CN109730935A - A kind of high-strength dentistry composite resin and preparation method thereof - Google Patents
A kind of high-strength dentistry composite resin and preparation method thereof Download PDFInfo
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- CN109730935A CN109730935A CN201910044740.8A CN201910044740A CN109730935A CN 109730935 A CN109730935 A CN 109730935A CN 201910044740 A CN201910044740 A CN 201910044740A CN 109730935 A CN109730935 A CN 109730935A
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Abstract
The present invention relates to a kind of high-strength dentistry composite resin and preparation method thereof, raw material includes inorganic filler, organic monomer and photoinitiator, and the inorganic filler is the total filler that spherical mesoporous filler and Ball-type packing form.Preparation method includes: after being premixed spherical mesoporous filler, organic monomer and photoinitiator, to be put into three-roll grinder and further mix, add Ball-type packing, handle through negative pressure of vacuum, obtains uncured compound resin cream；Finally pass through visible-light curing, obtains dentistry composite resin.Dentistry composite resin preparation method of the invention is easy, excellent in mechanical performance, has a good application prospect.
Description
Technical field
The invention belongs to dental prosthetic material field, in particular to a kind of high-strength dentistry composite resin and preparation method thereof.
Background technique
After having synthesized famous bisphenol-A-glycidyl methacrylate (Bis-GMA) from R.L.Bowen in 1962,
Resin base dentistry composite resin is ranked among by the features such as in beautiful color, convenient, the physical and chemical and biological property of operation is excellent as dental caries
With the important materials of defect of teeth treatment.The resinoid is mainly made of organic monomer, silanization inorganic filler and photoinitiator,
Inorganic filler can wherein be wrapped up at the organic monomer that continuous phase is distributed, form polymer network knot in Raolical polymerizable
Structure.Although researcher achieves numerous progress in terms of optimization organic monomer structure, inorganic filler composition, fracture is repaired
Be still the main reason for leading to compound resin treatment failure (K.Collares, et al.Journal of Dentistry,
2018,68,79-84.).Therefore, the mechanical property of dentistry composite resin still needs to further increase.
By forming it is found that type, partial size, the content etc. of inorganic filler determine the mechanical property of resin for compound resin.But
In complicated oral environment, the silanol and ester bond of silanization filler surface can occur to hydrolyze (T.Nihei.Journal of
Oral Science, 2016,58,151-155.), weaken the expression of material mechanical performance.In contrast to this, mesoporous filler passes through micro-
Mechanical interlock can penetrate into organic monomer in filler hole, to avoid stuffing surface modification process.Therefore, mesoporous filler
Concern of the application by researcher in dentistry composite resin.For example, patent CN 106038322A devises a kind of Jie
Hole SiO2The antibacterial filler of cladding, by with silanization SiO2Combination, effectively increase filer content and resin mechanical property,
But the highest content of mesoporous filler is only 10wt%.In addition, Samuel et al. uses mesoporous SiO2Compound resin is prepared, due to it
Specific surface area is higher, and the highest charging quantity of filler is only 40wt%, and the bending strength of corresponding resin is only 72 ± 16MPa
(S.P.Samuel,et al.Dental Materials,2009,25,296-301.).Although selecting non-porous SiO2It is mesoporous with this
SiO2Filler altogether is formed, optimizing its composition by trial-and-error method improves amount of filler to 70wt%, but still does not meet ISO 4049-
The minimum requirements (80MPa) of 2009 pairs of compound resin bending strengths.The studies above shows: (1) being total to containing for filler intermediary hole filler
It measures lower, is unfavorable for utmostly showing the advantage of mesoporous filler；(2) second level spherical SiO in total filler2Partial size and content
Trial-and-error method need to be employed many times to determine, time and effort consuming is unfavorable for industrialized production.
Summary of the invention
Technical problem to be solved by the invention is to provide a kind of high-strength dentistry composite resins and preparation method thereof, pass through
Big sphere closely packed model, theoretical calculation second level fill the maximum particle diameter of spheroidal particle, optimize filler composition altogether, improve compound
The mechanical property of resin.
The present invention provides a kind of high-strength dentistry composite resin, raw material includes inorganic filler, organic monomer and photoinitiator,
The inorganic filler is the total filler that inorganic filler is spherical mesoporous filler and Ball-type packing composition；Wherein, spherical mesoporous filler
Quality account for dentistry composite resin gross mass 40-55% (with highest content fill compound resin), the quality of Ball-type packing accounts for
The 10-25% of dentistry composite resin gross mass is (multiple with highest additive amount filling spherical mesoporous filler abutment section as secondary particle
Resin).
