Dental self-adhesive resin composition as well as preparation method and application thereof

Abstract

The invention provides a dental self-adhesive resin composition and a preparation method and application thereof, the dental self-adhesive resin composition comprises a matrix component and a catalyst component, the matrix component comprises a polymerizable monomer A without an acidic group, a polymerizable monomer containing an acidic group, a photoinitiator, a reducing agent, a flow regulator and a filler A, the catalyst component comprises a polymerizable monomer B which does not contain an acidic group, an oxidizing agent and a filler B; by adding the flow regulator into the matrix component, the obtained self-adhesive resin composition has low viscosity and good fluidity, further has high wettability on the surface of tooth tissue, and can fully penetrate into hard tissue of teeth to improve combination with dentin and enamel, so that the bonding strength is improved, and the service life of the self-adhesive resin composition is prolonged. Meanwhile, the high flexural strength can be kept, and the adhesive is very suitable for being used as a dental adhesive.

Description

Technical Field

[0001] The present invention belongs to the technical field of dental materials, and particularly relates to a self-adhesive resin composition for dental use, a preparation method thereof, and an application thereof. Background Art

[0002] When performing fixed dental restoration, the success mainly depends on the adhesion between the restoration and the tooth tissue, and a large part of the success of the adhesion depends on the adhesive material.

[0003] Currently, the conventional operation for adhesion is to separately apply an adhesive on the surfaces of the treated restoration and the tooth tissue, blow dry and cure it, and then apply a resin cement inside the restoration for the restoration to be seated. This method has complex operations, and the application time and uniformity of the adhesive will affect the final adhesion performance. In order to simplify the operation process, self-adhesive resin cements have emerged. Such substances do not require the use of an adhesive during use, directly combining the two-step operations of applying the adhesive and the cement into one step, simplifying the adhesion operation procedure, thereby greatly reducing the technical sensitivity and tooth sensitivity; however, such self-adhesive resin cements cannot achieve the same adhesion strength as that of applying an adhesive.

[0004] Therefore, there is an urgent need to develop a self-adhesive resin composition for dental use with high adhesion strength to solve the above technical problems. Summary of the Invention

[0005] Aiming at the deficiencies of the prior art, the purpose of the present invention is to provide a self-adhesive resin composition for dental use, a preparation method thereof, and an application thereof. The self-adhesive resin composition for dental use has a low viscosity, good fluidity, and thus has a high wettability on the surface of tooth tissue, can fully penetrate into the hard tooth tissue, improve the bonding with dentin and enamel, and thereby increase the adhesion strength.

[0006] To achieve this purpose, the present invention adopts the following technical solutions:

[0007] In the first aspect, the present invention provides a self-adhesive resin composition for dental use, and the self-adhesive resin composition for dental use includes a matrix component and a catalyst component;

[0008] The matrix component includes a polymerizable monomer A without acidic groups, a polymerizable monomer with acidic groups, a photoinitiator, a reducing agent, a flow regulator, and a filler A;

[0009] The catalyst component includes a polymerizable monomer B without acidic groups, an oxidizing agent, and a filler B.

[0010] The inventors of the present invention have found through research that the main reason for the low bonding strength of current self - adhesive resin compositions for dental use is that the self - adhesive resin compositions for dental use have a high consistency, resulting in a weak wetting effect on the surface of dental tissues, leading to low bonding strength and poor bonding effect. Therefore, improving the fluidity of the self - adhesive resin compositions for dental use and increasing the wetting effect between the self - adhesive resin compositions and the surfaces of dental tissues and restorative materials can significantly improve the bonding strength between the two.

[0011] Based on the above content, the self - adhesive resin composition for dental use provided by the present invention adds a flow regulator to the matrix component. The addition of the flow regulator, firstly, can effectively improve the fluidity of the self - adhesive resin composition, making its wetting effect on dental tissues stronger, and then being able to more fully contact the bonded surface, increasing the contact area to improve the bonding strength with the bonded dental tissues; secondly, the self - adhesive resin composition with good fluidity can more easily penetrate into the micropores and gaps on the surface of the bonded dental tissues, forming a mechanical locking effect with the dental tissues, enhancing the interaction force between the two, and further improving the bonding strength with the bonded dental tissues; in addition, the improvement of the fluidity of the self - adhesive resin composition can also improve the operability of doctors during clinical use, making the coating more uniform, and being easier to fill into narrow gaps, making the restorative body closer to the dental body, and at the same time being easier for doctors to make the restorative body in place, and also being able to avoid the problem of occlusal elevation caused by bonding.

[0012] Preferably, the matrix component comprises the following components by weight:

[0013]

[0014]

[0015] As a preferred technical solution of the present invention, limiting the amounts of various substances within the above - specified ranges can ensure that the obtained self - adhesive resin composition for dental use has the most excellent comprehensive performance and is more suitable for use as a dental cement.

[0016] Among them, the amount of the polymerizable monomer A without acidic groups can be 20 parts by weight, 22 parts by weight, 24 parts by weight, 26 parts by weight, 28 parts by weight, 30 parts by weight, 32 parts by weight, 34 parts by weight, 36 parts by weight, 38 parts by weight or 40 parts by weight, etc.

