CN117883290A

CN117883290A - Low-oxygen polymerization-inhibition adhesive for dentistry

Info

Publication number: CN117883290A
Application number: CN202410062644.7A
Authority: CN
Inventors: 孟祥树; 金光奎; 王刚
Original assignee: Shandong Huge Dental Material Co ltd
Current assignee: Shandong Huge Dental Material Co ltd
Priority date: 2024-01-16
Filing date: 2024-01-16
Publication date: 2024-04-16

Abstract

The invention relates to the technical field of dental restoration materials, in particular to a low-oxygen polymerization-inhibition dental adhesive. The low-oxygen polymerization-inhibition dental adhesive comprises the following components in percentage by weight: 20-90 wt% of matrix resin; 0-15 wt% of filler; 1 to 5 weight percent of tertiary amine compound; the matrix resin comprises a polymerizable resin monomer, a photopolymerization initiator and a photopolymerization promoter; the polymerizable resin monomer is a polymerizable acrylate monomer; the total content of the photopolymerization initiator and the photopolymerization promoter is less than 10wt%. The low-oxygen polymerization inhibition dental adhesive provided by the invention has high adhesive strength, good adhesive durability and low-oxygen polymerization inhibition effect, is suitable for pretreatment of dental restoration adhesive surfaces of enamel, dentin and various materials, and completes various direct restoration operations and indirect restoration operations in the oral restoration process.

Description

Low-oxygen polymerization-inhibition adhesive for dentistry

Technical Field

The invention relates to the technical field of dental restoration materials, in particular to a low-oxygen polymerization-inhibition dental adhesive.

Background

The polymer is a high molecular compound formed by connecting a large number of monomer molecules through chemical bonds, and when the polymer is subjected to polymerization reaction in the presence of oxygen, the oxygen can react with active intermediates in the polymer, so that an oxygen polymerization inhibition effect is initiated. The oxygen inhibition effect refers to a phenomenon in which the polymerization rate of a polymer is slowed or stopped by the influence of oxygen under certain conditions. Particularly in free radical polymerization, the oxygen inhibition effect is prevalent. The polymerization inhibition of oxygen molecules is mainly reflected in the following two aspects: (1) Quenching the excited state photoinitiator to prevent the generation of active free radicals; (2) Combines with the active free radical to form the peroxy free radical without addition activity.

Currently, most common adhesives contain photoinitiators, and most initiating systems are free radical reactions. Meanwhile, most of the photo-curing process is performed in an air environment, so that oxygen molecules have a non-negligible polymerization inhibition effect on radical polymerization. The photo-or chemical-cured dental composite resin, after polymerization, forms a soft, viscous surface layer, commonly referred to as an oxygen barrier layer. The thickness of the oxygen inhibition layer is increased to reduce the bonding strength between the lamination of the composite resin, and meanwhile, the excessively thick oxygen inhibition layer of the adhesive can cause the phenomenon of slipping during the filling of the composite resin, which is unfavorable for the direct repairing operation of the resin. The above drawbacks are to be overcome by those skilled in the art.

Disclosure of Invention

The present invention has been made to overcome the above-mentioned drawbacks of the prior art, and an object of the present invention is to provide a low oxygen polymerization inhibiting dental adhesive having the advantages of high adhesive strength and high adhesive durability.

In order to solve the technical problems, the invention adopts the following technical scheme:

The low-oxygen polymerization-inhibition dental adhesive comprises the following components in percentage by weight:

20-90 wt% of matrix resin;

0-15 wt% of filler;

1 to 5 weight percent of tertiary amine compound;

The matrix resin comprises a polymerizable resin monomer, a photopolymerization initiator and a photopolymerization promoter; the polymerizable resin monomer is a polymerizable acrylate monomer; the total content of the photopolymerization initiator and the photopolymerization promoter is less than 10wt%.

Further, the polymerizable acrylate monomer is any one or more of hydrophilic acrylic resin, hydrophobic acrylic resin and acidic acrylic resin.

