CN100584301C - Teeth repairing material of visible-light curing composite nano-resin and its production - Google Patents
Teeth repairing material of visible-light curing composite nano-resin and its production Download PDFInfo
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- CN100584301C CN100584301C CN200610017234A CN200610017234A CN100584301C CN 100584301 C CN100584301 C CN 100584301C CN 200610017234 A CN200610017234 A CN 200610017234A CN 200610017234 A CN200610017234 A CN 200610017234A CN 100584301 C CN100584301 C CN 100584301C
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- 239000011347 resin Substances 0.000 title claims abstract description 13
- 229920005989 resin Polymers 0.000 title claims abstract description 13
- 239000000463 material Substances 0.000 title claims description 10
- 239000002131 composite material Substances 0.000 title claims description 7
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 19
- 239000004593 Epoxy Substances 0.000 claims abstract description 13
- 239000000178 monomer Substances 0.000 claims abstract description 9
- 229920000728 polyester Polymers 0.000 claims abstract description 8
- 239000011256 inorganic filler Substances 0.000 claims abstract description 7
- 229910003475 inorganic filler Inorganic materials 0.000 claims abstract description 7
- 150000001875 compounds Chemical class 0.000 claims abstract description 4
- 239000003504 photosensitizing agent Substances 0.000 claims abstract description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 24
- 229910002012 Aerosil® Inorganic materials 0.000 claims description 16
- 229930006711 bornane-2,3-dione Natural products 0.000 claims description 13
- VNQXSTWCDUXYEZ-UHFFFAOYSA-N 1,7,7-trimethylbicyclo[2.2.1]heptane-2,3-dione Chemical compound C1CC2(C)C(=O)C(=O)C1C2(C)C VNQXSTWCDUXYEZ-UHFFFAOYSA-N 0.000 claims description 12
- 238000012986 modification Methods 0.000 claims description 11
- 230000004048 modification Effects 0.000 claims description 11
- 239000002114 nanocomposite Substances 0.000 claims description 11
- 238000002360 preparation method Methods 0.000 claims description 11
- 239000000203 mixture Substances 0.000 claims description 7
- 229960005274 benzocaine Drugs 0.000 claims description 4
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 claims description 3
- 239000003999 initiator Substances 0.000 claims description 3
- 229910052760 oxygen Inorganic materials 0.000 claims description 3
- 239000001301 oxygen Substances 0.000 claims description 3
- 238000013019 agitation Methods 0.000 claims description 2
- 150000001768 cations Chemical class 0.000 claims description 2
- 150000002118 epoxides Chemical group 0.000 claims description 2
- 238000002156 mixing Methods 0.000 claims description 2
- 239000003607 modifier Substances 0.000 claims description 2
- 125000002362 bornane-2,3-dione group Chemical group 0.000 claims 1
- 239000000805 composite resin Substances 0.000 abstract description 23
- -1 3,4-epoxy cyclohexyl Chemical group 0.000 abstract description 6
- 238000000034 method Methods 0.000 abstract description 6
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 abstract 2
- MTEZSDOQASFMDI-UHFFFAOYSA-N 1-trimethoxysilylpropan-1-ol Chemical compound CCC(O)[Si](OC)(OC)OC MTEZSDOQASFMDI-UHFFFAOYSA-N 0.000 abstract 1
- 125000003118 aryl group Chemical group 0.000 abstract 1
- 125000002091 cationic group Chemical group 0.000 abstract 1
- 229910052681 coesite Inorganic materials 0.000 abstract 1
- 229910052906 cristobalite Inorganic materials 0.000 abstract 1
- 239000011159 matrix material Substances 0.000 abstract 1
- 239000000377 silicon dioxide Substances 0.000 abstract 1
- 235000012239 silicon dioxide Nutrition 0.000 abstract 1
- 229910052682 stishovite Inorganic materials 0.000 abstract 1
- 229910052905 tridymite Inorganic materials 0.000 abstract 1