[0017] The amount of the polymerizable monomer containing acidic groups can be 1 part by weight, 2 parts by weight, 4 parts by weight, 6 parts by weight, 8 parts by weight, 10 parts by weight, 12 parts by weight, 14 parts by weight, 16 parts by weight, 18 parts by weight, 20 parts by weight, 22 parts by weight, 24 parts by weight or 25 parts by weight, etc.

[0018] The dosage of the photoinitiator can be 0.1 part by weight, 0.2 part by weight, 0.4 part by weight, 0.6 part by weight, 0.8 part by weight, 1 part by weight, 1.2 part by weight, 1.4 part by weight, 1.6 part by weight, 1.8 part by weight, 2 parts by weight, etc.

[0019] The dosage of the reducing agent can be 0.1 part by weight, 0.5 part by weight, 1 part by weight, 1.5 part by weight, 2 parts by weight, 2.5 parts by weight, 3 parts by weight, 3.5 parts by weight, 4 parts by weight, 4.5 parts by weight, 5 parts by weight, etc.

[0020] The dosage of the flow regulator can be 0.1 part 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, 9 parts by weight, 10 parts by weight, etc.

[0021] The dosage of the filler A can be 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, etc.

[0022] Preferably, the flow regulator is a cage compound with a cavity structure; the cage compound with a cavity structure has a hydrophobic cavity, through which small molecules in the system can be included to form a stable inclusion compound. This inclusion effect reduces the interaction between small molecules, thereby reducing the viscosity of the system. At the same time, when the flow regulator is connected with a hydrophilic group, it will have a hydrophilic outer surface, and its hydrophilic outer surface can interact with the fillers in the system to make the fillers evenly dispersed, reducing the friction between particles, thereby reducing the viscosity of the system. In addition, the cage compound with a cavity structure has a certain surface activity, which can reduce the surface tension of the system, thereby improving the wettability of the system to dental tissues and increasing the bonding strength.

[0023] Preferably, the flow regulator includes any one or a combination of at least two of cyclodextrin compounds, cage-type sesquisiloxanes, calixarenes, pillararenes, crown ethers, cucurbiturils or nanoporous particles, more preferably any one or a combination of at least two of cyclodextrin compounds, cage-type sesquisiloxanes or nanoporous particles, and even more preferably cyclodextrin compounds.

[0024] Preferably, the cyclodextrin compounds include any one or a combination of at least two of α-cyclodextrin, β-cyclodextrin, γ-cyclodextrin, hydroxypropyl-β-cyclodextrin (HP-β-CD) or sulfobutyl-β-cyclodextrin (SB-β-CD).

[0025] Preferably, the nanoporous particles include nanoporous starch.

[0026] Preferably, the calixarenes include amino calix[4]arene and / or carboxy calix[4]arene.

[0027] Preferably, the pillararene includes sulfonated pillararene and / or amino pillararene.

[0028] Preferably, the polymerizable monomer A without acidic groups includes any one or a combination of at least two of bisphenol A glycerol dimethacrylate (Bis-GMA), ethoxylated bisphenol A dimethacrylate (Bis-EMA), triethylene glycol dimethacrylate (TEGDMA), urethane dimethacrylate (UDMA), 2-hydroxyethyl methacrylate (HEMA), 2-methyl-acrylic acid-1,12-dodecanediol ester (HDDMA), ethoxylated bisphenol A dimethacrylate (BisEMA), glycerol dimethacrylate (GDMA), trimethylolpropane triacrylate (TMPTA), trimethylolpropane trimethacrylate (TMPTMA), pentaerythritol triacrylate (PETA), propoxylated glycerol triacrylate (GPTA), tris(2-hydroxyethyl) isocyanurate triacrylate (THEICTA), trimethylolpropane triacrylate (DTMPTTA), pentaerythritol tetraacrylate (PETTA), or dipentaerythritol hexaacrylate (DPHA); more preferably, a combination of at least two of bisphenol A glycerol dimethacrylate, ethoxylated bisphenol A dimethacrylate, triethylene glycol dimethacrylate, urethane dimethacrylate, 2-hydroxyethyl methacrylate, 2-methyl-acrylic acid-1,12-dodecanediol ester, ethoxylated bisphenol A dimethacrylate, glycerol dimethacrylate, trimethylolpropane triacrylate, trimethylolpropane trimethacrylate, pentaerythritol triacrylate, propoxylated glycerol triacrylate, tris(2-hydroxyethyl) isocyanurate triacrylate, trimethylolpropane triacrylate, pentaerythritol tetraacrylate, or dipentaerythritol hexaacrylate.

[0029] Preferably, the polymerizable monomer with acidic groups includes phosphate monomers and / or carboxylate monomers.

[0030] Preferably, the phosphate monomers include any one or a combination of at least two of 10-methacryloyloxydecyl dihydrogen phosphate (10-MDP), 2-methacryloyloxyethyl phenyl phosphate (Phenyl-P), pentaerythritol triacrylate phosphate (PENTA), or glycerol phosphate dimethacrylate (GPDM).