Further, the photopolymerization initiator is any one or more of alpha-diketones, ketals, thioxanthones, (di) acyl phosphine oxides, benzoin alkyl ethers, benzildimethyl ketals, coumarins, diaryliodonium hexafluorophosphates, triarylsulfonium hexafluorophosphates, triarylselenonium hexafluorophosphates, camphorquinone, and 2,4, 6-trimethylbenzoyl-diphenyl phosphine oxide (TPO);

The photopolymerization promoter is any one or more of mixture of 4-dimethylaminoethyl benzoate, N-dimethylaminoethyl ester and dimethylaminoethyl methacrylate.

Further, the matrix resin further comprises a polymerization inhibitor; the content of the polymerization inhibitor is less than 2wt%.

Preferably, the polymerization inhibitor is any one or a mixture of 2, 6-di-tert-butyl-p-cresol and p-hydroxyanisole.

Further, the filler is an inorganic filler or an organic filler or a mixture of an inorganic filler and an organic filler.

Preferably, the filler has an average particle diameter of 0.001 m to 1. Mu.m.

Further, the tertiary amine compound is any one of triethanolamine, triethylamine, triethanolamine phosphate, N-methyldiethanolamine, dodecylamine, hexadecylamine, octadecylamine, dioctadecylamine, N, N dimethylaniline, N, N diethylaniline, N, N dimethyl-p-toluidine, N, N dihydroxyethyl-p-toluidine, N-methyl-N hydroxyethyl-p-toluidine, N, N, N ', N ' -tetramethyl ethylenediamine, N, N dimethylethanolamine, N, N ' -dimethylpiperazine, N, N, N ', N ' -tetramethyl urea.

Further, the adhesive also comprises a solvent for diluting the adhesive and improving the system stability of the adhesive; the content of the solvent is 5-60 wt%.

Preferably, the solvent is any one or more of ethanol, isopropanol, acetone, methanol, n-butanol, cyclohexane, methylcyclohexane, dichloromethane, trichloroethylene, trichloromethane, methyl acetate, ethyl acetate, propyl acetate, isopropyl acetate, diethylene glycol monobutyl ether, butyl acetate, methyl ethyl ketone, cyclohexanone, turpentine, tetrahydrofuran and deionized water.

Compared with the prior art, the invention has the following beneficial effects:

according to the low-oxygen polymerization inhibition adhesive for dentistry, tertiary amine compounds are added into a system, and the tertiary amine compounds serve as active hydrogen donors, so that the tertiary amine compounds can rapidly react with peroxy free radicals, consume peroxy free radicals without addition activity and release alkoxy free radicals and hydroxyl free radicals; the released alkoxy free radical and hydroxyl free radical can also initiate the polymerization reaction of the polymerizable acrylate monomer in the dental adhesive, thereby improving the polymerization rate, promoting the curing of the dental adhesive and effectively reducing the thickness of the oxygen inhibition layer. The low-oxygen polymerization-inhibition dental adhesive has high adhesive strength, good adhesive durability and thinner oxygen polymerization-inhibition layer thickness, is favorable for avoiding the problem of slipping in the resin filling process, is suitable for pretreatment of adhesive surfaces of dental restorations of enamel, dentin and various materials, and completes various direct repair operations and indirect repair operations in the oral restoration process.

Detailed Description

For the purpose of making the objects, technical solutions and advantages of the embodiments of the present invention more apparent, the technical solutions in the embodiments of the present invention will be clearly and completely described below, and it is apparent that the described embodiments are some embodiments of the present invention, but not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.

The invention relates to a low-oxygen polymerization inhibition dental adhesive, which comprises the following components: matrix resin, filler, tertiary amine compound and solvent. The dental adhesive has high adhesive strength, high adhesive durability and low oxygen polymerization inhibition effect, and can be used for pretreatment of dental restoration adhesive surfaces of enamel, dentin and various materials, and various direct restoration operations and indirect restoration operations in the oral restoration process are completed.

The content of the matrix resin accounts for 20-90 wt% of the whole system; by way of example, the content of the matrix resin may be, but is not limited to, 20wt%, 30wt%, 35wt%, 40wt%, 45wt%, 50wt%, 55wt%, 60wt%, 65wt%, 70wt%, 80wt%, 90wt%. The matrix resin comprises polymerizable resin monomer, photopolymerization initiator, photopolymerization promoter and polymerization inhibitor.