- 230000000007 visual effect Effects 0.000 abstract 1
- 230000000052 comparative effect Effects 0.000 description 9
- 230000007547 defect Effects 0.000 description 6
- 239000000758 substrate Substances 0.000 description 6
- 238000011156 evaluation Methods 0.000 description 5
- 239000000945 filler Substances 0.000 description 5
- 238000005299 abrasion Methods 0.000 description 4
- 239000000470 constituent Substances 0.000 description 4
- 238000001723 curing Methods 0.000 description 4
- 238000011049 filling Methods 0.000 description 4
- 230000008602 contraction Effects 0.000 description 3
- 239000003822 epoxy resin Substances 0.000 description 3
- 238000005286 illumination Methods 0.000 description 3
- 229920000647 polyepoxide Polymers 0.000 description 3
- 229920006267 polyester film Polymers 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- AMFGWXWBFGVCKG-UHFFFAOYSA-N Panavia opaque Chemical compound C1=CC(OCC(O)COC(=O)C(=C)C)=CC=C1C(C)(C)C1=CC=C(OCC(O)COC(=O)C(C)=C)C=C1 AMFGWXWBFGVCKG-UHFFFAOYSA-N 0.000 description 2
- 239000007767 bonding agent Substances 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 239000007822 coupling agent Substances 0.000 description 2
- 238000011068 loading method Methods 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- MPDGHEJMBKOTSU-YKLVYJNSSA-N 18beta-glycyrrhetic acid Chemical compound C([C@H]1C2=CC(=O)[C@H]34)[C@@](C)(C(O)=O)CC[C@]1(C)CC[C@@]2(C)[C@]4(C)CC[C@@H]1[C@]3(C)CC[C@H](O)C1(C)C MPDGHEJMBKOTSU-YKLVYJNSSA-N 0.000 description 1
- UEKHZPDUBLCUHN-UHFFFAOYSA-N 2-[[3,5,5-trimethyl-6-[2-(2-methylprop-2-enoyloxy)ethoxycarbonylamino]hexyl]carbamoyloxy]ethyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCCOC(=O)NCCC(C)CC(C)(C)CNC(=O)OCCOC(=O)C(C)=C UEKHZPDUBLCUHN-UHFFFAOYSA-N 0.000 description 1
- 229910002020 Aerosil® OX 50 Inorganic materials 0.000 description 1
- 229910000497 Amalgam Inorganic materials 0.000 description 1
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 239000012153 distilled water Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000008187 granular material Substances 0.000 description 1
- 239000004973 liquid crystal related substance Substances 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 239000005543 nano-size silicon particle Substances 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 238000000016 photochemical curing Methods 0.000 description 1
- 238000013001 point bending Methods 0.000 description 1
- 238000005498 polishing Methods 0.000 description 1
- 229950000845 politef Drugs 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 229920005862 polyol Polymers 0.000 description 1
- 150000003077 polyols Chemical class 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 229910010271 silicon carbide Inorganic materials 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- 125000003003 spiro group Chemical group 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 238000004154 testing of material Methods 0.000 description 1
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- Dental Preparations (AREA)
Abstract
A nano-class composite resin solidified by visual light for repair tooth is composed of organic resin as matrix prepared proportionally from the epoxy monomer compound consisting of 3,4-epoxy cyclohexyl formic acid-3,4-epoxy cyclohexyl methylester and superbranched aromatic epoxy polyester, cationic light trigger, photosensitizer and co-trigger, and the inorganic filler which is the gamma-glycidic ether oxypropyl trimethoxy silane modified gas-phase SiO2 (OX-50). Its preparing process is also disclosed.
Description
Technical field
The present invention relates to a kind of visible-light curing composite nano-resin, be particularly useful for the direct filling reparation of multiple dental defect.The invention still further relates to the preparation method of this composite resin.