Preferably, the spherical mesoporous filler be sphericity mesoporous silicon dioxide, it is spherical mesoporous hydroxyapatite, spherical mesoporous
At least one of zinc oxide, spherical mesoporous titanium dioxide, partial size are 0.3-2 μm.
Preferably, the Ball-type packing is preparing spherical SiO 2, ball shaped hydroxy-apatite, spherical zinc oxide, spherical dioxy
Change at least one of titanium；Partial size be using spherical mesoporous filler as primary particle, by etc. big sphere closely packed model calculate
Fill the maximum gauge of secondary particle obtained in its tetrahedron gap and octahedral interstices.
Preferably, the organic monomer is made of main monomer and diluent monomer, and quality accounts for the total matter of dentistry composite resin
The 20-50% of amount.
Preferably, the main monomer be bisphenol-A-glycidyl methacrylate Bis-GMA, the double methyl of carbamate
At least one of acrylate UDMA；The diluent monomer be double ethoxylated bisphenol-A dimethylacrylate EBPADMA,
Diethylene glycol dimethacrylate TEGDMA, 1,6 hexanediol diacrylate, 4- hydroxybutyl acrylate, metering system
At least one of sour methyl esters MMA.
Preferably, the mass ratio of the main monomer and diluent monomer is 1-4:1.
Preferably, the photoinitiator is made of main initiator and aided initiating, and quality is the 1- of organic monomer quality
3%.
Preferably, the main initiator is at least one of camphorquinone CQ, benzophenone, diphenylethan；It is described to help
Initiator is (dimethylamino)-ethyl benzoate 4-EDMAB, trimethylbenzoyl phenyl phosphinic acid ethyl ester, methyl benzoylformate
At least one of.
Preferably, the mass ratio of the main initiator and aided initiating is 1:1-5.
The present invention also provides a kind of preparation methods of high-strength dentistry composite resin, comprising:
After spherical mesoporous filler, organic monomer and photoinitiator are premixed, it is put into three-roll grinder and further mixes
It closes, adds Ball-type packing, handled through negative pressure of vacuum, obtain uncured compound resin cream；Finally pass through visible-light curing, obtains
To dentistry composite resin.
Spherical mesoporous filler is considered as primary particle by the present invention, when it reaches the filling of highest content in compound resin,
By etc. big sphere closely packed model, the maximum that theoretical calculation can fill second level spheroidal particle in primary particle internal voids it is straight
Diameter finally instructs the composition of the partial size of second level Ball-type packing and the inorganic filler altogether of optimization in an experiment, improves compound resin
Mechanical property.
Beneficial effect
The inorganic filler that dentistry composite resin in the present invention is selected is spherical mesoporous filler and what Ball-type packing formed is total to
Filler.As the Ball-type packing of secondary particle, partial size is no longer pass through traditional trial-and-error method and determines, but by etc. big sphere it is tight
Closs packing model theory calculates；Its content can be added under conditions of spherical mesoporous filler highest fills dentistry composite resin
Add to the highest additive amount in compound resin.
The present invention not only realize spherical mesoporous filler in compound resin high-content filling, but also by etc. big sphere
The smooth, spherical filler of closely packed model screening appropriate particle size fills the gap between spherical mesoporous filler as secondary particle,
To improve the mechanical property of inorganic filler total content and compound resin.
Detailed description of the invention
Fig. 1 is spherical mesoporous SiO in embodiment 12The TEM picture of particle；
Fig. 2 is the bending strength for the compound resin that embodiment 1-3 is obtained；
Fig. 3 is the bending modulus for the compound resin that embodiment 1-3 is obtained.
Specific embodiment
Present invention will be further explained below with reference to specific examples.It should be understood that these embodiments are merely to illustrate the present invention
Rather than it limits the scope of the invention.In addition, it should also be understood that, after reading the content taught by the present invention, those skilled in the art
Member can make various changes or modifications the present invention, and such equivalent forms equally fall within the application the appended claims and limited
Range.
Embodiment 1
(1) composition of inorganic filler
By etc. big sphere closely packed model it is found that big sphere (primary particle) octahedral interstices and the tetrahedron such as can fill
The calculation formula of the maximum gauge of spheroidal particle is respectively d in gap8=0.828R and d4(R such as is at the half of big ball to=0.45R
Diameter).The sphericity mesoporous silicon dioxide that partial size is 550nm is selected to be used as primary particle, according to calculated result, selection partial size is respectively
The preparing spherical SiO 2 of 227nm and 123nm is as secondary particle.