The polymerizable resin monomer is a polymerizable acrylate monomer; the polymerizable acrylate monomer can be polymerized under the action of a photopolymerization initiator and a photopolymerization promoter. The polymerizable acrylate monomer is any one or more of hydrophilic acrylic resin, hydrophobic acrylic resin and acidic acrylic resin. Hydrophilic acrylic resins include, but are not limited to, the following resins: hydroxyethyl methacrylate (HEMA), hydroxypropyl methacrylate (HPMA), glycerol Dimethacrylate (GDMA), monoglyceride methacrylate (GMMA), 2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate, 2-hydroxybutyl acrylate, 2-hydroxy-3-phenoxypropyl acrylate, 4-hydroxybutyl acrylate or propylene glycol mono-methacrylate.

Hydrophobic acrylic resins include, but are not limited to, the following resins: dimethacrylate polyurethane (UDMA), di-urethane di (meth) acrylate (DUDMA), bisphenol A-dimethacrylate polyoxyethylene Ether (EBPADMA), bisphenol A-dimethacrylate glycidyl (Bis-GMA), triethylene glycol dimethacrylate (TEGDMA), methyl methacrylate, ethyl methacrylate, propyl methacrylate, butyl methacrylate, hexyl methacrylate, cyclohexyl methacrylate, ethoxydiglycol methacrylate, methoxytriethylene glycol methacrylate, phenoxyethyl methacrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl methacrylate, 2-hydroxybutyl methacrylate, 2-hydroxy-3-phenoxypropyl methacrylate, 4-hydroxybutyl methacrylate, 1, 4-cyclohexanedimethanol monomethacrylate, methyl acrylate, ethyl acrylate, propyl acrylate, butyl acrylate, hexyl acrylate, cyclohexyl acrylate, ethoxydiglycol acrylate, methoxytriethylene glycol acrylate, phenoxyethyl acrylate, 1, 4-butanediol di (meth) acrylate dodecanediol, di (meth) acrylate, 1, 6-hexanediol methacrylate, trimethylolpropane (meth) acrylate, trimethylolpropane (TMA), trimethylolpropane (meth) acrylate (TMA), trimethylolpropane (TMA), pentaerythritol di (meth) acrylate or pentaerythritol tri (meth) acrylate.

Acidic acrylic resins include, but are not limited to, the following resins: 10-methacryloyloxydecyl phosphate (10-MDP), alkyl acrylic acid phosphate, glycerol dimethacrylate phosphate (Bis-GDMAP), 2-hydroxyethyl methacrylate phosphate, di (methacryloyloxyethyl) phosphate, ethylene glycol methacrylate phosphate, methacryloyloxyethyl trimellitic anhydride, 4- [2- [ (meth) acryloyloxy ] ethoxycarbonyl ] phthalic acid, acrylic acid-itaconic acid copolymer, mercaptomethyl methacrylate, 5- (meth) acryloyloxypentyl-3-phosphonopropionate or ethylene glycol di (3-mercaptopropionate) and trimethylolpropane tri (3-mercaptopropionate).

The total content of photopolymerization initiator and photopolymerization accelerator is less than 10wt%; preferably, the total content of the photopolymerization initiator and the photopolymerization accelerator accounts for 2-6wt% of the whole system. As an example, the total content of the photopolymerization initiator and the photopolymerization accelerator may be, but is not limited to 0.5wt1wt1.5wt2wt2.5wt3wt3.5wt4wt4.5wt5wt5.5wt6wt6.5wt7wt7.5wt8wt8.5wt9wt9.5wt10wt.

The photopolymerization initiator initiates the polymerizable acrylate monomer to perform polymerization reaction by absorbing light energy; the photopolymerization initiator can control the setting time and hardening degree of the dental adhesive, thereby ensuring good fluidity and adaptability of the dental adhesive during the bonding process. The photopolymerization initiator is any one or more of alpha-diketone, ketal, thioxanthone, (bi) acyl phosphine oxide, benzoin alkyl ether, benzil dimethyl ketal, coumarin, diaryl iodonium hexafluorophosphate, triarylsulfonium hexafluorophosphate, triarylselenonium hexafluorophosphate, camphorquinone and 2,4, 6-trimethyl benzoyl-diphenyl phosphine oxide (TPO); preferably, the photopolymerization initiator is camphorquinone. The photopolymerization accelerator is used for assisting the photopolymerization initiator and enhancing the light energy absorption capacity of the photopolymerization initiator, so that the polymerization rate and the polymerization efficiency of the polymerizable acrylate monomer are improved. The photopolymerization promoter is any one or more of 4-dimethylaminoethyl benzoate, N-dimethylaminoethyl ester and dimethylaminoethyl methacrylate.