Background technology
The sixties in 20th century, Bowen successfully synthesized a kind of resin monomer BIS-GMA with special construction and performance, and recognized that inorganic filler carries out the surface-treated significance.On this basis, various composite resins develop rapidly, have now become the requisite important materials of dental defect repairing and treating, run neck and neck with silver amalgam.And that light-cured composite has is simple and convenient, the advantage of processing ease, is subjected to people's welcome deeply.
The composite resin teeth repairing material that to be a class combined by organic resin substrate and surface treated inorganic filler and initiator system is widely used in directly and indirectly repairing of all kinds of dental defect.Composite resin mainly comprises four parts: organic resin substrate, inorganic filler, coupling agent, light-initiated system.Although four parts are all influential to the overall performance of composite resin, what influence the composite resin physical and mechanical properties mainly is organic resin substrate and inorganic filler part.
What the resinous substrates application was maximum is methyl acrylic ester monomer and derivants thereof such as BIS-GMA, UDMA, the shortcoming that this class composite resin exists has: double bond conversion rate is low, contraction is big, viscosity is big and influence the addition of filler, thereby influences the mechanical performance of composite resin.Tilbrook D.A. studies epoxy resin/polyol resinous substrates system in addition, has improved the mechanical strength of composite resin, has improved its contractility.Also some research in addition about spiro original magnesium ester and liquid crystal base, but owing to there is the too high shortcoming of consistency problem or cost, Yan Jiu finished product is almost nil till now.
Press filler, that composite resin can be divided into is traditional, granule type, superminiature, mixed type composite resin.The difference of the sharp class of filler all has very big influence to the mechanical strength of composite resin, the transparency, abrasion resistance etc.In general, the granularity of filler is more little, and the abrasion resistance of composite resin is also good more.
The composite resin of using clinically generally all is a methyl acrylic ester now, and the major defect of existence is: contraction is big, conversion ratio is low.The home products mechanical strength is very low, higher abroad as U.S. Dentsply company, 3M company product strength, obtained very big success clinically, but still be necessary improving mechanical strength, reducing to shrink and improve aspect such as abrasion resistance and further improve.
Summary of the invention
The object of the present invention is to provide a kind of teeth repairing material of visible-light curing composite nano-resin and preparation method.
Dissaving polymer is a kind of novel high polymer material that just comes out nearly decades, it has good hydrodynamic performance and unique viscosity, it has toughening effect to epoxy resin, and because the special structure of dissaving polymer can reduce the contraction of epoxy resin.
The present invention uses the part of a kind of novel epoxy group aromatic series hyper-branched polyester monomer as composite resin organic resin substrate, nano silicon is the abrasion resistance that filler improves composite resin, and the gained composite resin has higher flexural strength and diameter tensile strength.
Composition of the present invention and mass percentage content thereof are:
(1) the epoxide group monomeric compound is by epoxide group aromatic series hyper-branched polyester monomer (HTDE-2), 3,4-epoxy radicals hexahydrobenzoid acid-3, and 4-epoxy radicals cyclohexyl methyl ester (UVR6105) is formed; (HTDE-2) mass percentage content is 1-5%, and (UVR6105) mass percentage content is 42-48%; Wherein, the structure of HTDE-2 is:
(2) cation light initiator is that the mass percentage content of diphenyl iodine hexafluoro antimonate (CD1012) is 1-2%.
(3) photosensitizer is that the mass percentage content of camphorquinone (CQ) is 0.4-0.6%.
(4) coinitiator is that the mass percentage content of 4-dimethyl ethyl aminobenzoate (EDMAB) is 0.15-0.3%.
(5) inorganic filler is the aerosil (OX-50) of modification, and mass percentage content is 45-55%.
Preparation method of the present invention is: in 40 ℃ of water-baths, press proportioning with UVR6105, HTDE-2, CD1012, CQ and EDMAB mix homogeneously.It is in the absolute methanol of 5 times of its quality that the aerosil (OX-50) of modification is scattered in, and joins then among UVR6105, HTDE-2, CD1012, CQ and the EDMAB of mix homogeneously.Lucifuge stirred 30 minutes, put into vacuum desiccator and removed absolute methanol and make nanocomposite.
