Detailed Description
The invention provides a dental adhesion pretreatment system of cationic polymer-metal complex and a using method thereof, wherein the pretreatment agent is composed of cationic polymer-metal complex solution and is used for treating the surface of a tooth body after acid etching and before coating an adhesive, and the cationic polymer-metal complex and negative charge groups such as carboxyl groups, phosphate groups and the like in a demineralized dentin organic matrix form a complex through electrostatic interaction so as to promote the penetration of the adhesive and provide protection for collagen and provide the dental adhesion pretreatment agent with antibacterial/remineralization performance of an adhesion surface.
The invention provides a dentin adhesive pretreatment agent of a cationic polymer-metal complex, wherein a pretreatment system is a cationic polymer-metal complex solution.
Wherein the solvent can be water, ethanol water solution, and acetone water solution.
In the invention, the concentration of the cationic polymer is 0.0001-500 mg/mL, preferably 0.1-10 mg/mL.
In the adhesion pretreating agent, an accelerator sodium chloride, potassium chloride, sodium fluoride or a mixture thereof can be added as an accelerator, and the concentration of the accelerator is 0.01-100 mg/mL.
The cationic polymer is polyhexamethylene biguanide and its salt, polydiallyldimethylamine and its salt, polyethyleneimine and its salt, polyallylamine and its salt, chitosan and its salt, polylysine and its salt, polyhistidine and its salt, polyarginine and its salt or the mixture of two or more of the above polymers, and the molecular weight is 100-5000000 Da, preferably 500-50000 Da.
The cationic polymer-metal complex is a complex formed by the cationic polymer and one or more of metal ions such as copper, zinc, iron, magnesium, calcium, barium, strontium, silver, lanthanum and the like.
The metal element in the cationic polymer-metal complex is derived from soluble metal salt and metal nanoparticles.
The cationic polymer-metal complex may be formed prior to treatment of the tooth surface or may be formed in situ during treatment.
The cationic polymer-metal complex solution may contain a cationic polymer that is not complexed with a metal ion.
The cationic polymer-metal complex solution may contain metal ions that are not complexed with the cationic polymer.
The pretreatment agent of the present invention is applied to the surface of the tooth after acid etching and before the application of the adhesive.
In the invention, the pretreatment agent can accelerate the action on the surface of the tooth body in a coating mode, so that the treatment is more uniform, the treatment is carried out by water vapor flushing after the treatment, and the treatment time of the pretreatment agent is 3-360 s, preferably 10-30 s; the pretreatment agent can repeatedly treat the tooth surface for a plurality of times, wherein the treatment time is 1 to 10 times, and preferably 1 to 3 times.
In the present invention, the surface of the tooth body after pretreatment and before application of the adhesive can be kept wet or blown dry.
The pretreatment agent and the pretreatment method for the dental bonding based on the cationic polymer-metal complex are suitable for all dental bonding with bonding surfaces containing dentin.
The dental bonding pretreatment system based on the cationic polymer-metal complex can be matched with all dental bonding materials for use.
According to the invention, a cationic polymer-metal complex is formed by a cationic polymer and functional metal ions, and a complex is formed by electrostatic interaction between the cationic polymer and negative charge groups such as carboxyl groups and phosphate groups in an organic matrix of demineralized dentin, so that a gel-like structure formed by strong electronegativity of non-collagen is broken, adverse effects on adhesive permeation in an adhesion process caused by the gel-like structure are reduced, and a formed complex film covers the surface of the demineralized dentin matrix, so that collagen in the dentin matrix is protected, and the resistance of the demineralized dentin matrix to external stimulation is enhanced; the complexed metal ions further endow the interface with antibacterial and remineralization performances and the like, and the dental adhesive pretreatment agent can improve the durability of the dentin adhesive from multiple angles.
The following examples are provided to illustrate the pretreatment for dental adhesion based on cationic polymer-metal complex and the method for using the same according to the present invention, but they should not be construed as limiting the scope of the present invention.
Example 1
After phosphoric acid etching treatment, washing with water vapor, coating pretreating agent PEI-Cu (2mg/ml PEI, Mw 1800Da, 2mmol/L CuCl)2Solution, complex formation) 20s, water vapor rinsed, kept wet, coated with Spectrum adhesive 20s, lightly blown for 5s, light cured lamp illumination for 20s, and then layered with resin on the surface.
Comparative example 1
After phosphoric acid etching treatment, the surface of the tooth body is washed by water vapor and kept wet, a Spectrum adhesive is coated for 20s, light blowing is carried out for 5s, a light curing lamp irradiates for 20s, and then resin is layered and stacked on the surface.