The content of polymerization inhibitor is less than 2wt%; by way of example, the content of the polymerization inhibitor may be, but is not limited to, 0wt%, 0.2wt%, 0.4wt%, 0.6wt%, 0.8wt%, 1wt%, 1.2wt%, 1.4wt%, 1.6wt%, 1.8wt%, 2wt%. The polymerization inhibitor is any one or a mixture of 2, 6-di-tert-butyl-p-cresol and p-hydroxyanisole. The polymerization inhibitor is used to control the polymerization rate of the polymerizable acrylate monomer, preventing the photopolymerization initiator from initiating the polymerization too quickly, so that when the dental adhesive is cured using light, it is ensured that a doctor has enough time to adapt and shape the dental adhesive.

The content of the filler accounts for 0 to 15 weight percent of the whole system; preferably, the filler content is 1wt% to 8wt% of the whole system. By way of example, the filler content may be, but is not limited to, 0wt%, 1wt%, 2wt%, 3wt%, 4wt%, 5wt%, 6wt%, 7wt%, 8wt%, 9wt%, 10wt%, 11wt%, 12wt%, 13wt%, 14wt%, 15wt%. The filler in the dental adhesive is used for improving the operability of the material and enhancing the mechanical strength and the adhesiveness of the dental adhesive after being cured.

Specifically, the filler may be any one of an inorganic filler, an organic filler, and a mixture of an inorganic filler and an organic filler. The average particle diameter of the filler is 0.001-1 mu m; preferably, the filler has an average particle diameter of 0.001 m to 0.1. Mu.m. As an example, the average particle size of the filler may be, but is not limited to 0.001m0.003m0.005m0.007m0.009m0.01m0.03m0.05m0.07m0.09m0.1m0.2m0.4m0.6m0.8m1m.

The inorganic filler has higher hardness, strength and durability, can provide good optical performance and color stability, and is not easy to be influenced by external environment to change color or fade. The inorganic filler may be a silica-based filler, a glass-based filler or other commonly used dental inorganic fillers. Wherein the silica filler is selected from amorphous silica micropowder, spherical silica micropowder, kaolin and other minerals with silica as base materials; commercial ultrafine particulate silica, having a primary particle diameter of 0.001 m to 0.1 m, such as OX50, A200, A380, R974, R972, R711, R709, H30, H20, T30, T40, similar sized particulate silica, fumed silica, and the like. The glass filler is selected from barium glass, lanthanum glass, strontium glass, sodium glass, lithium borosilicate glass, zinc glass, fluoroaluminosilicate glass, borosilicate glass and bioglass. Other common dental inorganic fillers are selected from zirconia, hydroxyapatite, alumina, titania, sodium fluoride, potassium fluoride, strontium fluoride, trifluoride, iron oxide, and the like. The organic filler has better processability and fluidity and is used for filling small defects or weak adhesion tooth parts. The mixture of the inorganic filler and the organic filler is prepared by compounding the inorganic filler and the organic filler according to a certain proportion, and has the characteristics of the inorganic filler and the organic filler. Preferably, the filler is a silanized fumed silica; the silanized fumed silica can enhance the mechanical properties and durability of the dental adhesive and improve compatibility.

The content of the tertiary amine compound accounts for 1 to 5 weight percent of the whole system; as an example, the content of the tertiary amine compound may be, but is not limited to 1wt1.2wt1.4wt1.6wt1.8wt2wt2.2wt2.4wt2.6wt2.8wt3wt3.2wt3.4wt3.6wt3.8wt4wt4.2wt4.4wt4.6wt4.8wt5wt.