(2) preparation of compound resin
It is formulated according to shown in table 1, first by the way of premixing by hand, the spherical mesoporous titanium dioxide for being 550nm by partial size
Silicon, organic monomer and photoinitiator mixing, when filler is sufficiently soaked by resin matrix, are put into three-roll grinder (EXAKT
80E, Germany) secondary mixing.Secondly, adding partial size after the preparing spherical SiO 2 to highest additive amount that partial size is 227nm is added
For 123nm preparing spherical SiO 2 to highest additive amount.After negative pressure of vacuum is handled, uncured compound resin cream is obtained.By
Visible light (460-480nm) solidifies 60s, obtains dentistry composite resin.
The component of 1. compound resin of table and the content of each component
(3) characterization of compound resin
Referring to international standard " ISO 4049-2009 ", dentistry is tested using universal testing machine (Instron 5900, the U.S.)
The bending strength and bending modulus of compound resin, as a result respectively 122.7 ± 6.2MPa and 9.8 ± 1.3GPa.
Embodiment 2
(1) composition of inorganic filler
Select the spherical mesoporous zinc oxide that partial size is 900nm as primary particle, according to formula shown in embodiment 1,
Select the spherical tio2 that partial size is 372nm and 202nm as secondary particle respectively.
(2) preparation of compound resin
According to shown in table 2 be formulated, first using premixing by hand by the way of, by partial size for 900nm spherical mesoporous zinc oxide,
Organic monomer and photoinitiator mixing, when filler is sufficiently soaked by resin matrix, are put into three-roll grinder (EXAKT 80E, moral
State) secondary mixing.Secondly, adding partial size is after the spherical tio2 to highest additive amount that partial size is 372nm is added
The spherical tio2 of 202nm is to highest additive amount.After negative pressure of vacuum is handled, uncured compound resin cream is obtained.By can
Light-exposed (460-480nm) solidifies 60s, obtains dentistry composite resin.
The component of 2. compound resin of table and the content of each component
(3) characterization of compound resin
The characterizing method of compound resin made from embodiment 2 is same as Example 1, measure compound resin bending strength and
Bending modulus is respectively 131.8 ± 5.9MPa and 10.6 ± 1.4GPa.
Embodiment 3
(1) composition of inorganic filler
Select the sphericity mesoporous silicon dioxide that partial size is 1.2 μm as primary particle, according to public affairs shown in embodiment 1
Formula selects the ball shaped hydroxy-apatite that partial size is 496nm and 270nm as secondary particle respectively.
(2) preparation of compound resin
It is formulated according to shown in table 3, first by the way of premixing by hand, the spherical mesoporous titanium dioxide for being 1.2 μm by partial size
Silicon, organic monomer and photoinitiator mixing, when filler is sufficiently soaked by resin matrix, are put into three-roll grinder (EXAKT
80E, Germany) secondary mixing.Secondly, adding grain after the ball shaped hydroxy-apatite to highest additive amount that partial size is 496nm is added
Diameter is the ball shaped hydroxy-apatite of 270nm to highest additive amount.After negative pressure of vacuum is handled, uncured compound resin cream is obtained.
Visible light (460-480nm) solidification is then passed through, dentistry composite resin is obtained.
The component of 3. compound resin of table and the content of each component
(3) characterization of compound resin
The characterizing method of compound resin made from embodiment 3 is same as Example 1, measure compound resin bending strength and
Bending modulus is respectively 138.3 ± 5.1MPa and 11.5 ± 1.5GPa.
By Fig. 2 and Fig. 3 it is found that spherical mesoporous filler and Ball-type packing is selected to prepare high-strength tooth as filler altogether in the present invention
The partial size and content of section's compound resin, intermediary hole filler and second level Ball-type packing influence the mechanical property of compound resin.Implement
The mechanical property that compound resin is made in example 3 is optimal value, bending strength far more than ISO 4049 requirement (>=80MPa).
The present invention gives up traditional trial-and-error method, optimizes inorganic filler composition by theoretical model calculating method, realizes high inorganic filler content
The preparation constructed with high-strength compound resin.
