CN115894773B - Photo-curing 3D printing resin for dentistry and preparation method thereof - Google Patents
Photo-curing 3D printing resin for dentistry and preparation method thereof Download PDFInfo
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- CN115894773B CN115894773B CN202211567196.3A CN202211567196A CN115894773B CN 115894773 B CN115894773 B CN 115894773B CN 202211567196 A CN202211567196 A CN 202211567196A CN 115894773 B CN115894773 B CN 115894773B
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- 239000011347 resin Substances 0.000 title claims abstract description 83
- 229920005989 resin Polymers 0.000 title claims abstract description 83
- 238000010146 3D printing Methods 0.000 title claims abstract description 63
- 238000000016 photochemical curing Methods 0.000 title claims abstract description 45
- 238000002360 preparation method Methods 0.000 title abstract description 13
- 239000000178 monomer Substances 0.000 claims abstract description 48
- 239000003153 chemical reaction reagent Substances 0.000 claims abstract description 29
- 239000012949 free radical photoinitiator Substances 0.000 claims abstract description 29
- -1 acrylic ester Chemical class 0.000 claims abstract description 20
- 239000003085 diluting agent Substances 0.000 claims abstract description 17
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims abstract description 11
- KFDVPJUYSDEJTH-UHFFFAOYSA-N 4-ethenylpyridine Chemical compound C=CC1=CC=NC=C1 KFDVPJUYSDEJTH-UHFFFAOYSA-N 0.000 claims abstract description 6
- ISXSCDLOGDJUNJ-UHFFFAOYSA-N tert-butyl prop-2-enoate Chemical compound CC(C)(C)OC(=O)C=C ISXSCDLOGDJUNJ-UHFFFAOYSA-N 0.000 claims abstract description 6
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 claims abstract description 5
- QNILTEGFHQSKFF-UHFFFAOYSA-N n-propan-2-ylprop-2-enamide Chemical compound CC(C)NC(=O)C=C QNILTEGFHQSKFF-UHFFFAOYSA-N 0.000 claims abstract description 5
- DXPPIEDUBFUSEZ-UHFFFAOYSA-N 6-methylheptyl prop-2-enoate Chemical compound CC(C)CCCCCOC(=O)C=C DXPPIEDUBFUSEZ-UHFFFAOYSA-N 0.000 claims abstract description 4
- VOZRXNHHFUQHIL-UHFFFAOYSA-N glycidyl methacrylate Chemical compound CC(=C)C(=O)OCC1CO1 VOZRXNHHFUQHIL-UHFFFAOYSA-N 0.000 claims abstract description 4
- GNSFRPWPOGYVLO-UHFFFAOYSA-N 3-hydroxypropyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCCCO GNSFRPWPOGYVLO-UHFFFAOYSA-N 0.000 claims abstract description 3
- 238000006116 polymerization reaction Methods 0.000 claims description 30
- 239000011159 matrix material Substances 0.000 claims description 25
- 239000002994 raw material Substances 0.000 claims description 25
- 239000012752 auxiliary agent Substances 0.000 claims description 16
- 238000006243 chemical reaction Methods 0.000 claims description 12
- 238000002156 mixing Methods 0.000 claims description 10
- 239000011521 glass Substances 0.000 claims description 8
- 239000003960 organic solvent Substances 0.000 claims description 8
- 238000007789 sealing Methods 0.000 claims description 8
- 238000003756 stirring Methods 0.000 claims description 8
- 239000002202 Polyethylene glycol Substances 0.000 claims description 7
- 229920001223 polyethylene glycol Polymers 0.000 claims description 7
- VFLDPWHFBUODDF-FCXRPNKRSA-N curcumin Chemical compound C1=C(O)C(OC)=CC(\C=C\C(=O)CC(=O)\C=C\C=2C=C(OC)C(O)=CC=2)=C1 VFLDPWHFBUODDF-FCXRPNKRSA-N 0.000 claims description 6
- VFHVQBAGLAREND-UHFFFAOYSA-N diphenylphosphoryl-(2,4,6-trimethylphenyl)methanone Chemical compound CC1=CC(C)=CC(C)=C1C(=O)P(=O)(C=1C=CC=CC=1)C1=CC=CC=C1 VFHVQBAGLAREND-UHFFFAOYSA-N 0.000 claims description 6
- LYCAIKOWRPUZTN-UHFFFAOYSA-N ethylene glycol Natural products OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 6
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 claims description 6
- SEACYXSIPDVVMV-UHFFFAOYSA-L eosin Y Chemical compound [Na+].[Na+].[O-]C(=O)C1=CC=CC=C1C1=C2C=C(Br)C(=O)C(Br)=C2OC2=C(Br)C([O-])=C(Br)C=C21 SEACYXSIPDVVMV-UHFFFAOYSA-L 0.000 claims description 5