The tertiary amine compound can effectively reduce the oxygen polymerization inhibition layer and avoid the slipping problem in the resin filling process. The main principle is as follows: the tertiary amine compound can be used as an active hydrogen donor, and can quickly react with peroxy free radicals generated in the polymerization process to regenerate the active free radicals. Specifically, tertiary amine compounds react with peroxy radicals, and the peroxy radicals take hydrogen to generate alkyl hydroperoxide; alkyl hydroperoxides can still further generate alkoxy radicals and hydroxyl radicals. The specific reaction is as follows:

ROO+R'CH₂NR₂ROOH+R'CHNR₂ROOH

ROOHRO+OH

The reaction of the tertiary amine compound and the peroxy radical can consume the peroxy radical, and the released alkoxy radical and hydroxyl radical can initiate the polymerization reaction of the polymerizable acrylate monomer in the dental adhesive, so that the polymerization rate is improved and the curing of the dental adhesive is promoted. Therefore, the tertiary amine compound can be used as a co-initiator in the dental adhesive to promote the curing of the dental adhesive, and effectively reduce the thickness of the oxygen inhibition layer.

The tertiary amine compound is any one of triethanolamine, triethylamine, triethanolamine phosphate, N-methyldiethanolamine, dodecylamine, hexadecylamine, octadecylamine, dioctadecylamine, N, N dimethylaniline, N, N diethylaniline, N, N dimethyl p-toluidine, N, N dihydroxyethyl p-toluidine, N-methyl-N hydroxyethyl p-toluidine, N, N, N ', N ' -tetramethyl ethylenediamine, N, N dimethylethanolamine, N, N ' -dimethylpiperazine, N, N, N ', N ' -tetramethyl urea.

The content of the solvent accounts for 5 to 60 weight percent of the whole system; preferably, the solvent content is 5wt% to 15wt% of the whole system. As an example, the solvent content may be, but is not limited to, 5wt6wt7wt8wt9wt10wt11wt12wt13wt14wt15wt20wt25wt30wt35wt40wt45wt50wt55wt60wt. solvents for diluting the adhesive, improving the stability of the dental adhesive system and improving the permeability of the dental adhesive during use. The solvent is any one or more of ethanol, isopropanol, acetone, methanol, n-butanol, cyclohexane, methylcyclohexane, dichloromethane, trichloroethylene, trichloromethane, methyl acetate, ethyl acetate, propyl acetate, isopropyl acetate, diethylene glycol monobutyl ether, butyl acetate, methyl ethyl ketone, cyclohexanone, turpentine, tetrahydrofuran and deionized water.

For better illustrating the objects, technical solutions and advantageous effects of the present invention, the present invention will be further described with reference to examples. It should be noted that the following implementation of the method is a further explanation of the present invention and should not be taken as limiting the present invention.

Example 1

The embodiment provides a low-oxygen polymerization inhibition adhesive for dentistry, which comprises the following raw materials in parts by weight: 10 parts of trimethylolpropane trimethacrylate, 5 parts of glycerol dimethacrylate, 16 parts of bisphenol A-glycidyl dimethacrylate, 25 parts of hydroxyethyl methacrylate, 10 parts of 10-methacryloyloxydecyl phosphate, 0.1 part of camphorquinone, 0.3 part of 4-dimethylaminoethyl benzoate, 0.05 part of 2, 6-di-tert-butyl-p-cresol, 0.05 part of p-hydroxyanisole, 3.5 parts of fumed silica, 30 parts of absolute ethyl alcohol and 2 parts of triethanolamine;

Weighing the raw materials according to the parts by weight; the components such as resin, auxiliary agent, filler, solvent and the like are respectively stirred, and the components are uniformly mixed to obtain the low-oxygen polymerization-inhibition dental adhesive.