[0031] Preferably, the carboxylate monomers include any one or a combination of at least two of 4-methacryloyloxyethyl trimellitic anhydride ester (4-META), 4-acryloyloxyethyl trimellitic anhydride ester (4-AET), or 11-methacryloyloxyundecanedioic acid (MAC-10).

[0032] Preferably, the photoinitiator includes any one or a combination of at least two of camphorquinone (CQ), 9,10-phenanthrenequinone, α-diketone, 1-phenylpropane-1,2-dione, 2,2-dimethoxy-2-phenylacetophenone, diphenyl-(2,4,6-trimethylbenzoyl)phosphine oxide (TPO), ethyl 2,4,6-trimethylbenzoyl phenylphosphinate (TPO-L), bis(4-methylphenyl)(2,4,6-trimethylbenzoyl)phosphine oxide (TMO), dibenzoyldiethylgermane, tetrabenzoyl germanium, tetrakis(o-methylbenzoyl)germanium, tetrakis(acyl)stannane, or triphenylantimony.

[0033] Preferably, the reducing agent is an amine compound.

[0034] Preferably, the amine compound includes any one or a combination of at least two of N,N-dimethyl-p-toluidine (DMPT), N,N-di(2-hydroxyethyl)-p-toluidine (DHEPT), N,N-dimethyl-p-toluidine (DMT), ethyl 4-dimethylaminobenzoate (EDB), or N-acetylthiourea (ATU).

[0035] For the self-adhesive resin composition for dentistry provided by the present invention, there are no special requirements for the specific type of the filler A, and conventional substances in the art can be selected.

[0036] Preferably, the filler A is any one or a combination of at least two of silica-based fillers, glass-based fillers, or other fillers.

[0037] Preferably, the silica-based fillers include particulate silica and / or fumed silica.

[0038] Preferably, the glass-based fillers include any one or a combination of at least two of barium glass, strontium glass, lanthanum glass, lithium borosilicate glass, or borosilicate glass.

[0039] Preferably, the other fillers include any one or a combination of at least two of zirconia, alumina, ytterbium trifluoride, or titanium dioxide.

[0040] And as a preferred technical solution of the present invention, the above-mentioned filler A can be subjected to silanization treatment, which is more beneficial to improving the mechanical properties of the self-adhesive resin composition.

[0041] Preferably, the matrix component further includes a photo-curing accelerator.

[0042] Preferably, the content of the photo-curing accelerator in the matrix component is 0.1 to 5 parts by weight, such as 0.1 part by weight, 0.5 part 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, 4.5 parts by weight, or 5 parts by weight, etc.

[0043] Preferably, the photo-curing accelerator includes aromatic tertiary amine and / or aliphatic tertiary amine, more preferably any one or at least two combinations of dimethylaminoethyl methacrylate (DMAEMA), ethyl 4-dimethylaminobenzoate, N,N-dimethylaminoethyl ester or N,N-diethylaniline.

[0044] Preferably, inhibitor A is further included in component A.

[0045] Preferably, the content of inhibitor A in component A is 0.01-0.5 parts by weight, such as 0.01 part by weight, 0.05 part by weight, 0.1 part by weight, 0.15 part by weight, 0.2 part by weight, 0.25 part by weight, 0.3 part by weight, 0.35 part by weight, 0.4 part by weight, 0.45 part by weight or 0.5 part by weight, etc.

[0046] Preferably, inhibitor A includes any one or at least two combinations of 2,6-di-tert-butyl-p-cresol (BHT), p-methoxyphenol or 2-hydroxy-4-methoxybenzophenone.

[0047] Preferably, other additives are further included in the matrix component.

[0048] For the self-adhesive resin composition for dental use provided by the present invention, other additives except flow regulators, photoinitiators, reducing agents, inhibitors and photo-curing accelerators can be added to the matrix component as needed, such as colorants, defoamers, etc., and the present invention has no special requirements for the specific types and dosages of the other additives, and conventional substances in the art can be selected and the dosages can be added as needed.

[0049] Preferably, the colorant can be selected from iron oxide yellow, iron oxide red, zirconium oxide, etc.

[0050] Preferably, the defoamer can be selected from dimethyl silicone oil, modified polysiloxane, etc.

[0051] Preferably, the content of other additives in the matrix component is 0.1-10 parts by weight, such as 0.1 part by weight, 1 part 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, 9 parts by weight or 10 parts by weight, etc.

[0052] Preferably, the catalyst component includes the following components by weight:

[0053] Polymerizable monomer B without acidic group 20-40 parts by weight;

[0054] Oxidizing agent 0.1-5 parts by weight;

[0055] Filler B 40-70 parts by weight.

[0056] Among them, the dosage of the polymerizable monomer B without acidic groups can be 20 parts by weight, 22 parts by weight, 24 parts by weight, 26 parts by weight, 28 parts by weight, 30 parts by weight, 32 parts by weight, 34 parts by weight, 36 parts by weight, 38 parts by weight, 40 parts by weight, etc.