Example 2
Rinsing with water vapor after phosphoric acid etching treatment, coating pretreating agent PEI-Cu (2mg/ml PEI, Mw 1800Da, adding 2mmol/L CuCl)2Solution to form PEI-Cu complex), water vapor rinsing, blow-drying, coating a Spectrum adhesive for 20s, light blowing for 5s, irradiating by a photocuring lamp for 20s, and then layering and stacking resin on the surface.
Comparative example 2
After phosphoric acid etching treatment on the surface of the tooth body, water vapor is washed and dried, a Spectrum adhesive is coated for 20s, light blowing is carried out for 5s, a light curing lamp irradiates for 20s, and then resin is layered and stacked on the surface.
Example 3
Rinsing with water vapor after phosphoric acid etching treatment, coating PEI-Cu (2mg/ml PEI, Mw 1800Da, adding 2mmol/L CuCl) as pretreatment agent2Solution, complex formation) 20s, water vapor rinsing, keeping wet, coating Single bond 2 adhesive 20s, light blowing for 5s, light curing lamp illumination for 20s, and then layering resin on the surface.
Comparative example 3
After phosphoric acid etching treatment, the surface of the tooth body is washed by water vapor and kept wet, a Single bond 2 adhesive is coated for 20s, light blowing is carried out for 5s, a photocuring lamp is used for illuminating for 20s, and then resin is layered and stacked on the surface.
Example 4
Rinsing with water vapor after phosphoric acid etching treatment of tooth surface, coating pretreating agent PEI-Cu (2mg/ml PEI, Mw 1800Da, adding equal volume of 2mmol/L CuCl2Solution to form complex) for 20s, water vapor rinsing, blow-drying, coating Single bond 2 adhesive for 20s, light blowing for 5s, irradiating by a photocuring lamp for 20s, and then layering resin on the surface.
Comparative example 4
After phosphoric acid etching treatment, the surface of the tooth body is washed by water vapor, dried, coated with a Single bond 2 adhesive for 20s, lightly blown for 5s, illuminated by a photocuring lamp for 20s, and then layered and stacked with resin on the surface.
Cutting along the direction perpendicular to the bonding interface of the long axis of the tooth body under the flowing water cooling of a slow cutting instrument to prepare a resin-tooth body strip sample with a bonding surface of 1mm multiplied by 1mm, and carrying out a micro-stretching experiment. The resin-dentin strip samples were randomly divided into 2 equal parts, half of the samples were subjected to a micro-stretching experiment immediately after preparation, and the other half of the samples were immersed in artificial saliva and subjected to a micro-stretching experiment after being aged in a water bath at 37 ℃ for a certain period of time. And (3) carrying out micro-tensile test on each group of resin-tooth body samples by using a micro-tensile tester until the samples break, and recording the load measured by the micro-tensile tester when the samples break. The interfacial width of the sample was measured and the micro tensile strength per unit cross-sectional area of the sample was calculated and the results are shown in table 1.
Example 5
Rinsing with water vapor after dental surface acid etching treatment, coating pretreating agent PEI-Cu (0.0001mg/mL PEI, Mw 1800Da, adding 0.0001mmol/L CuCl2Solution, complex formation), coated for 20s, water vapor rinsed, kept wet, and bond repair was performed.
Example 6
Rinsing with water vapor after dental surface acid etching treatment, coating pretreating agent PEI-Cu (0.0001mg/mL PEI, Mw 1800Da, adding 0.0001mmol/L CuCl2Solution to form a complex), 20s, water vapor rinsing, re-application of the pretreatment agent, keeping wet, and adhesion repair.
Example 7
Rinsing with water vapor after dental surface acid etching treatment, coating pretreating agent PEI-Cu (0.0001mg/mL PEI, Mw 1800Da, adding 0.0001mmol/L CuCl2Solution, complex formation), 20s of coating, water vapor rinsing, repeated application of the pretreatment agent 10 times, keeping wet, and adhesion repair.
Example 8
Rinsing with water vapor after dental surface acid etching treatment, coating pretreating agent PEI-Cu (0.0001mg/mL PEI, Mw 1800Da, adding 0.0001mmol/L CuCl2Solution to form complex), coating for 20s, washing with water vapor, drying, and performing bonding repair.
Example 9
Rinsing with water vapor after dental surface acid etching treatment, coating pretreating agent PEI-Cu (0.0001mg/mL PEI, Mw 1800Da, adding 0.0001mmol/L CuCl2Solution to form complex), coating for 20s, washing with water vapor, coating the pretreating agent again, drying, and performing bonding repair.