Example 2

The embodiment provides a low-oxygen polymerization inhibition adhesive for dentistry, which comprises the following raw materials in parts by weight: 10 parts of trimethylolpropane trimethacrylate, 5 parts of glycerol dimethacrylate, 16 parts of bisphenol A-glycidyl dimethacrylate, 25 parts of hydroxyethyl methacrylate, 10 parts of 10-methacryloyloxydecyl phosphate, 0.1 part of camphorquinone, 0.3 part of 4-dimethylaminoethyl benzoate, 0.05 part of 2, 6-di-tert-butyl-p-cresol, 0.05 part of p-hydroxyanisole, 3.5 parts of fumed silica, 30 parts of absolute ethyl alcohol and 2 parts of triethylamine;

Comparative example

The comparative example provides an adhesive, which comprises the following raw materials in parts by weight: 10 parts of trimethylolpropane trimethacrylate, 5 parts of glycerol dimethacrylate, 16 parts of bisphenol A-glycidyl dimethacrylate, 25 parts of hydroxyethyl methacrylate, 10 parts of 10-methacryloyloxydecyl phosphate, 0.1 part of camphorquinone, 0.3 part of 4-dimethylaminobenzoic acid ethyl ester, 0.05 part of 2, 6-di-tert-butyl-p-cresol, 0.05 part of p-hydroxyanisole, 3.5 parts of fumed silica and 30 parts of absolute ethyl alcohol;

weighing the raw materials according to the parts by weight; and respectively stirring the components such as the resin, the auxiliary agent, the filler, the solvent and the like, and uniformly mixing the components to obtain the adhesive.

In summary, the compositions and amounts of the low oxygen polymerization-inhibiting dental adhesives prepared in examples 1 to 2 and the adhesives prepared in comparative examples are shown in Table 1 below;

Table 1: component meter

	Comparative example	Example 1	Example 2
				10-MDP	10	10	10
HEMA	25	25	25
				GDMA	5	5	5
Bis-GMA	16	16	16
				TMPTMA	10	10	10
CQ	0.5	0.5	0.5
				EDB	1	1	1
BHT	0.05	0.05	0.05
				MEHQ	0.05	0.05	0.05
R974	2.4	2.4	2.4
				Absolute ethyl alcohol	30	30	30
P1		2
				P2			2

Note that chinese names corresponding to shorthand symbols used in table 1 are as follows:

< polymerizable acrylic resin >

10-MDP: 10-Methacryloyloxy decyl phosphate

HEMA: hydroxyethyl methacrylate

Bis-GMA: bisphenol A-glycidyl dimethacrylate

TMPTMA: trimethylolpropane tri (meth) acrylate

GDMA: glycerol dimethacrylate

< Inorganic filler >

R974: fumed silica

< Curing initiation System >

CQ: camphorquinone (photopolymerization initiator)

EDB: 4-Dimethylaminobenzoic acid ethyl ester (photopolymerization promoter)

< Tertiary amine >

P1: triethanolamine salt

P2: triethylamine

< Others >

BHT:2, 6-Di-tert-butyl-p-cresol (polymerization inhibitor)

MEHQ: para hydroxy anisole (polymerization inhibitor)

Product performance test

1. The bonding strength and the bonding durability are important indexes for evaluating the mechanical property of the bonding system, and the higher bonding strength and bonding durability can provide a basis for good bonding effect. The adhesive for dental use obtained in examples 1 to 2 and the adhesive obtained in comparative example were tested for adhesive strength (enamel adhesive strength and dentin adhesive strength), adhesive durability (enamel adhesive strength and dentin adhesive strength) and uncured layer thickness (i.e., oxygen-inhibited layer) using YY 1042-2011, YY T0519-2009 and YY 0622-2008 dental resin-based pit sealer, respectively, as reference standards. The test results are shown in table 2 below.

TABLE 2 test results of bond Strength, bond durability and uncured layer thickness Table

As can be seen from Table 2, the thicknesses of the uncured layers of the low oxygen polymerization-inhibiting dental adhesives prepared in examples 1 and 2 were all smaller than those of the uncured layers of the adhesives prepared in comparative examples under the same conditions; meanwhile, the bonding strength and bonding durability meet the standard requirements without obvious reduction. Therefore, the above test shows that the addition of the tertiary amine compound can reduce the thickness of the uncured layer, effectively improve the curing effect of the dental adhesive, and further obtain an ideal repairing effect in clinical adhesive repairing filling.

2. The dental adhesive having low oxygen inhibition obtained in example 1 was taken and the uncured layer thicknesses of the three were compared with two commercially available similar products (commercially available product 1 and commercially available product 2). The test results are shown in table 3 below.