[0057] The dosage of the oxidant can be 0.1 part by weight, 0.5 part 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, 4.5 parts by weight, 5 parts by weight, etc.

[0058] The dosage of the filler B can be 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, etc.

[0059] Preferably, the polymerizable monomer B without acidic groups includes any one or a combination of at least two of bisphenol A glycerol dimethacrylate (Bis-GMA), ethoxylated bisphenol A dimethacrylate (Bis-EMA), triethylene glycol dimethacrylate (TEGDMA), urethane dimethacrylate (UDMA), 2-hydroxyethyl methacrylate (HEMA), 1,12-dodecanediol dimethacrylate (HDDMA), ethoxylated bisphenol A bis-methacrylate (BisEMA), glycerol dimethacrylate (GDMA), trimethylolpropane triacrylate (TMPTA), trimethylolpropane trimethacrylate (TMPTMA), pentaerythritol triacrylate (PETA), propoxylated glycerol triacrylate (GPTA), tris(2-hydroxyethyl) isocyanurate triacrylate (THEICTA), trimethylolpropane triacrylate (DTMPTTA), pentaerythritol tetraacrylate (PETTA), or dipentaerythritol hexaacrylate (DPHA). More preferably, it is a combination of at least two of bisphenol A glycerol dimethacrylate, ethoxylated bisphenol A dimethacrylate, triethylene glycol dimethacrylate, urethane dimethacrylate, 2-hydroxyethyl methacrylate, 1,12-dodecanediol dimethacrylate, ethoxylated bisphenol A bis-methacrylate, glycerol dimethacrylate, trimethylolpropane triacrylate, trimethylolpropane trimethacrylate, pentaerythritol triacrylate, propoxylated glycerol triacrylate, tris(2-hydroxyethyl) isocyanurate triacrylate, trimethylolpropane triacrylate, pentaerythritol tetraacrylate, or dipentaerythritol hexaacrylate.

[0060] Preferably, the oxidant is a peroxide, including organic peroxide and / or inorganic peroxide.

[0061] Preferably, the peroxide includes any one or a combination of at least two of benzoyl peroxide (BPO), dicumyl peroxide (DCP), di-tert-butyl peroxide (DTBP), lauroyl peroxide (LPO), cumene hydroperoxide (CHP), tert-butyl peroxybenzoate (TBPB), or tert-butyl peroxyacetate (TBPA).

[0062] For the dental self-adhesive resin composition provided by the present invention, there are no special requirements for the specific type of filler B, and conventional substances in the art can be selected.

[0063] Preferably, the filler B is any one or a combination of at least two of silica-based fillers, glass-based fillers, or other fillers.

[0064] Preferably, the silica-based filler includes particulate silica and / or fumed silica.

[0065] Preferably, the glass-based filler includes any one or a combination of at least two of barium glass, strontium glass, lanthanum glass, lithium borosilicate glass, or borosilicate glass.

[0066] Preferably, the other filler includes any one or a combination of at least two of zirconia, alumina, ytterbium trifluoride, or titanium dioxide.

[0067] And as a preferred technical solution of the present invention, the above-mentioned filler B can be subjected to silanization treatment, which is more beneficial to improving the mechanical properties of the self-adhesive resin composition.

[0068] Preferably, the catalyst component further includes inhibitor B.

[0069] Preferably, the content of inhibitor B in the catalyst component is 0.01 to 0.5 parts by weight, such as 0.01 part by weight, 0.05 part by weight, 0.1 part by weight, 0.15 part by weight, 0.2 part by weight, 0.25 part by weight, 0.3 part by weight, 0.35 part by weight, 0.4 part by weight, 0.45 part by weight, or 0.5 part by weight, etc.

[0070] Preferably, the inhibitor B includes any one or a combination of at least two of 2,6-di-tert-butyl-p-cresol, p-methoxyphenol, or 2-hydroxy-4-methoxybenzophenone.

[0071] Preferably, the catalyst component further includes other additives.

[0072] Similarly, for the self-adhesive resin composition for dental use provided by the present invention, other additives such as colorants, defoamers, etc. can be added to the catalyst component as needed, in addition to polymerization inhibitors and antioxidants. The present invention has no special requirements for the specific types and dosages of the other additives. Conventional substances in the art can be selected and the dosages can be added as needed.

[0073] Preferably, the colorant can be selected from iron oxide yellow, iron oxide red, zirconium oxide, etc.

[0074] Preferably, the defoamer can be selected from dimethyl silicone oil, modified polysiloxane, etc.

[0075] Preferably, the content of other additives in the catalyst component is 0.1 to 10 parts by weight, such as 0.1 part by weight, 1 part 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, 9 parts by weight or 10 parts by weight, etc.