Claims (10)
1. a kind of high-strength dentistry composite resin, raw material includes inorganic filler, organic monomer and photoinitiator, it is characterised in that: institute
Stating inorganic filler is the total filler that inorganic filler is spherical mesoporous filler and Ball-type packing composition；Wherein, spherical mesoporous filler
Quality accounts for the 40-55% of dentistry composite resin gross mass, and the quality of Ball-type packing accounts for the 10- of dentistry composite resin gross mass
25%.
2. a kind of high-strength dentistry composite resin according to claim 1, it is characterised in that: the spherical mesoporous filler is ball
Shape mesoporous silicon oxide, spherical mesoporous hydroxyapatite, spherical mesoporous zinc oxide, at least one in spherical mesoporous titanium dioxide
Kind, partial size is 0.3-2 μm.
3. a kind of high-strength dentistry composite resin according to claim 1, it is characterised in that: the Ball-type packing is spherical shape two
At least one of silica, ball shaped hydroxy-apatite, spherical zinc oxide, spherical tio2；Partial size is filled out with spherical mesoporous
Material is primary particle, by etc. big sphere closely packed model calculate and fill obtained in its tetrahedron gap and octahedral interstices
The maximum gauge of secondary particle.
4. a kind of high-strength dentistry composite resin according to claim 1, it is characterised in that: the organic monomer is by main monomer
It is formed with diluent monomer, quality accounts for the 20-50% of dentistry composite resin gross mass.
5. a kind of high-strength dentistry composite resin according to claim 4, it is characterised in that: the main monomer is bisphenol-A-first
At least one of base glycidyl acrylate Bis-GMA, carbamate double methyl methacrylate UDMA；The diluent
Monomer is double ethoxylated bisphenol-A dimethylacrylate EBPADMA, diethylene glycol dimethacrylate TEGDMA, 1,6- oneself
At least one of omega-diol diacrylate, 4- hydroxybutyl acrylate, methyl methacrylate MMA.
6. a kind of high-strength dentistry composite resin according to claim 4, it is characterised in that: the main monomer and diluent list
The mass ratio of body is 1-4:1.
7. a kind of high-strength dentistry composite resin according to claim 1, it is characterised in that: the photoinitiator is by main initiation
Agent and aided initiating composition, quality are the 1-3% of organic monomer quality.
8. a kind of high-strength dentistry composite resin according to claim 7, it is characterised in that: the main initiator is camphorquinone
At least one of CQ, benzophenone, diphenylethan；The aided initiating be (dimethylamino)-ethyl benzoate 4-EDMAB,
At least one of trimethylbenzoyl phenyl phosphinic acid ethyl ester, methyl benzoylformate.
9. a kind of high-strength dentistry composite resin according to claim 7, it is characterised in that: the main initiator and help initiation
The mass ratio of agent is 1:1-5.
10. a kind of preparation method of high-strength dentistry composite resin as described in claim 1, comprising:
After spherical mesoporous filler, organic monomer and photoinitiator are premixed, it is put into three-roll grinder and further mixes, then
Ball-type packing is added, is handled through negative pressure of vacuum, obtains uncured compound resin cream；Finally pass through visible-light curing, obtains tooth
Section's compound resin.
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Cited By (3)
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| CN110606913A (en) * | 2019-09-11 | 2019-12-24 | 国网吉林省电力有限公司电力科学研究院 | Acrylate material capable of being rapidly cured by visible light and preparation method thereof |
| CN114349903A (en) * | 2021-12-20 | 2022-04-15 | 华南理工大学 | Bisphenol A structure-free flowable bulk filling composite resin and preparation and application thereof |
| CN115413271A (en) * | 2020-04-15 | 2022-11-29 | Agc硅素技术株式会社 | Hydroxyapatite-supported porous silica particles, method for producing hydroxyapatite-supported porous silica particles, and composition containing hydroxyapatite-supported porous silica particles |
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN110606913A (en) * | 2019-09-11 | 2019-12-24 | 国网吉林省电力有限公司电力科学研究院 | Acrylate material capable of being rapidly cured by visible light and preparation method thereof |
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| CN115413271B (en) * | 2020-04-15 | 2024-02-27 | Agc硅素技术株式会社 | Hydroxyapatite-supported porous silica particles, method for producing same, and composition containing same |
| CN114349903A (en) * | 2021-12-20 | 2022-04-15 | 华南理工大学 | Bisphenol A structure-free flowable bulk filling composite resin and preparation and application thereof |
| CN114349903B (en) * | 2021-12-20 | 2022-10-25 | 华南理工大学 | Bisphenol A structure-free flowable bulk filling composite resin and preparation and application thereof |
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