添加剂进行反应，得到所述树脂陶瓷修复材料。
  22. 根据权利要求22所述的制备方法，其特征在于，所述反应的时间不小于1h。
  23. 根据权利要求22或23所述的制备方法，其特征在于，所述反应的压力不小于1Mpa。
  24. 根据权利要求22或23所述的制备方法，其特征在于，所述反应的温度不小于80℃。
  25. 一种如权利要求10～21任一项所述的树脂陶瓷修复材料或如权利要求22～25任一项所述制备方法制备得到的树脂陶瓷修复材料在牙科修复材料中的应用。
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CN113563504B (zh) * 2021-07-21 2023-09-15 爱迪特（秦皇岛）科技股份有限公司 一种用于牙科修复的聚合性单体组合物及其制备方法和应用
CN115350335B (zh) * 2022-08-16 2023-08-01 爱迪特（秦皇岛）科技股份有限公司 一种牙科修复用仿生复合材料及其应用
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