[0076] In a second aspect, the present invention provides a preparation method of the self-adhesive resin composition for dental use as described in the first aspect. The preparation method includes the preparation of the matrix component and the preparation of the catalyst component;

[0077] The preparation method of the matrix component includes: first mixing a flow regulator, a polymerizable monomer A without an acidic group, a polymerizable monomer with an acidic group, a photoinitiator, a reducing agent, optionally a photo-curing accelerator, optionally a polymerization inhibitor, and optionally other additives, and then adding filler A for mixing to obtain the matrix component;

[0078] The preparation method of the catalyst component includes: first mixing a polymerizable monomer B without an acidic group, an oxidizing agent, optionally a polymerization inhibitor, and optionally other additives, and then adding filler for mixing to obtain the catalyst component.

[0079] The above two are filled separately, and when in use, they are mixed in equal proportions.

[0080] In a third aspect, the present invention provides a dental fixed restoration material, and the dental fixed restoration material includes the self-adhesive resin composition for dental use as described in the first aspect.

[0081] Compared with the prior art, the present invention has the following beneficial effects:

[0082] The self - adhesive resin composition for dental use provided by the present invention comprises a matrix component and a catalyst component. The matrix component includes a polymerizable monomer A without acidic groups, a polymerizable monomer with acidic groups, a photo - initiator, a photo - curing accelerator, a reducing agent, a flow regulator, and filler A. The catalyst component includes a polymerizable monomer B without acidic groups, an oxidizing agent, and filler B. By adding a flow regulator to the matrix component, the resulting self - adhesive resin composition for dental use has a lower viscosity, good fluidity, and thus has a very high wettability on the surface of dental tissues, can fully penetrate into the hard dental tissues, improve the bonding with dentin and enamel, thereby increasing the bonding strength, and at the same time can maintain a relatively high flexural strength, being suitable for dental cementation. Detailed implementation modes

[0083] The technical solutions of the present invention will be further described below through specific implementation modes. Those skilled in the art should understand that the embodiments are only for helping to understand the present invention and should not be regarded as specific limitations to the present invention.

[0084] Unless otherwise specified, the raw materials involved in the following specific implementation modes of the present invention are all conventional materials in the art and can be obtained by purchasing commercially available products. In particular, the information of some of the raw materials involved is as follows:

[0085] (1) Barium glass powder: D 50 The particle size is 0.4 μm.

[0086] Examples 1 - 10 and Comparative Examples 1 - 2

[0087] Examples 1 - 10 and Comparative Examples 1 - 2 respectively provide a self - adhesive resin composition for dental use, both of which contain a matrix component and a catalyst component;

[0088] The various substances and their dosages included in the matrix component and the catalyst component are shown in Table 1 and Table 2. In Table 1 and Table 2, the dosage unit of each substance is "parts by weight";

[0089] Table 1

[0090]

[0091]

[0092] Table 2

[0093]

[0094]

[0095] The preparation methods of the self - adhesive resin compositions for dental use respectively provided by Examples 1 - 10 and Comparative Examples 1 - 2 include the preparation of the matrix component and the preparation of the catalyst component;

[0096] The preparation method of the matrix component includes: first, uniformly mix a flow regulator, a polymerizable monomer without acidic groups, a polymerizable monomer with acidic groups, a photoinitiator, a photo-curing accelerator, a reducing agent, and a polymerization inhibitor, then add barium glass powder, stir at 200 rpm for 10 min, then add fumed silica, stir at 200 rpm for 10 min, and then continuously stir for 120 min to obtain the matrix component;

[0097] The preparation method of the catalyst component includes: first, uniformly mix a polymerizable monomer without acidic groups, an oxidizing agent, and a polymerization inhibitor, then add barium glass powder, stir at 200 rpm for 10 min, then add fumed silica, stir at 200 rpm for 10 min, and then continuously stir for 120 min to obtain the catalyst component;

[0098] The above matrix component and catalyst component are filled separately. During use, mix the two according to a mass ratio of 1:1.

[0099] Performance test:

[0100] (1) Viscosity: Test according to the standard of GB / T 2794-2013; specifically, use a viscometer to test the viscosity of the matrix component. The smaller the viscosity value, the better the fluidity of the obtained dental self-adhesive resin composition.

[0101] (2) Contact angle: Test according to the standard of GB / T 30693-2014; specifically, use a contact angle measuring instrument to test the wetting ability of the dental self-adhesive resin composition on dentin. The test steps are as follows: first, mix the matrix component and the catalyst component according to a mass ratio of 1:1, evenly apply it on the surface of dentin, and when the self-adhesive resin composition spreads on the surface of dentin to reach an equilibrium state, take a photo of the self-adhesive resin composition on the surface of dentin. The smaller the contact angle, the better the wettability of the matrix component and the catalyst component with dentin.