The modifier of aerosil of the present invention (OX-50) is γ-glycidyl ether oxygen propyl trimethoxy silicane (GPS); Aerosil (OX-50) is modified as: OX-50,
GPS and absolute methanol are mixing in 20: 3: 60 by weight, and magnetic agitation is 24 hours in 50 ℃ of oil baths, and cool to room temperature is centrifugal, and be dry in 50 ℃ of baking ovens, obtains the aerosil (OX-50) of modification.
The nanocomposite of the present invention's preparation adopts three-point bending to estimate its flexural strength, the steps include:
The nanocomposite for preparing is put into down the mould of microscope slide and polyester film (preventing composite resin and microscope slide bonding) { in (25 ± 2) mm * (2 ± 0.1) mm * (2 ± 0.1) mm}, another polyester film and microscope slide are placed on die tip, clamp gently with clip, unnecessary material is overflowed, kept 30 seconds.Microscope slide irradiation 40 seconds is also being supported in the center of light source window registration coupon section, the center of another section of mobile light source window registration coupon, and make each illumination part and last time the illumination part was overlapping to some extent, irradiation time is the same.Carry out so successively, all illuminated up to the sample each several part.Then the sample another side is carried out same operation.Illumination finishes, and takes away microscope slide and polyester film, and the careful sample that takes out was put into 37 ± 1 ℃ of distilled water 24 hours from mould.5 samples of every group of preparation.With the polishing under 1000 order carborundum papers water spray of all samples, in full accord until the size of sample.
Sample is placed on distance on two strong points of 20mm, carries out loading,, note the size that maximum loading value is tried to achieve flexural strength until sample breakage with the speed of 0.5mm/min.
The evaluation of nanocomposite diameter tensile strength:
Sample is put well in the politef mould of high 3mm at internal diameter 6mm, each photocuring of both sides 60 seconds.
The cured sample flush end vertically is placed on the platen of general-purpose material testing machine, the size of the power the during fracture of record sample.Crosshead speed is 1mm/min.The diameter tensile strength is calculated by DTS=2P/ л dl, and wherein P is a maximum, force, and d is the sample diameter, and l is a sample length.
The usage of material of the present invention is as follows:
The present invention can be used for the direct filling reparation of dental defect, during operation, be coated with 2 times bonding agent earlier at the dental defect place, air gun featheriness 10 seconds, with visible-light curing light irradiation 10 seconds, adopt increment filling method filling composite resin, every layer of resin thickness is no more than 2 millimeters, and each layer shone 60 seconds with light-solidified lamp.The present invention also can be used for making dummy such as inlay etc., earlier composite resin is made into and dummy that tooth body hole type coincide, again by bonding agent with this dummy cementation in the type of tooth body hole.
Beneficial effect of the present invention:
The present invention has higher flexural strength and diameter tensile strength as can be seen from Table 1, and wherein the flexural strength of embodiment has improved 3.95%-27.6% than comparative example 1, has improved 26.6%-55.4% than comparative example 2.The diameter tensile strength of embodiment has improved 6.9%-25.1% than comparative example 1 the highest raising 17% than comparative example 2.
The specific embodiment
Need to prove that all material that the present invention adopts is known products, wherein HTDE-2 is provided by South China Science ﹠ Engineering University; Aerosil OX-50 provides mean diameter 50nm by sea, Shanghai ease scientific ﹠ trading Co., Ltd.; GPS buys from Jintan City, Jiangsu Province East China coupling agent factory; CD1012 buys from Sartomer company; Other chemical compounds are bought from Aldrich company.
