CN101239024B - Nano silver fluorine-containing self-acid pickling single bottle dental adhesive - Google Patents
Nano silver fluorine-containing self-acid pickling single bottle dental adhesive Download PDFInfo
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- CN101239024B CN101239024B CN2008100505246A CN200810050524A CN101239024B CN 101239024 B CN101239024 B CN 101239024B CN 2008100505246 A CN2008100505246 A CN 2008100505246A CN 200810050524 A CN200810050524 A CN 200810050524A CN 101239024 B CN101239024 B CN 101239024B
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Abstract
The invention relates to a nanometer silver fluorinated self-etching single bottle dentistry adhesive, belonging to the technical field of dentistry material. The component and the percentage of total weight is: 3.7 to 4.5 percent of initiator, 0.02 to 3.13 percent of additive, 0 to 2.0 percent of nanometer silver antimicrobial, 0 to 60 percent of methyl methacrylate monomer, 20 to 85.3 percent of acidity monomer and 0 to 53.3 percent of solvent. The acidity monomer comprises a phosphoric acid monomer or/and a carbonic acid monomer; the solvent is 0 to 4 kinds of materials selected from ethanol, propanol, normal butanol, acetone, methyl ethyl ketone, ethyl acetate and water. The nanometer silver of the invention can resist multiple bacterial and the nanometer biological ceramic powder canreduce regeneration caries; the single bottle self-etching function simplifies the using procedure; the mixture of multiple solvents with different permittivity can remarkably reduce the self hydrolysis of the acidity monomer and increase the chemical stability.
Description
Technical field
The invention belongs to the technical field of dental materials, particularly a kind of single bottle of multi-functional bonding agent.
Background technology
Organic resin class bonding agent the repairing of dental materials, repair, reproduce and just abnormal in be used widely.Product from multistep operation, simple function, is transformed into simple operations, multi-functional.So far the world developed the 7th generation bonding agent.With early stage the 4th generation bonding agent compare, with technical qualitative leap arranged all in theory.The 4th generation bonding agent adopt full acid etching and wet method adhesive technology, service routine comprises acid etching, priming paint, bonding, is generally finished by many vial formulations.During its operating cost, adhesive effect is subjected to operator's individual skill and empirical the influence.In the 5th generation product, priming paint and bonding agent merge into one, but still keep the acid etching step, still need flushing behind the acid etching and dry up, and the degree that needs control to dry up, both can not overdrying, and can not there be too many water to remain in dentin or enamel surface again.
In recent years, higher level is pushed dental adhesive in the appearance of All-in-One bonding agent again, and its method is that etching agent, priming paint and bonding agent are mixed, and once finishes dentin or adamantine bonding.Here it is from one step of acid etching All-in-One bonding agent.This bonding agent is formed by two bottles, be called the 6th generation bonding agent.The latest generation bonding agent is formed by single bottle, be called the 7th generation bonding agent.Single bottle of same component is given and is produced and application brings great convenience, but poor chemical stability, this mainly since acrylate and phosphate ester hydrolysis in sour environment cause.How preventing or delay hydrolysis, is the subject matter that the All-in-One bonding agent need solve.
The product of All-in-One is most at present adopts following several ways to reduce hydrolysis.First kind of way is to improve pH value.Generally speaking, pH value is higher than 2, and hydrolysis will obviously weaken, but can cause the acid etching effect to reduce.Second kind of way is to adopt the not amide-type monomer of facile hydrolysis, but its free crowd speed is lower, and the combination property of material is poor than polyacrylate.The third way is the novel monomeric of synthetic hydrolysis, as the phosphoric acid ester monomer.
Another problem of All-in-One bonding agent is that adhesive strength descends relatively, compares with full acid etch technique, and Dentinal pollution layer fails to remove fully, so resin monomer can not infiltrate gutta-percha fibril net preferably, and hybrid layer (also claiming mixed layer) is thinner.And because of its acidity a little less than, can not acid etching to adamantine profound, it is bonding to be difficult to form more physical mechanical. above factors cause the adhesive strength of All-in-One agent to be lower than full acid etching system.But, greatly reduce various mistakes because of technical operation or clinical experience generation because its operation sequence is simple.And might improve little seepage, its reason is that pollution layer is not removed fully, still has the certain protection effect.