[0102] (3) Shear bond strength: Test according to the standard of YY / T 0518-2009;

[0103] ①Adhesive strength with zirconia, PMMA resin, and titanium metal: Sandblast zirconia (resin / metal) with 50 μm alumina, then ultrasonically clean it in absolute ethanol for 1 min, dry it with anhydrous and oil-free gas for standby. Use a mold to fill the dental self-adhesive resin composition on the zirconia (composite resin / metal) block, cure it with a handheld light-curing lamp (Bluephase) at High gear for 1 min to obtain a sample. Store the sample in water at 37 °C for 24 h, and then use a universal testing machine to test the shear strength of the sample at a test speed of 0.75 mm / min;

[0104] ②Adhesive strength with dentin and enamel: Wet-polish the buccal side of the tooth with a coarse grinding wheel until the enamel (dentin) is slightly exposed. Seal the pulp cavity of the tooth with wax. Then, use a guide resin to complete the embedding of the dentin under natural light. Use a mold to fill the self-adhesive resin composition on the enamel (dentin), cure it with a handheld light-curing lamp (Bluephase) at High gear for 1 min to obtain a sample. Store the sample in water at 37 °C for 24 h, and then use a universal testing machine to test the shear strength of the sample at a test speed of 0.75 mm / min.

[0105] (4) Flexural strength: Test according to the standard of YY / T 1042-2023; the specific test steps are as follows: Fill the sample into a mold with a width of 2 mm × a thickness of 2 mm × a length of 25 mm. Use a dental handheld curing lamp (power: 800 mW / cm 2 ), select the high gear, irradiate three regions (upper, middle, and lower) for 40 s each, then demold. Repeat the above steps to prepare 5 specimens. Then, wet-polish the surface with 2000-mesh sandpaper. Use a tensile testing machine to conduct a three-point bending test under the conditions of a span of 20 mm and a loading speed of 0.75 mm / min, and evaluate with the average value of ten specimens.

[0106] (5) Film thickness: Test according to the standard of YY / T 1042-2023, and the test steps are as follows:

[0107] ①Test the thickness of the glass plate: Measure the thickness (reading A, accuracy: 1 μm) when two optical glass plates are in close contact with a micrometer;

[0108] ②Coat the release agent: If the glass plate needs to be reused, a non-affecting release agent can be coated;

[0109] ③Add the sample to be tested: Remove the upper glass plate, place the lower glass plate on the positioning device, and then place the positioning device at the center of the loading device. Take 0.1 mL of the adhesive sample to be tested and place it at the center of the lower glass slide. Then, place the upper glass plate along the original measurement direction on the sample to be tested (the positioning device can assist in positioning the glass plate);

[0110] ④ Specimen loading: Immediately apply 150 N vertically towards the center of the specimen and hold for 180 s to fully fill the space between the two glass plates with the specimen;

[0111] ⑤ Light curing: Remove the load and irradiate the specimen through the center of the upper glass plate. Cure it by irradiating with a handheld blue light for 20 s;

[0112] ⑥ Measure the overall thickness: After the light irradiation ends, remove the glass plates from the loading device and measure the total thickness of the two glass plates and the specimen film (reading B);

[0113] ⑦ Calculate the thickness of the film: Subtract the thickness A when the two optical glass plates are in close contact from the total thickness B of the two glass plates and the specimen film.

[0114] The self - adhesive resin compositions for dentistry provided in Examples 1 - 10 and Comparative Examples 1 - 2 were tested according to the above - mentioned test method, and the test results are shown in Table 3:

[0115] Table 3

[0116]

[0117]

[0118] It can be seen from the data in Table 3 that:

[0119] Compared with Comparative Examples 1 - 2, after adding a flow regulator to the self - adhesive resin compositions for dentistry provided in Examples 1 - 10, the viscosity of the obtained matrix component is significantly reduced, indicating that the addition of the flow regulator helps to improve the fluidity of the obtained self - adhesive resin composition for dentistry; and the more the content of the flow regulator, the more the viscosity is reduced; by testing the contact angle between the self - adhesive resin composition and the dentin surface, it is found that the contact angle is significantly reduced after adding the flow regulator, indicating that the wettability between the self - adhesive resin composition and the dentin surface is significantly improved; further through the shear bond strength test, the results show that the shear bond strength of the self - adhesive resin composition with zirconia, PMMA, titanium metal, dentin, and enamel is significantly improved after adding the flow regulator.

[0120] In addition, the flexural strength tests were respectively carried out on Examples 1 - 10 and Comparative Examples 1 - 2. The results show that after adding a certain amount of flow regulator, the flexural strength of the obtained self - adhesive resin composition does not increase or decrease significantly, indicating that a certain amount of flow regulator will not reduce the mechanical properties of the self - adhesive resin composition;

[0121] Moreover, the film thicknesses of Examples 1 to 10 and Comparative Examples 1 to 2 were tested respectively. The results showed that the addition of the flow regulator could significantly reduce the film thickness, which was beneficial to improving the fit of the restoration, increasing the contact area between the tooth and the restoration so as to increase the bonding strength, and also avoiding the problem of occlusal elevation caused by adhesive restoration.

[0122] By comparing the data of Example 1 and Examples 4 to 7, it can also be seen that within a certain range, the more the amount of the flow regulator added, the smaller the viscosity of the matrix component of the obtained self-adhesive resin composition, the better the surface wettability, and the higher the bonding strength. However, when the addition amount is too much, its flexural strength will be significantly reduced. Therefore, the addition amount of the flow regulator should not be too little or too much.