Embodiment 1:
The component of nanocomposite and each components contents are:
Constituent mass content (%)
HTDE-2 1.43
UVR6105 46.41
CD1012 1.44
CQ 0.48
EDMAB 0.24
The aerosil of modification (OX-50) 50
The preparation of nanocomposite:, that HTDE-2, UVR6105, CD1012, CQ and EDMAB is even 40 ℃ of stirred in water bath according to the ratio of above-mentioned prescription.It is in the absolute methanol of 5 times of its quality that the aerosil (OX-50) of modification is scattered in, join then among UVR6105, HTDE-2, CD1012, CQ and the EDMAB of mix homogeneously, lucifuge stirred 30 minutes, put into vacuum desiccator and removed absolute methanol in 24 hours, make nanocomposite.The value that records its flexural strength and diameter tensile strength is respectively at table 1.
Embodiment 2:
Constituent mass content (%)
HTDE-2 2.87
UVR6105 44.97
CD1012 1.44
CQ 0.48
EDMAB 0.24
The aerosil of modification (OX-50) 50
The preparation of nanocomposite is identical with embodiment 1 with evaluation methodology.The value that records its flexural strength and diameter tensile strength is respectively at table 1.
Embodiment 3:
Constituent mass content (%)
HTDE-2 4.31
UVR6105 43.53
CD1012 1.44
CQ 0.48
EDMAB 0.24
The aerosil of modification (OX-50) 50
The preparation of nanocomposite is identical with embodiment 1 with evaluation methodology.The value that records its flexural strength and diameter tensile strength is respectively at table 1.
Comparative example 1:
Constituent mass content (%)
UVR6105 47.84
CD1012 1.44
CQ 0.48
EDMAB 0.24
The aerosil of modification (OX-50) 50
The preparation of nanocomposite is identical with embodiment 1 with evaluation methodology.The value that records its flexural strength and diameter tensile strength is respectively at table 1.
Comparative example 2: traditional methyl acrylic ester composite resin finished product-Ka Ruisima.
The evaluation methodology of composite resin is identical with embodiment 1.The value that records its flexural strength and diameter tensile strength is respectively at table 1.
Flexural strength that table 1 embodiment and comparative example obtain and the contrast of diameter tensile strength result
| Flexural strength (MPa) | Diameter tensile strength (Mpa) | |
| Embodiment 1: embodiment 2: embodiment 3: comparative example 1: comparative example 2: | 89.4(7.6) 101(6.4) 109.7(6.6) 86(7.8) 70.6(10) | 42.3(4.8) 40.1(2.6) 46.9(3.9) 40.1(3.4) 37.5(3.5) |
Annotate: data are standard deviation in the bracket in the table.
Claims (2)
1, a kind of teeth repairing material of visible-light curing composite nano-resin is characterized in that, its composition and mass percentage content are:
(1) the epoxide group monomeric compound is by epoxide group aromatic series hyper-branched polyester monomer, 3,4-epoxy radicals hexahydrobenzoid acid-3, and 4-epoxy radicals cyclohexyl methyl ester is formed; Epoxide group aromatic series hyper-branched polyester monomer mass degree is 1-5%, 3, and 4-epoxy radicals hexahydrobenzoid acid-3,4-epoxy radicals cyclohexyl methyl ester mass percentage content is 42-48%; Wherein, the monomeric structure of epoxide group aromatic series hyper-branched polyester is:
(2) cation light initiator is a diphenyl iodine hexafluoro antimonate, and mass percentage content is 1-2%;
(3) photosensitizer is a camphorquinone, and mass percentage content is 0.4-0.6%;
(4) coinitiator is the 4-dimethyl ethyl aminobenzoate, and mass percentage content is 0.15-0.3%;
(5) inorganic filler is the aerosil of modification, and mass percentage content is 45-55%.