Another developing direction of dental adhesive is a multifunction, comprising the introducing of antibiotic preparation.Often with dental tissue certain clearance is arranged behind the present widely used compoite resin adhesive, this gap mainly is because shrinkage stress that produces during unsuitable bonding, monomer polymerization or heat and mechanical stress cause.Consequent tiny leakage can cause the dental caries of regenerating, and therefore, has the composite resin of antibacterial action and bonding agent that the growth that suppresses antibacterial is had very important significance.Confirm that now some organic antibacterial agents have good bacteriostasis as glucose chlorhexidine, chlorohaxanpyridine acetate, and be applied to obtain clinical checking in the dental materials.But such antibacterial is using the initial stage effect better, and its effect obviously weakens after a period of time, can not continue the long time.Such antibacterial belongs to releasable material in addition, together plays bactericidal action by diffusion and oral fluid.Such antibacterial is many to be used in the methyl acrylic ester monomer, and it can influence the mechanical property of material.Silver joins silver in the adhesive bandage as the effective existing very long history of antibacterial, at US 6,605, and 751 and US 6,897,349 existing examples.Silver also is used for synthetism or sticking bone preparation, (US 4,849,22).Be used for medical apparatus and instruments, silver can deposit to the titania powder surface with ionic means, (US 4,906, and 466 and US 5,413,788) stablized silver ion, (US 4,849 to have strengthened silver-colored bactericidal activity again, 223), US 7,011, and 839 have reported sulfadiazine silver can be used for handling and burn.Silver is not applied in the dental materials as yet as antibacterial.
Summary of the invention
The technical problem to be solved in the present invention is, select acid monomer, low-k solvent and use nanometer silver and biological ceramic powder to make additive, make single bottle of multi-functional dental adhesive, with the shortcoming that poor chemical stability, the adhesive strength that overcomes prior art All-in-One bonding agent descends relatively, the antibiotic persistent period is short.
Nano silver fluorine-containing self-acid pickling single bottle dental adhesive of the present invention, component and the percentage ratio that accounts for gross weight are: initiator 3.7～4.5%, additive 0.02～3.13%, nano silver antimicrobials 0～2.0%, methyl acrylic ester monomer 0～60%, acid monomer 20～85.3%, solvent 0～53.3%; Described initiator is camphorquinone, 4-dimethyl amine ethyl benzoate, 2,4, in 6-(trimethyl benzoyl) diphenyl phosphate oxidation a kind; Described additive comprises radical polymerization inhibitor, surfactant, UV absorbers, fluorine releasing agent; Described acid monomer comprises phosphorus acid monomer or/and carbonate monomer; Described solvent is 0～4 kind in ethanol, propanol, n-butyl alcohol, acetone, butanone, ethyl acetate, the water.
Acid monomer of the present invention is to contain to have acid corrosion action and the polymeric monomer of energy, comprises phosphorus acid monomer, carbonate monomer and sulphuric acid monomer.Acid monomer mainly is made up of three parts: acid function base (A), acrylate-based (L) and at interval basic (R);
An-(R)-Lm
The acid function base can dissociate hydrion, has acid corrosion action; The acrylate-based polyreaction that is used for forms macromolecular scaffold; Base provides different performances at interval, comprises hydrophilic or hydrophobicity, molecule chain flexibility and the mobility etc. of molecule.
In a molecule, can contain a plurality of A and L, but general as many as 5 to 6, and the acid function base generally is made up of carbonic acid, phosphoric acid or sulphuric acid.Because acid etching is effective, it is more extensive that phosphate group uses.Phosphate group can provide two can dissociated hydrion, can form chelate structure preferably with calcium ion, thereby improve adhesive strength.Phosphorus acid monomer comprises: biphosphate 5-(methyl) acryloxy pentyl ester, the own ester of biphosphate 6-(methyl) acryloxy, biphosphate 7-(methyl) acryloxy heptyl ester, biphosphate 8-(methyl) acryloxy monooctyl ester, biphosphate 9-(methyl) acryloxy ester in the ninth of the ten Heavenly Stems, biphosphate 10-(methyl) acryloxy ester in the last of the ten Heavenly stems, biphosphate 11-(methyl) acryloxy pentyl ester, biphosphate 12-(methyl) acryloxy ten diester, biphosphate 4-[(methyl) acryloyl-oxy methyl] the cyclohexyl methyl ester, biphosphate 2-[is right-{ 2-(methacryloxy) ethyoxyl } phenoxy group] and ethyl ester or 2-[be right-{ 2-(methacryloxy) ethyoxyl } phenoxy group] the ethanol dihydrogen phosphate, biphosphate 3-[is right-{ 3-(methacryloxy) propoxyl group } phenoxy group] and propyl ester or 3-[be right-{ 3-(methacryloxy) propoxyl group } phenoxy group] the propanol dihydrogen phosphate, biphosphate 4-[is right-{ 4-(methacryloxy) butoxy } phenoxy group] and butyl ester or 4-[be right-{ 4-(methacryloxy) butoxy } phenoxy group] the butanols dihydrogen phosphate, phenol-2-methacryloxy ethanol phosphate ester or phosphoric acid (phenol-2-methacryloxy ethanol ester, di(2-ethylhexyl)phosphate (acryloyl-oxy ethyl glycol) ester, di(2-ethylhexyl)phosphate (2-acryloxy propylene glycol) ester, dioxygen-2,1,3 glycerol 2-methyl phosphorodithioate.The effective carbonate monomer of acid etching is an acrylic acid.