[0123] Finally, by comparing the data of Example 1 and Examples 8 to 9, it can be seen that changing the type of the flow regulator will also affect the viscosity of the obtained dental self-adhesive resin composition. Among them, the performance of β-cyclodextrin is better than that of cage-like silsesquioxane, porous starch and calix[4]arene with amino group, and it is the most preferred flow regulator.

[0124] The applicant declares that the present invention illustrates a dental self-adhesive resin composition 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 examples to be implemented. Those skilled in the art should understand that any improvement of the present invention, the equivalent substitution of each raw material of the products of the present invention, the addition of auxiliary components, the selection of specific methods, etc. all fall within the protection scope and the disclosure scope of the present invention.

Claims

1. A self-adhesive resin composition for dental use, characterized in that, The self - adhesive resin composition for dentistry comprises a matrix component and a catalyst component; The matrix component comprises a polymerizable monomer A without acidic groups, a polymerizable monomer with acidic groups, a photoinitiator, a reducing agent, a flow regulator, and filler A; The catalyst component comprises a polymerizable monomer B without acidic groups, an oxidizing agent, and filler B.

2. The self-adhesive resin composition for dentistry according to claim 1, wherein The matrix component comprises the following components by weight parts:

3. The self-adhesive resin composition for dental use according to claim 1 or 2, wherein The flow regulator is a cage - shaped compound with a cavity structure; Preferably, the flow regulator comprises any one or at least two combinations of cyclodextrin - like compounds, cage - type sesquisiloxanes, calixarenes, pillararenes, crown ethers, cucurbiturils, or nanoporous particles, more preferably any one or at least two combinations of cyclodextrin - like compounds, cage - type sesquisiloxanes, or nanoporous particles, and even more preferably a cyclodextrin - like compound; Preferably, the cyclodextrin - like compounds comprise any one or at least two combinations of α - cyclodextrin, β - cyclodextrin, γ - cyclodextrin, hydroxypropyl - β - cyclodextrin, or sulfobutyl - β - cyclodextrin; Preferably, the nanoporous particles comprise nanoporous starch; Preferably, the calixarenes comprise amino - calix[4]arene and / or carboxy - calix[4]arene; Preferably, the pillararenes comprise sulfonated pillararene and / or amino - pillararene.

4. The self-adhesive resin composition for dental use according to any one of claims 1 to 3, characterized in that, The polymerizable monomer A without acidic groups comprises any one or at least two combinations of bisphenol A glycerol dimethacrylate, ethoxylated bisphenol A dimethacrylate, triethylene glycol dimethacrylate, dimethacrylate carbamate, 2 - hydroxyethyl methacrylate, 2 - methyl - acrylic acid - 1,12 - dodecanediol ester, ethoxylated bisphenol A dimethacrylate, glycerol dimethacrylate, trimethylolpropane triacrylate, trimethylolpropane trimethacrylate, pentaerythritol triacrylate, propoxylated glycerol triacrylate, tris(2 - hydroxyethyl) isocyanurate triacrylate, trimethylolpropane triacrylate, pentaerythritol tetraacrylate, or dipentaerythritol hexaacrylate, preferably at least two combinations of bisphenol A glycerol dimethacrylate, ethoxylated bisphenol A dimethacrylate, triethylene glycol dimethacrylate, dimethacrylate carbamate, 2 - hydroxyethyl methacrylate, 2 - methyl - acrylic acid - 1,12 - dodecanediol ester, ethoxylated bisphenol A dimethacrylate, glycerol dimethacrylate, trimethylolpropane triacrylate, trimethylolpropane trimethacrylate, pentaerythritol triacrylate, propoxylated glycerol triacrylate, tris(2 - hydroxyethyl) isocyanurate triacrylate, trimethylolpropane triacrylate, pentaerythritol tetraacrylate, or dipentaerythritol hexaacrylate; Preferably, the polymerizable monomer with acidic groups comprises a phosphate monomer and / or a carboxylate monomer; Preferably, the phosphate monomer comprises any one or at least two combinations of 10 - methacryloyloxydecyl dihydrogen phosphate, 2 - methacryloyloxyethyl phenyl phosphate, pentaerythritol triacrylate phosphate, or glycerol phosphate dimethacrylate; Preferably, the carboxylic acid ester monomer includes any one or a combination of at least two of 4-methacryloyloxyethyl trimellitate, 4-acryloyloxyethyl trimellitate, or 11-methacryloyloxyundecanedioic acid.

5. The self-adhesive resin composition for dental use according to any one of claims 1 to 4, characterized in that, The photoinitiator includes any one or a combination of at least two of camphorquinone, 9,10-phenanthrenequinone, α-diketone, 1-phenylpropane-1,2-dione, 2,2-dimethoxy-2-phenylacetophenone, diphenyl-(2,4,6-trimethylbenzoyl)phosphine oxide, ethyl 2,4,6-trimethylbenzoyl phenylphosphinate, 2,4,6-trimethylbenzoyl-bis(p-tolyl)phosphine oxide, dibenzoyldiethylgermane, tetrabenzoyl germanium, tetra(o-methylbenzoyl)germanium, tetra(acyl)stannane, or triphenylantimony; Preferably, the reducing agent includes an amine compound; Preferably, the amine compound includes any one or a combination of at least two of N,N-dimethyl-p-toluidine, N,N-di(hydroxyethyl)-p-toluidine, N,N-dimethyl-p-toluidine, ethyl 4-dimethylaminobenzoate, or N-acetylthiourea.