Example 10
Rinsing with water vapor after dental surface acid etching treatment, coating pretreating agent PEI-Cu (0.0001mg/mL PEI, Mw 1800Da, adding 0.0001mmol/L CuCl2Solution to form complex), coating for 20s, washing with water vapor, repeatedly coating the pretreating agent for 10 times, drying, and performing bonding repair.
Example 11
Rinsing with water vapor after dental surface acid etching treatment, coating pretreating agent PEI-Cu (200mg/mL PEI, Mw 1800Da, adding 0.0001mmol/L CuCl2Solution, complex formation), coated for 20s, water vapor rinsed, kept wet, and bond repair was performed.
Example 12
Rinsing with water vapor after dental surface acid etching treatment, coating pretreating agent PEI-Cu (200mg/mL PEI, Mw 1800Da, adding 0.0001mmol/L CuCl2Solution, complex formation) for 20s, water vapor rinsing, repeated application of the pretreatment agent for 3 times, keeping wet, and performing adhesion repair.
Example 13
After the surface of the tooth was acid-etched, the tooth was water-vapor washed and coated with a pretreating agent PEI-Cu (200 mg)PEI, Mw 1800Da, add 0.0001mmol/L CuCl2Solution to form complex), coating for 20s, washing with water vapor, drying, and performing bonding repair.
Example 14
Rinsing with water vapor after dental surface acid etching treatment, coating pretreating agent PEI-Cu (200mg/mL PEI, Mw 1800Da, adding 0.0001mmol/L CuCl2Solution to form complex), coating for 20s, washing with water vapor, repeatedly coating the pretreating agent for 10 times, drying, and performing bonding repair.
Example 15
Rinsing with water vapor after dental surface acid etching treatment, coating pretreating agent PEI-Cu (2mg/mL PEI, Mw 1800Da, 1mmol/L CuSO)4Complex formation), coating for 20s, water vapor rinsing, keeping wet, and performing bonding repair.
Example 16
Rinsing with water vapor after the tooth surface is subjected to acid etching treatment, and coating a pretreating agent PEI-Cu (3mmol/L CuSO)4Adding equal volume of 2mmol/L Na3PO4After the metal salt nano particles are formed, mixing the metal salt nano particles with 2mg/mL PEI aqueous solution with the same volume, coating the mixture for 20s, washing the mixture with water vapor, keeping the mixture wet, and performing bonding repair.
Example 17
Rinsing with water vapor after dental surface acid etching treatment, coating pretreating agent PEI-Zn (2mg/mL PEI, Mw 1800Da, adding 1mmol/L ZnCl)2Solution, complex formation), coated for 20s, water vapor rinsed, kept wet, and bond repair was performed.
Example 18
Rinsing with water vapor after dental surface acid etching treatment, coating pretreating agent PEI-Cu-Zn (1mg/mL PEI, Mw 1800Da, adding 0.01mmol/L CuCl20.01mmol/L ZnCl2 solution to form a complex), coating for 20s, rinsing with water vapor, repeatedly coating the pretreating agent 3 times, keeping wet, and performing adhesion repair.
Example 19
Rinsing with water vapor after dental surface acid etching treatment, coating pretreating agent PEI-Zn (2mg/mL PEI, Mw 1800Da, adding 1mmol/L ZnSO)4Solution, complex formation) 20s, water vapor rinse, keep wet, inAnd (5) performing row bonding repair.
Example 20
Rinsing with water vapor after dental surface acid etching treatment, coating pretreating agent PEI-Ag (2mg/mL PEI, Mw 1800Da, adding 1mmol/L AgNO)3Solution, complex formation), coated for 20s, water vapor rinsed, kept wet, and bond repair was performed.
Example 21
After the surface of the tooth is subjected to acid etching treatment, the tooth is washed by water vapor and coated with a pretreating agent PEI-Ag (1mmol/L AgNO)3The solution was added dropwise to 1mmol/L NaCl solution until an equal volume was added, 2mg/mL PEI, Mw 1800Da, complex formation), coated for 20s, rinsed with water vapor, kept wet, and the bond was repaired.
Example 22
Rinsing with water vapor after dental surface acid etching treatment, coating pretreating agent PEI-Mg (1Mg/mL PEI, Mw 1800Da, adding 1mmol/L MgCl2Complex formation), 20s coating, water vapor rinsing, keeping wet,
example 23
Rinsing with water vapor after dental surface acid etching treatment, coating pretreating agent PEI-Fe (1mg/mL PEI, Mw 1800Da, adding 1mmol/L FeCl2Complex formation) for 20s, washing with water vapor, and maintaining the wet state for bonding repair.