Now commercial phosphorus acid monomer response speed is slower, and polymerisation conversion is lower, and the poly-effect of the resistance of oxygen is obvious.For improving rate of polymerization, conversion ratio and material property, the present invention adopts methyl acrylic ester monomer and acid monomer and usefulness, and the methyl acrylic ester monomer of selecting for use all is that prior art is employed.The methyl acrylic ester monomer comprises following A, B, C, D four class monomers.
The category-A monomer is the monomer of a kind of low-molecular-weight list or difunctional, is used as viscosity modifier or reactive diluent; The category-B monomer is generally the bifunctional monomer who contains aromatic group or urethano, makes the polymer body after the polymerization have mechanical property preferably; C class monomer is multi-functional monomer, also claim cross-linking agent, have 3～6 polymerisable functional groups, comprise methacrylic acid or esters of acrylic acid, this class monomer is very important to forming three-dimensional macromolecular structure, can obviously have influence on the degree of polymerization, modulus, elasticity and the toughness of goods, significant to the mechanical property of dental materials; D class monomer is a kind of low-molecular-weight polymer, i.e. oligomer, and its effect is many-sided, comprises the toughness that increases product material, improves impact resistance, reduces the material polymerization shrinkage, changes the hydrophilic or hydrophobicity of material etc.Such monomeric shortcoming is that viscosity is big, and polymerization speed is slow.
Be applicable to that category-A monomer of the present invention comprises: methacrylic acid beta-hydroxy ethyl ester, acrylic acid four Hydrogen bran esters, methacrylic acid 3-hydroxy propyl ester, the triethylene-glycol dimethylacrylate, the tetraethylene-glycol dimethylacrylate, the diglycol dimethylacrylate, ethylene glycol dimethacrylate, 1,10-decanediol dimethylacrylate, 1,12-dodecanol dimethylacrylate, 1.4-butanediol dimethylacrylate, the propylene glycol dimethylacrylate, the dipropylene glycol dimethylacrylate, the tripropylene glycol dimethylacrylate, the three four propylene glycol dimethylacrylates that contract, 1, the 6-hexanediol dimethacrylate, the tetradecanol methacrylate, ten (gathering) ethyoxyl hydroxyl ethanol methacrylate, ten (gathering) of methacrylic acid ethoxy ethyl ester 1,6-cyclohexanedimethanol methacrylate, neopentylglycol dimethacrylate, two (gathering) propoxyl group neopentylglycol dimethacrylate.
Be applicable to that category-B monomer organic monomer of the present invention comprises: bisphenol-A 2-glycidyl double methyl methacrylate, γ-methacryloxypropyl trimethoxy silane, 4-methacryloxyethyl trimellitic anhydride, bisphenol a dimethacrylate, methacrylic acid benzoyl (base) ethyl ester, two-2-methylacryoyloxyethyl-2,2,4-trimethyl cyclohexane (base) diurethane (UDMA), two-2-methylacryoyloxyethyl 2,4 (or 2,6)-toluene diurethanes, di(2-ethylhexyl)phosphate (2-acryloxy propylene glycol) ester (BisGMA-P), di(2-ethylhexyl)phosphate (acryloyl-oxy ethyl glycol) ester (BisMEP), methacrylic acid two (gathering) ethyoxyl (is changed) Hydroxyalkyl base ethyl ester, four (gathering) ethyoxyl (change) nonyl phenol methacrylate, two (gathering) ethyoxyl (change) nonyl phenol methacrylate, isobornyl methacrylate, isodecyl methacrylate, first is admired acrylic acid dodecane alcohol ester, 2-Propenoic acid, 2-methyl-, octyl ester, methacrylic acid two (gathering) propoxyl group (change) allyl ester, the octadecanol methacrylate, ten (gathering) ethyoxyl (change) bisphenol a dimethacrylate, 30 (gathering) ethyoxyl (change) bisphenol a dimethacrylate, eight (gathering) ethyoxyl (change) bisphenol a dimethacrylate, four (gathering) ethyoxyl (change) bisphenol a dimethacrylate, three (gathering) ethyoxyl (change) bisphenol a dimethacrylate.
Be applicable to that C class monomer organic monomer of the present invention comprises: trimethylol-propane trimethacrylate, three (gathering) ethyoxyl trimethylol-propane trimethacrylate, the blue methacrylate of 15 (gathering) ethyoxyl trimethylolpropane, six (gathering) ethyoxyl trimethylol-propane trimethacrylate, nine (gathering) ethyoxyl trimethylol-propane trimethacrylate, nine (gathering) propoxyl group trimethylol-propane trimethacrylate, new penta triol trimethyl acrylic ester, three (gathering) propoxyl group glycerol trimethyl acrylic ester, three (gathering) propoxyl group trimethylol-propane trimethacrylate, trimethylol-propane trimethacrylate, three (2-ethoxy) isocyanuric acid ester trimethyl acrylic ester, two seasons penta 4 ferment pentamethyl acrylate, four (gathering) ethyoxyl tetramethylolmethane tetramethyl acrylate.