6. The self-adhesive resin composition for dental use according to any one of claims 1 to 5, characterized in that, The matrix component further includes a photocuring accelerator; Preferably, the content of the photocuring accelerator in the matrix component is 0.1 to 5 parts by weight; Preferably, the photocuring accelerator includes an aromatic tertiary amine and / or an aliphatic tertiary amine, and more preferably any one or a combination of at least two of dimethylaminoethyl methacrylate, ethyl 4-dimethylaminobenzoate, N,N-dimethylaminoethyl ester, or N,N-diethylaniline; Preferably, the matrix component further includes inhibitor A; Preferably, the content of inhibitor A in the matrix component is 0.01 to 0.5 parts by weight; Preferably, inhibitor A includes any one or a combination of at least two of 2,6-di-tert-butyl-p-cresol, p-methoxyphenol, or 2-hydroxy-4-methoxybenzophenone; Preferably, the matrix component further includes other additives; Preferably, the content of other additives in the matrix component is 0.1 to 10 parts by weight.

7. The self-adhesive resin composition for dental use according to any one of claims 1 to 6, characterized in that, The catalyst component includes the following components by weight: Polymerizable monomer B without acidic groups 20 to 40 parts by weight; Oxidizing agent 0.1 to 5 parts by weight; Filler B 40 to 70 parts by weight; Preferably, the polymerizable monomer B without acidic groups includes any one or a combination of at least two of bisphenol A glycerol dimethacrylate, ethoxylated bisphenol A dimethacrylate, triethylene glycol dimethacrylate, dimethylcarbamate dimethacrylate, 2-hydroxyethyl methacrylate, 2-methyl-acrylic acid-1,12-dodecanediol ester, ethoxylated bisphenol A dimethacrylate, glycerol dimethacrylate, trimethylolpropane triacrylate, trimethylolpropane trimethacrylate, pentaerythritol triacrylate, propoxylated glycerol triacrylate, tris(2-hydroxyethyl)isocyanurate triacrylate, trimethylolpropane triacrylate, pentaerythritol tetraacrylate, (4-ethoxy)pentaerythritol tetraacrylate or dipentaerythritol hexaacrylate, preferably a combination of at least two of bisphenol A glycerol dimethacrylate, ethoxylated bisphenol A dimethacrylate, triethylene glycol dimethacrylate, dimethylcarbamate dimethacrylate, 2-hydroxyethyl methacrylate, 2-methyl-acrylic acid-1,12-dodecanediol ester, ethoxylated bisphenol A dimethacrylate, glycerol dimethacrylate, trimethylolpropane triacrylate, trimethylolpropane trimethacrylate, pentaerythritol triacrylate, propoxylated glycerol triacrylate, tris(2-hydroxyethyl)isocyanurate triacrylate, trimethylolpropane triacrylate, pentaerythritol tetraacrylate, (4-ethoxy)pentaerythritol tetraacrylate or dipentaerythritol hexaacrylate; Preferably, the oxidant is a peroxide; Preferably, the peroxide includes any one or a combination of at least two of benzoyl peroxide, dicumyl peroxide, di-tert-butyl peroxide, dilauroyl peroxide, cumene hydroperoxide, tert-butyl peroxybenzoate or tert-butyl peroxyacetate.

8. The self-adhesive resin composition for dental use according to any one of claims 1 to 7, characterized in that, The catalyst component further includes inhibitor B; Preferably, the content of inhibitor B in the catalyst component is 0.01 to 0.5 parts by weight; Preferably, the inhibitor B includes any one or a combination of at least two of 2,6-di-tert-butyl-p-cresol, p-methoxyphenol or 2-hydroxy-4-methoxybenzophenone; Preferably, the component B further includes other additives; Preferably, the content of other additives in the component B is 0.1 to 10 parts by weight.

9. A method for preparing a self-adhesive resin composition for dental use according to any one of claims 1 to 8, characterized in that, The preparation method includes the preparation of the matrix component and the preparation of the catalyst component: The preparation method of the matrix component includes: first mixing a flow regulator, a polymerizable monomer A without acidic groups, a polymerizable monomer with acidic groups, a photoinitiator, a reducing agent, optionally a photocuring accelerator, optionally an inhibitor and optionally other additives, and then adding filler A for mixing to obtain the matrix component; The preparation method of the catalyst component includes: first mixing a polymerizable monomer B without acidic groups, an oxidant, optionally an inhibitor and optionally other additives, and then adding filler B for mixing to obtain the catalyst component.

10. A dental fixed restoration material, characterized in that, The dental fixed restoration material includes the dental self-adhesive resin composition according to any one of claims 1 to 8.

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