Example 24
Rinsing with water vapor after dental surface acid etching treatment, coating with PEI-Cu (1mg/mL PEI, Mw 1800Da, 1mg/mL PEI, Mw 600 Da) as pretreatment agent, adding 1mmol/L CuCl2Solution, complex formation), coating for 30s, water vapor rinsing, keeping wet, and performing adhesion repair.
Example 25
After the dental surface had been pickled, it was water vapor rinsed, coated with PEI-Cu (1mg/mL PEI, Mw 1800 Da; 1mg/mL polyhexamethylene biguanide hydrochloride, Mw 2500 Da) and 1mmol/L CuCl2Solution, complex formation), coating for 30s, water vapor rinsing, keeping wet, and performing adhesion repair.
Example 26
After the surface of the tooth is acid etched, the tooth is washed by water vapor and is coated with PEI-Cu (1mg/mL PEI, Mw 1800 Da; 1mg/mL polyhexamethylene bis (hexamethylene-bis))Guanidine hydrochloride, Mw 2500Da, 1mmol/L CuCl was added2Solution, 1mmol/L ZnCl2Solution formed complex), coated for 30s, water vapor rinsed, kept wet, and bond repair was performed.
Example 27
After the dental surface is acid etched, the tooth surface is rinsed with water vapor and coated with PEI-Sr (1mg/mL PEI, Mw 1800Da, 1mmol/L SrCl is added2Solution, complex formation), coated for 30s, rinsed with water vapor to keep wet, and the bond was repaired.
Example 28
Rinsing with water vapor after dental surface acid etching treatment, coating pretreating agent polyhexamethylene biguanide hydrochloride-Cu (5mg/mL PHMB, Mw 2500Da, adding 1mmol/L CuF2Complex formation), coating for 20s, water vapor rinsing, keeping wet, and performing bonding repair.
Example 29
After the surface of the tooth is subjected to acid etching treatment, the tooth is subjected to water vapor washing, a pretreatment agent polyhexamethylene biguanide villiaumite-Cu (5mg/mL PHMB, Mw 2500Da, 1mmol/L CuCl is added to form a complex), the tooth is coated for 20s, and the tooth is subjected to water vapor washing, kept wet and bonded and repaired.
Example 30
Rinsing with water vapor after the tooth surface is acid-etched, coating a pretreating agent poly (diallyldimethylammonium chloride-Cu) (1mg/mL PDDA, Mw 200,000-350,000Da, adding 0.001mmol/L CuCl2Complex formation), coating for 20s, water vapor rinsing, keeping wet, and performing bonding repair.
Example 31
Rinsing with water after dental surface acid etching treatment, coating pretreatment agent poly (allylamine) -Cu (2mg/mL PAA water solution, Mw 17000Da, adding 0.001mmol/L CuCl2Complex formation), coating for 20s, water vapor rinsing, keeping wet, and performing bonding repair.
Example 32
Rinsing with water vapor after the tooth surface is subjected to acid etching treatment, coating with chitosan-Cu (chitosan content of 1mg/mL (deacetylation degree of 80-90%)), adding 0.1mmol/L CuCl2Solution, complex formation), coated for 20s, water vapor rinsed, kept wet, and bond repair was performed.
Example 33
Rinsing with water vapor after dental surface acid etching treatment, coating polylysine-Cu (1mg/mL polylysine aqueous solution, adding 0.1mmol/L CuCl2Solution, complex formation), coated for 20s, water vapor rinsed, kept wet, and bond repair was performed.
Example 34
Rinsing with water vapor after the surface of the tooth is subjected to acid etching treatment, coating a pretreatment agent poly-L-arginine hydrochloride-Cu-Zn (1mg/mL poly-L-arginine hydrochloride aqueous solution, Mw 3-7 ten thousand Da), and adding 0.1mmol/L CuSO4Solution, 0.2mmol/L ZnCl2Complex formation) for 20s, washing with water vapor, keeping wet, and performing bonding repair.
The results of the micro-tensile test after Spectrum bonding were carried out for examples 16, 17, 20, 28, 32 and are shown in Table 2.
TABLE 1
TABLE 2
The foregoing is only a preferred embodiment of the present invention, and it should be noted that, for those skilled in the art, various modifications and decorations can be made without departing from the principle of the present invention, and these modifications and decorations should also be regarded as the protection scope of the present invention.