Be applicable to that D class monomer organic monomer of the present invention comprises: the poly-the third two ferment methacrylates of polyethylene glycol dimethacrylate, 20 (gathering) ethoxylated bisphenol A dimethylacrylate, polypropylene glycol dimethacrylate, methoxy polyethylene glycol methacrylate-styrene polymer, methoxyl group, ethyoxyl polypropylene glycol methacrylate.
The monomer of facile hydrolysis substitutes widely used common phosphorus acid monomer at present though can use not, carbonate monomer, and the sulphuric acid monomer comprises on this class monomer overall performance that acid etching effect, polymerization speed are all not really desirable.The monomer of the not facile hydrolysis that research is synthetic new is not only consuming time, and cost is high, and therefore, seeking the new way that delays the bonding agent hydrolysis has become one of research focus of a step bonding agent.
The hydrolysis of esters in sour environment not only is subjected to the influence of this body structure of molecule, also is subjected to the influence of external factor.Solvent is one of main external factor that influences hydrolysis.Discover that hydrolysis rate and polarity of solvent are closely related, generally speaking, the polarity of solvent height, hydrolysis is fast.Below simple example the influence of solvent polarity just can be described.
The hydrolysis rate (with acid catalysis is example) of table 1 phosphate ester in several dicyandiamide solutions
| Solvent | Water | Acetone | Ethanol/water | Dioxane/water |
| Hydrolysis rate (mole/second) | 0.36 | 0.33 | 0.17 | 0.16 |
Usually, polarity of solvent can characterize by dielectric constant, and dielectric constant is high more, and polarity of solvent is strong more, and example has gone out the dielectric constant of common solvent in the table 2.
The dielectric constant of table 2 common solvent
| Solvent | Dielectric constant | Solvent | Dielectric constant | Solvent | Dielectric constant |
| Water | 80 | Acetone | 20.7 | Ethane | 2.02 |
| Methanol | 33 | Oxolane | 7.52 | Benzene | 2.28 |
| Ethanol | 24.3 | Butanone | 18.5 | Anaesthetie Ether | 4.34 |
| Propanol | 20.1 | Ethyl acetate | 6.02 | Dichloromethane | 9.08 |
| N-butyl alcohol | 17.8 | Methanamide | 109 | Tetrachloromethane | 2.24 |
| Acetic acid | 6.15 | The dimethyl propylene amide | 38.3 |
The present invention proposes a kind of method that suppresses or slow down hydrolysis rate with mixed solvent.Here should consider the dissolubility of solvent, boiling point, polarity also will be considered the convenience used, the safety of storage, and toxicity and to the adverse effect of polyreaction, as make free radical chain transfer etc.
The present invention has following requirement to solvent: (1) has good dissolubility to monomer, and dissolves each other with water; (2) boiling point is not less than 35 ℃; (3) low polarity; (4) nontoxic.
Single solvent is difficult to satisfy above-mentioned requirements, needs 2 kinds or multiple solvent.
In solvent preferred alcohol of the present invention, propanol, n-butyl alcohol, acetone, butanone, ethyl acetate, the water 0～4 kind is preferably 2～3 kinds.
Additive radical polymerization inhibitor of the present invention, surfactant, UV absorbers, fluorine releasing agent are identical with the additive of common dental materials.The fluorine releasing agent can select fluorine-based silicate biological ceramic powder, and its component is CaO-SiO
2-Al
2O
5-P
2O
5-F, particle size distribution can be at 20～100nm, 40～80nm preferably, consumption accounts for 0～2.5% of bonding agent gross weight.Fluorine-based silicate biological ceramic powder can reduce the regeneration of tooth dental caries.
Antibacterial nanometer silver of the present invention can be resisted many antibacterials.The particle size distribution of nanometer silver can be at 1nm～40nm, 10nm～20nm preferably, and consumption accounts for 0～2% of bonding agent gross weight, and preferred 0.5～1%.
In the bonding agent of the present invention, pH value should not be lower than 1.8.
The preparation of nano silver fluorine-containing self-acid pickling single bottle dental adhesive of the present invention is fluorine-based silicate biological ceramic powder to be carried out silanization handle, and more all components is mixed by weight proportion, forms homogeneous mixture.
Bonding agent of the present invention can form hard membrane material under different radiation conditions, these radiation comprise visible light photograph, laser light photograph, ultraviolet illumination, microwave radiation and electron radiation etc.
Process for photocuring is simple, quick, sclerosis or extent of polymerization height.Light trigger comprises camphorquinone, hydroxy-cyclohexyl acetophenone, two hexyloxy acetophenones, two (2,4,6-trimethyl benzoyl) phenyl phosphorous oxide, 2,4,6-(trimethyl benzoyl) diphenyl phosphate oxidation, 2,4,5, the 7-tetraiodo-3 hydroxyl-10 cyano group-6-fluorone, 2,4,5, the 7-tetraiodo-3 hydroxyls-6-fluorone etc.For some initiator systems, also need and the tertiary amine coupling, as: 4-dimethyl amine ethyl benzoate etc.