2, a kind of teeth repairing material of visible-light curing composite nano-resin preparation method as claimed in claim 1, it is characterized in that, step and condition are: in 40 ℃ of water-baths, press proportioning with 3,4-epoxy radicals hexahydrobenzoid acid-3,4-epoxy radicals cyclohexyl methyl ester, epoxide group aromatic series hyper-branched polyester monomer, diphenyl iodine hexafluoro antimonate, camphorquinone and 4-dimethyl ethyl aminobenzoate mix homogeneously, it is in the absolute methanol of 5 times of its quality that the aerosil of modification is scattered in, join 3 of mix homogeneously then, 4-epoxy radicals hexahydrobenzoid acid-3,4-epoxy radicals cyclohexyl methyl ester, epoxide group aromatic series hyper-branched polyester monomer, diphenyl iodine hexafluoro antimonate, in camphorquinone and the 4-dimethyl ethyl aminobenzoate, lucifuge stirred 30 minutes, put into vacuum desiccator and removed absolute methanol and make nanocomposite;
The modifier of described aerosil is γ-glycidyl ether oxygen propyl trimethoxy silicane; Being modified as of aerosil: aerosil, γ-glycidyl ether oxygen propyl trimethoxy silicane and absolute methanol are mixing in 20: 3: 60 by weight, magnetic agitation is 24 hours in 50 ℃ of oil baths, cool to room temperature, centrifugal, dry in 50 ℃ of baking ovens, obtain the aerosil of modification.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
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| CN200610017234A CN100584301C (en) | 2006-10-04 | 2006-10-04 | Teeth repairing material of visible-light curing composite nano-resin and its production |
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| CN200610017234A CN100584301C (en) | 2006-10-04 | 2006-10-04 | Teeth repairing material of visible-light curing composite nano-resin and its production |
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| CN1939251A CN1939251A (en) | 2007-04-04 |
| CN100584301C true CN100584301C (en) | 2010-01-27 |
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| CN101804012B (en) * | 2010-03-25 | 2012-02-22 | 东华大学 | Photo-curing compound resin used for dental repair and using diatomite as stuffing and preparation method thereof |
| CN101914361A (en) * | 2010-06-02 | 2010-12-15 | 中国科学院长春应用化学研究所 | Wettable binder and preparation method thereof |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1209821A (en) * | 1996-11-21 | 1999-03-03 | 埃斯佩牙科股份公司 | Polymerizable compositions based on epoxides |
| CN1252137A (en) * | 1997-04-11 | 2000-05-03 | 美国3M公司 | Ternary photoinitiator system for curing of epoxy/polyol resin compositions |
| US6458865B2 (en) * | 1999-01-15 | 2002-10-01 | Curators Of The University Of Missouri | Photopolymerizable vinyl ether based monomeric formulations and polymerizable compositions which may include certain novel spiroorthocarbonates |
| CN1838934A (en) * | 2003-09-05 | 2006-09-27 | 罗狄亚化学公司 | Polymerizable dental composition having a high content of loading material |
-
2006
- 2006-10-04 CN CN200610017234A patent/CN100584301C/en not_active Expired - Fee Related
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1209821A (en) * | 1996-11-21 | 1999-03-03 | 埃斯佩牙科股份公司 | Polymerizable compositions based on epoxides |
| CN1252137A (en) * | 1997-04-11 | 2000-05-03 | 美国3M公司 | Ternary photoinitiator system for curing of epoxy/polyol resin compositions |
| US6458865B2 (en) * | 1999-01-15 | 2002-10-01 | Curators Of The University Of Missouri | Photopolymerizable vinyl ether based monomeric formulations and polymerizable compositions which may include certain novel spiroorthocarbonates |
| CN1838934A (en) * | 2003-09-05 | 2006-09-27 | 罗狄亚化学公司 | Polymerizable dental composition having a high content of loading material |
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Effective date of registration: 20190412 Address after: 130015 No. 5218 Longhu Road, High-tech North District, Changchun City, Jilin Province Patentee after: Changchun applied chemical science and Technology General Corporation of Chinese Academy of Sciences Address before: 130022 No. 5625 Renmin Street, Jilin, Changchun Patentee before: CHANGCHUN INSTITUTE OF APPLIED CHEMISTRY CHINESE ACADEMY OF SCIENCES |
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