TABLE 3 test results of bond Strength, bond durability and uncured layer thickness Table

As is clear from Table 3, the thickness of the uncured layer of the low oxygen polymerization inhibitor of the dental adhesive prepared in example 1 after curing was smaller than that of the uncured layer of the commercial products 1 and 2; meanwhile, the adhesive strength and the adhesive durability of the low oxygen polymerization inhibitor prepared in example 1 in the self-curing mode were substantially the same as those of the commercial products 1 and 2. Therefore, the above test shows that the dental adhesive provided by the present invention has an advantage that the uncured layer is thinner than the commercially available products.

The dental adhesive provided by the invention has high bonding strength, good bonding durability and thinner oxygen inhibition layer thickness, is beneficial to avoiding the slipping problem in the resin filling process, is suitable for the pretreatment of the bonding surface of dental restorations of enamel, dentin and various materials, and completes various direct repair operations and indirect repair operations in the oral restoration process.

The above examples are preferred embodiments of the present invention, but the embodiments of the present invention are not limited to the above examples, and any other changes, modifications, substitutions, combinations, and simplifications that do not depart from the spirit and principle of the present invention should be made in the equivalent manner, and the embodiments are included in the protection scope of the present invention.

Claims

1. The low-oxygen polymerization-inhibition dental adhesive is characterized by comprising the following components in percentage by weight:

20-90 wt% of matrix resin;

0-15 wt% of filler;

1 to 5 weight percent of tertiary amine compound;

2. The adhesive of claim 1, wherein the polymerizable acrylate monomer is any one or more of a hydrophilic acrylic resin, a hydrophobic acrylic resin, and an acidic acrylic resin.

3. The adhesive of claim 1, wherein the photopolymerization initiator is any one or more of -diketones, ketals, thioxanthones, (bis) acyl phosphine oxides, benzoin alkyl ethers, benzildimethyl ketals, coumarins, diaryliodonium hexafluorophosphate, triarylsulfonium hexafluorophosphate, triarylselenonium hexafluorophosphate, camphorquinone, and 2,4, 6-trimethylbenzoyl-diphenyl phosphine oxide (TPO);

4. The low oxygen polymerization inhibiting dental adhesive of claim 1, wherein the matrix resin further comprises a polymerization inhibitor; the content of the polymerization inhibitor is less than 2wt%.

5. The adhesive for dental use having low oxygen inhibition according to claim 4, wherein the polymerization inhibitor is any one of 2, 6-di-t-butyl-p-cresol, p-hydroxyanisole or a mixture of both.

6. The low oxygen inhibition dental adhesive according to claim 1, wherein the filler is an inorganic filler or an organic filler or a mixture of an inorganic filler and an organic filler.

7. The adhesive for dental use having low oxygen inhibition according to claim 6, wherein the filler has an average particle diameter of 0.001 m to 1 m.

8. The adhesive for dental use having low oxygen inhibition according to claim 1, wherein the tertiary amine compound is triethanolamine, triethylamine, triethanolamine phosphate, N-methyldiethanolamine, dodecylamine, hexadecylamine, octadecylamine, dioctadecylamine, N, any one of N dimethylaniline, N, N diethylaniline, N, N dimethyl-p-toluidine, N, N dihydroxyethyl-p-toluidine, N-methyl-N hydroxyethyl-p-toluidine, N, N, N ', N ' -tetramethyl ethylenediamine, N, N dimethylethanolamine, N, N ' -dimethylpiperazine, N, N, N ', N ' -tetramethyl urea.

9. The low oxygen polymerization inhibiting dental adhesive of claim 1, further comprising a solvent for diluting said adhesive and improving the system stability of said adhesive; the content of the solvent is 5-60 wt%.

10. The adhesive of claim 9, wherein the solvent is any one or more of ethanol, isopropanol, acetone, methanol, n-butanol, cyclohexane, methylcyclohexane, dichloromethane, trichloroethylene, trichloromethane, methyl acetate, ethyl acetate, propyl acetate, isopropyl acetate, diethylene glycol monobutyl ether, butyl acetate, methyl ethyl ketone, cyclohexanone, turpentine, tetrahydrofuran, and deionized water.