Of the present invention single bottle from the multi-functional dental adhesive of acid etching, preparation method is simple, service routine is simplified, operating technology requires low.Use mixed solvent,, reach the effect that suppresses hydrolysis by reconciling and control the dielectric constant of solvent.Theory and practice all confirms, uses the solvent of low polarity, low-k, and hydrolysis rate is descended.The present invention comprises dissolubility, boiling point and dielectric constant with all multifactor taking into account, in the hope of optimized dicyandiamide solution.Obviously reduce self hydrolysis of acid monomer, increased chemical stability.
High-efficiency sustained-release type antibacterial is introduced in the dental materials.Such antibacterial comprises the ionic inorganic oxide of argentiferous such as pottery or silica gel, has stronger antibacterial action.Be expected to solve release type antibacterial life-span weak point, or processing and the hot problems such as cracking that cause.
The specific embodiment
Provide component of the present invention in following examples and account for the percentage ratio of gross weight.
The initiator system that is adopted in following examples, monomer and solvent are labeled as respectively:
Initiator is camphorquinone, 4-dimethyl amine ethyl benzoate, 2,4, a kind of in 6-(trimethyl benzoyl) diphenyl phosphate oxidation.
In the methyl acrylic ester monomer,
Monomer a is a methacrylic acid beta-hydroxy ethyl ester; Monomer b is a dipentaerythritol pentamethyl acrylate; Monomer c is a polyethylene glycol dimethacrylate 200; Monomer d is a polyethylene glycol dimethacrylate 400; Monomer e is a polyethylene glycol dimethacrylate 600; Monomer f is a bisphenol-A 2-glycidyl double methyl methacrylate; Monomer g is two-2-methylacryoyloxyethyl-2,2,4-trimethyl cyclohexane diurethane (UDMA).
In the acid monomer,
Monomer h is biphosphate 5-(methyl) acryloxy pentyl ester; Monomer i is biphosphate 8-(methyl) acryloxy monooctyl ester; Monomer j is biphosphate 12-(methyl) acryloxy ten diester; Monomer k is di(2-ethylhexyl)phosphate (acryloyl-oxy ethyl glycol) ester; Monomer l is di(2-ethylhexyl)phosphate (2-acryloxy propylene glycol) ester; Monomer m be biphosphate 2-[right-{ 2-(methacryloxy) ethyoxyl } phenoxy group] ethyl ester;
Monomer n is a carbonate monomer: acrylic acid.
In the solvent,
Solvent a is an ethanol; Solvent b is a propanol; Solvent c is an acetone; Solvent d is a butanone; Solvent e is an ethyl acetate; Solvent f is n-butyl alcohol, water.
In the additive,
Additive a is a radical polymerization inhibitor; Additive b is a surfactant; Additive c is a UV absorbers; Additive e is fluorine releasing agent-fluorine-based silicate biological ceramic powder.
Antibacterial is a nano silver antimicrobials.
Embodiment 1
Initiator 3.86%;
Additive b 0.50%; Additive c 0.95%; Additive a 0.03%;
Monomer j 45.00%; Monomer a 2.26%; Monomer d 10.00%; Monomer b 5.00%;
Solvent a 20.40%;
Surplus is a water.
Embodiment 2
Initiator 3.86%;
Additive b 0.50%; Additive c 0.95%; Additive a 0.03%;
Monomer j 45.00%; Monomer a 2.26%; Monomer d 10.00%; Monomer b 5.00%;
Solvent a 20.40%; Solvent d 12.00%.
Embodiment 3
Initiator 3.86%;
Additive b 0.50%; Additive c 0.95%; Additive a 0.03%;
Monomer i 45.00%; Monomer d 7.26%; Monomer b 10.00%;
Solvent c 30.40%;
Surplus is a water.
Embodiment 4
Initiator 3.86%;
Additive b 0.50%; Additive c 0.95%; Additive a 0.03%;
Monomer i 45.00%; Monomer a 2.26%; Monomer d 10.00%; Monomer b 5.00%;
Solvent a 16.20%; Solvent e 16.20%.
Embodiment 5
Initiator 3.86%;
Nanometer silver 0.50%;
Additive a 0.03%; Additive e 2.00%; Additive c 0.95%;
Monomer h 43.00%; Monomer a 2.26%; Monomer d 10.00%; Monomer b 5.00%;
Solvent e 20.40%;
Surplus is a water.
Embodiment 6
Initiator 4.00%;
Nanometer silver 0.01%;
Additive b 0.50%; Additive e 1.00%; Additive c 1.00%;
Monomer h 30.00%; Monomer a 15.00%; Monomer e 10.00%; Monomer b 10.00%;
Solvent a 20.00%;
Surplus is a water.
Embodiment 7
Initiator 4.00%;
Nanometer silver 2.00%;
Additive b 0.50%; Additive a 0.03%; Additive e 1.00%;
Monomer h 30.00%; Monomer a 10.00%; Monomer c 15.00%; Monomer b 5.00%;
Solvent a 15.00%; Solvent c 15.00%;
Surplus is a water.
Embodiment 8
Initiator 4.48%;
Additive a 0.03%; Additive b 0.60%; Additive c 1.00%;
Monomer k 53.72%; Monomer a 2.70%; Monomer d 11.94%; Monomer b 6.00%;
Solvent e 15.00%;
Surplus is a water.
Embodiment 9
Initiator 4.48%;
Nanometer silver 0.50%;
Additive a 0.03%; Additive b 0.60%; Additive c 1.00%;
Monomer j 53.72%; Monomer a 2.70%; Monomer d 11.94%; Monomer b 6.00%;
Surplus is a water.
Embodiment 10
Initiator 4.48%;
Nanometer silver 1.00%;
Additive a 0.03%; Additive c 0.60%; Additive e 2.50%;
Monomer h 25.00%; Monomer n 20.00%; Monomer a 10.00%; Monomer f 10.00%;
Solvent b 12.00%; Solvent c 10.00%;
Surplus is a water.
Embodiment 11
Initiator 4.48%;
Nanometer silver 0.50%;
Additive a 0.03%; Additive c 1.00%; Additive e 2.00%;
Monomer a 10.00%; Monomer b 15.00%; Monomer f 10.00%; Monomer n 20.00%;
Solvent b 30.00%;
Surplus is a water.
Embodiment 12
Initiator 4.48%;
Nanometer silver 0.50%;
Additive a 0.03%; Additive c 1.00%; Additive e 2.00%;
Monomer a 10.00%; Monomer b 10.00%; Monomer g 10.00%; Monomer h 20.00%;
Solvent b 20.00%;
Surplus is a water.
Embodiment 13
Initiator 4.48%;
Nanometer silver 0.50%;
Additive a 0.03%; Additive c 1.00%; Additive e 2.00%;
Monomer a 10.00%; Monomer b 5.00%; Monomer f 30.00%; Monomer h 20.00%;
Solvent a 10.00%; Solvent d 10.00%;
Surplus is a water.
Embodiment 14
Initiator 3.86%;
Nanometer silver 0.50%;
Additive a 0.03%; Additive c 1.00%; Additive e 0.50%;
Monomer l 65.27%; Monomer b 10.00%;
Solvent a 5.00%; Solvent d 5.00%;
Surplus is a water.
Embodiment 15
Initiator 3.86%;
Nanometer silver 0.50%;
Additive a 0.03%; Additive c 1.00%; Additive e 0.50%;
Monomer m 70.27%; Monomer b 5.00%;
Solvent a 5.00%; Solvent b 5.00%; Solvent e 2.84%;
Surplus is a water.
Embodiment 16
Initiator 3.86%;
Nanometer silver 0.50%;
Additive a 0.03%; Additive c 1.00%; Additive e 0.50%;
Monomer l 75.27%; Monomer b 10.00%;
Solvent a 5.00%;
Surplus is a water.
Embodiment 17
Initiator 3.86%;
Nanometer silver 0.50%;
Additive a 0.03%; Additive c 1.00%; Additive e 0.50%;
Monomer m 85.27%;
Solvent a 5.00%;
Surplus is a water.
Embodiment 18
Initiator 3.76%;
Nanometer silver 0.50%;
Additive a 0.03%; Additive c 1.00%; Additive e 1.00%;
Monomer a 3.26%; Monomer b 13.00%; Monomer c 13.00%; Monomer h 46.00%;
Solvent a 9.00%; Solvent b 9.45%.
Embodiment 19
Initiator 3.76%;
Nanometer silver 0.50%;
Additive a 0.03%; Additive c 1.00%; Additive e 1.00%;
Monomer a 4.26%; Monomer b 15.00%; Monomer c 15.00%; Monomer h 51.00%;
Solvent a 4.00%; Solvent b 4.45%.
Embodiment 20
Initiator 3.76%;
Nanometer silver 0.50%;
Additive a 0.03%; Additive c 1.00%; Additive e 1.00%;
Monomer a 3.71%; Monomer b 17.00%; Monomer c 17.00%; Monomer j 50.00%;
Solvent a 6.00%.
Embodiment 21
Initiator 3.76%;
Nanometer silver 0.50%;
Additive a 0.03%; Additive c 1.00%; Additive e 0.50%;
Monomer a 3.26%; Monomer b 14.00%; Monomer c 18.00%; Monomer j 20.00%; Monomer m 20.00%;
Solvent a 5.00%; Solvent f 5.00%;
Surplus is a water.
Embodiment 22
Initiator 3.76%;
Nanometer silver 0.50%;
Additive a 0.03%; Additive c 1.00%; Additive e 0.50%;
Monomer a 20.00%; Monomer h 26.26%; Monomer f 20.00%;
Solvent a 10.00%; Solvent d 10.00%;
Surplus is a water.
Embodiment 23
Initiator 3.76%;
Nanometer silver 0.50%;
Additive a 0.03%; Additive c 1.00%; Additive e 0.50%;
Monomer a 20.00%; Monomer h 26.26%; Monomer f 20.00%;
Solvent b 10.00%; Solvent e 10.00%;
Surplus is a water.
Embodiment 24
Initiator 3.76%;
Nanometer silver 0.50%;
Additive a 0.03%; Additive c 1.00%; Additive e 0.50%;
Monomer a 14.00%; Monomer b 8.00%; Monomer e 8.00%; Monomer f 16.00%; Monomer g 10.21%; Monomer h 38.00%.
Embodiment 25
Initiator 3.76%;
Nanometer silver 0.50%;
Additive a 0.03%; Additive c 1.00%; Additive e 0.50%;
Monomer a 10.00%; Monomer b 5.00%; Monomer e 5.00%; Monomer f 10.00%; Monomer g 7.21%; Monomer h 27.00%;
Solvent a 30.00%
Embodiment 26
Initiator 3.70%;
Nanometer silver 0.50%;
Additive a 0.03%; Additive c 1.00%; Additive e 0.50%;
Monomer a 10.00%; Monomer f 10.00%; Monomer h 5.00%; Monomer n 16.00%;
Solvent e 25.00%; Solvent d 25.00%;
Surplus is a water.
Embodiment 27
Initiator 3.76%;
Nanometer silver 0.50%;
Additive a 0.03%; Additive c 1.00%; Additive e 0.50%;
Monomer f 20.00%; Monomer h 5.00%; Monomer n 16.00%;
Solvent e 25.00%; Solvent d 25.00%;
Surplus is a water.
The product that part embodiment is obtained detects, and gained the results are shown in table 3.
Table 3 performance
| Embodiment | Cell toxicity test | Salmonella reversion test | Sensitization test (STT) | Film thickness (μ m) | Enamel adhesive shear strength (MPa) | Dentin adhesive shear strength (MPa) |
| 2 | 0 grade of toxicity | Mutation sample feminine gender | 0 grade of anaphylaxis | 7 | 35 | 26 |
| 4 | 0 grade of toxicity | Mutation sample feminine gender | 0 grade of anaphylaxis | 6 | 31 | 24 |
| Embodiment | Cell toxicity test | Salmonella reversion test | Sensitization test (STT) | Film thickness (μ m) | Enamel adhesive shear strength (MPa) | Dentin adhesive shear strength (MPa) |
| 12 | 0 grade of toxicity | Mutation sample feminine gender | 0 grade of anaphylaxis | 11 | 33 | 27 |
| 6 | 0 grade of toxicity | Mutation sample feminine gender | 0 grade of anaphylaxis | 9 | 32 | 25 |
| 15 | 0 grade of toxicity | Mutation sample feminine gender | 0 grade of anaphylaxis | 8 | 31 | 23 |
| 21 | 0 grade of toxicity | Mutation sample feminine gender | 0 grade of anaphylaxis | 10 | 39 | 24 |
| 9 | 0 grade of toxicity | Mutation sample feminine gender | 0 grade of anaphylaxis | 7 | 36 | 21 |
| 18 | 0 grade of toxicity | Mutation sample feminine gender | 0 grade of anaphylaxis | 8 | 32 | 22 |
Claims (3)
1. nano silver fluorine-containing self-acid pickling single bottle dental adhesive, component and the percentage ratio that accounts for gross weight are: initiator 3.7～4.5%, additive 0.02～3.13%, nano silver antimicrobials 0～2.0%, methyl acrylic ester monomer 0～60%, acid monomer 20～85.3%, solvent 0～53.3%; Described initiator is camphorquinone, 4-dimethyl amine ethyl benzoate, 2,4, in 6-(trimethyl benzoyl) diphenyl phosphate oxidation a kind; Described additive comprises radical polymerization inhibitor, surfactant, UV absorbers, fluorine releasing agent; Described acid monomer is that phosphorus acid monomer is or/and carbonate monomer, phosphorus acid monomer comprises: biphosphate 5-(methyl) acryloxy pentyl ester, the own ester of biphosphate 6-(methyl) acryloxy, biphosphate 7-(methyl) acryloxy heptyl ester, biphosphate 8-(methyl) acryloxy monooctyl ester, biphosphate 9-(methyl) acryloxy ester in the ninth of the ten Heavenly Stems, biphosphate 10-(methyl) acryloxy ester in the last of the ten Heavenly stems, biphosphate 11-(methyl) acryloxy pentyl ester, biphosphate 12-(methyl) acryloxy ten diester, biphosphate 4-[(methyl) acryloyl-oxy methyl] the cyclohexyl methyl ester, biphosphate 2-[is right-{ 2-(methacryloxy) ethyoxyl } phenoxy group] and ethyl ester, biphosphate 3-[is right-{ 3-(methacryloxy) propoxyl group } phenoxy group] and propyl ester, biphosphate 4-[is right-{ 4-(methacryloxy) butoxy } phenoxy group] and butyl ester, phenol-2-methacryloxy ethanol phosphate ester, di(2-ethylhexyl)phosphate (acryloyl-oxy ethyl glycol) ester or di(2-ethylhexyl)phosphate (2-acryloxy propylene glycol) ester, carbonate monomer is an acrylic acid; Described solvent is 0～4 kind in ethanol, propanol, n-butyl alcohol, acetone, butanone, ethyl acetate, the water.
2. according to the described nano silver fluorine-containing self-acid pickling single bottle dental adhesive of claim 1, it is characterized in that, described phosphorus acid monomer is or/and carbonate monomer, comprise biphosphate 5-(methyl) acryloxy pentyl ester, biphosphate 8-(methyl) acryloxy monooctyl ester, biphosphate 12-(methyl) acryloxy ten diester, di(2-ethylhexyl)phosphate (acryloyl-oxy ethyl glycol) ester, di(2-ethylhexyl)phosphate (2-acryloxy propylene glycol) ester, biphosphate 2-[right-{ 2-(methacryloxy) ethyoxyl } phenoxy group] ethyl ester, acrylic acid.
3. according to claim 1 or 2 described nano silver fluorine-containing self-acid pickling single bottle dental adhesives, it is characterized in that, described nanometer silver, particle size distribution is at 1nm～40nm, and consumption accounts for 0.5～1% of bonding agent gross weight.
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| CN101239024B true CN101239024B (en) | 2010-06-23 |
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| JP6888760B2 (en) * | 2016-03-24 | 2021-06-16 | エスディーアイ リミテッド | Dental adhesive composition |
| CN106860027A (en) * | 2016-12-29 | 2017-06-20 | 广州凯耀资产管理有限公司 | A kind of tooth filling material of sterilizing and its production and use |
| CN112494339B (en) * | 2020-11-02 | 2021-08-20 | 浙江大学 | Dental bonding pretreatment composition based on in-situ deposition of nano silver particles and application |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4046732A (en) * | 1975-01-09 | 1977-09-06 | Infante Samuel J | Dispersant for the application of dental ceramic |
| US4909887A (en) * | 1986-11-06 | 1990-03-20 | Gdf Gesellschaft Fur Dentale Forschung Und Innovationen Gmbh | Dental adhesive compound |
| CN1234733A (en) * | 1997-01-18 | 1999-11-10 | 赫罗伊斯库尔泽公司 | Dental adhesive |
| CN1270016A (en) * | 1999-03-03 | 2000-10-18 | 可乐丽股份有限公司 | Dental bottom |
| CN1977787A (en) * | 2005-11-30 | 2007-06-13 | 中国科学院兰州化学物理研究所 | Dental antibacterial false tooth base material |
| CN101119700A (en) * | 2005-02-15 | 2008-02-06 | 株式会社德山 | Dental mucosal adjustment material |
-
2008
- 2008-03-20 CN CN2008100505246A patent/CN101239024B/en active Active
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4046732A (en) * | 1975-01-09 | 1977-09-06 | Infante Samuel J | Dispersant for the application of dental ceramic |
| US4909887A (en) * | 1986-11-06 | 1990-03-20 | Gdf Gesellschaft Fur Dentale Forschung Und Innovationen Gmbh | Dental adhesive compound |
| CN1234733A (en) * | 1997-01-18 | 1999-11-10 | 赫罗伊斯库尔泽公司 | Dental adhesive |
| CN1270016A (en) * | 1999-03-03 | 2000-10-18 | 可乐丽股份有限公司 | Dental bottom |
| CN101119700A (en) * | 2005-02-15 | 2008-02-06 | 株式会社德山 | Dental mucosal adjustment material |
| CN1977787A (en) * | 2005-11-30 | 2007-06-13 | 中国科学院兰州化学物理研究所 | Dental antibacterial false tooth base material |
Non-Patent Citations (4)
| Title |
|---|
| 朱洪水，胡晓萍，郭菁.氟化聚甲基丙烯酸甲酯体外释氟率的测定.口腔颌面修复学杂志7 4.2006,7(4),第282-283页. |
| 朱洪水,胡晓萍,郭菁.氟化聚甲基丙烯酸甲酯体外释氟率的测定.口腔颌面修复学杂志7 4.2006,7(4),第282-283页. * |
| 陈扬熙摘.正畸用氟素缓释性抗龋粘接剂.国外医学口腔医学分册18 5.1991,18(5),第313页. |
| 陈扬熙摘.正畸用氟素缓释性抗龋粘接剂.国外医学口腔医学分册18 5.1991,18(5),第313页. * |
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