- ZDQNWDNMNKSMHI-UHFFFAOYSA-N 1-[2-(2-prop-2-enoyloxypropoxy)propoxy]propan-2-yl prop-2-enoate Chemical compound C=CC(=O)OC(C)COC(C)COCC(C)OC(=O)C=C ZDQNWDNMNKSMHI-UHFFFAOYSA-N 0.000 claims description 4
- RBTBFTRPCNLSDE-UHFFFAOYSA-N 3,7-bis(dimethylamino)phenothiazin-5-ium Chemical compound C1=CC(N(C)C)=CC2=[S+]C3=CC(N(C)C)=CC=C3N=C21 RBTBFTRPCNLSDE-UHFFFAOYSA-N 0.000 claims description 4
- IOLQWGVDEFWYNP-UHFFFAOYSA-N ethyl 2-bromo-2-methylpropanoate Chemical compound CCOC(=O)C(C)(C)Br IOLQWGVDEFWYNP-UHFFFAOYSA-N 0.000 claims description 4
- 229960000907 methylthioninium chloride Drugs 0.000 claims description 4
- 239000012956 1-hydroxycyclohexylphenyl-ketone Substances 0.000 claims description 3
- AOBIOSPNXBMOAT-UHFFFAOYSA-N 2-[2-(oxiran-2-ylmethoxy)ethoxymethyl]oxirane Chemical compound C1OC1COCCOCC1CO1 AOBIOSPNXBMOAT-UHFFFAOYSA-N 0.000 claims description 3
- SHKUUQIDMUMQQK-UHFFFAOYSA-N 2-[4-(oxiran-2-ylmethoxy)butoxymethyl]oxirane Chemical compound C1OC1COCCCCOCC1CO1 SHKUUQIDMUMQQK-UHFFFAOYSA-N 0.000 claims description 3
- UGVRJVHOJNYEHR-UHFFFAOYSA-N 4-chlorobenzophenone Chemical compound C1=CC(Cl)=CC=C1C(=O)C1=CC=CC=C1 UGVRJVHOJNYEHR-UHFFFAOYSA-N 0.000 claims description 3
- MQDJYUACMFCOFT-UHFFFAOYSA-N bis[2-(1-hydroxycyclohexyl)phenyl]methanone Chemical compound C=1C=CC=C(C(=O)C=2C(=CC=CC=2)C2(O)CCCCC2)C=1C1(O)CCCCC1 MQDJYUACMFCOFT-UHFFFAOYSA-N 0.000 claims description 3
- 229940109262 curcumin Drugs 0.000 claims description 3
- 235000012754 curcumin Nutrition 0.000 claims description 3
- 239000004148 curcumin Substances 0.000 claims description 3
- VFLDPWHFBUODDF-UHFFFAOYSA-N diferuloylmethane Natural products C1=C(O)C(OC)=CC(C=CC(=O)CC(=O)C=CC=2C=C(OC)C(O)=CC=2)=C1 VFLDPWHFBUODDF-UHFFFAOYSA-N 0.000 claims description 3
- 238000000034 method Methods 0.000 claims description 3
- 229920001451 polypropylene glycol Polymers 0.000 claims description 3
- WTOUYJXPUNLWSZ-UHFFFAOYSA-N 2,4-diethyl-1,3-thiazole 1-oxide Chemical compound C(C)C=1S(C=C(N1)CC)=O WTOUYJXPUNLWSZ-UHFFFAOYSA-N 0.000 claims description 2
- KUAUJXBLDYVELT-UHFFFAOYSA-N 2-[[2,2-dimethyl-3-(oxiran-2-ylmethoxy)propoxy]methyl]oxirane Chemical compound C1OC1COCC(C)(C)COCC1CO1 KUAUJXBLDYVELT-UHFFFAOYSA-N 0.000 claims description 2
- FIHBHSQYSYVZQE-UHFFFAOYSA-N 6-prop-2-enoyloxyhexyl prop-2-enoate Chemical compound C=CC(=O)OCCCCCCOC(=O)C=C FIHBHSQYSYVZQE-UHFFFAOYSA-N 0.000 claims description 2
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 claims description 2
- LNBSKWVLUJUCLA-UHFFFAOYSA-N C(C=C)(=O)OOCC.C(C=C)(=O)OOCC.OCC(C)(CO)C Chemical compound C(C=C)(=O)OOCC.C(C=C)(=O)OOCC.OCC(C)(CO)C LNBSKWVLUJUCLA-UHFFFAOYSA-N 0.000 claims description 2
- 240000001972 Gardenia jasminoides Species 0.000 claims description 2
- FZUGPQWGEGAKET-UHFFFAOYSA-N parbenate Chemical compound CCOC(=O)C1=CC=C(N(C)C)C=C1 FZUGPQWGEGAKET-UHFFFAOYSA-N 0.000 claims description 2
- 239000000843 powder Substances 0.000 claims description 2
- 238000005303 weighing Methods 0.000 claims description 2
- 230000002087 whitening effect Effects 0.000 claims description 2
- 238000007639 printing Methods 0.000 abstract description 16
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 12
- 238000005516 engineering process Methods 0.000 description 12
- 238000001723 curing Methods 0.000 description 11
- 239000000203 mixture Substances 0.000 description 11
- 238000004519 manufacturing process Methods 0.000 description 7
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- 230000001678 irradiating effect Effects 0.000 description 6
- 230000004048 modification Effects 0.000 description 6
- 238000012986 modification Methods 0.000 description 6
- 238000009210 therapy by ultrasound Methods 0.000 description 6
- 230000009286 beneficial effect Effects 0.000 description 5
- 238000010550 living polymerization reaction Methods 0.000 description 5
- 125000005396 acrylic acid ester group Chemical group 0.000 description 3
- 238000011282 treatment Methods 0.000 description 3
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 description 2
- 230000006978 adaptation Effects 0.000 description 2
- 238000004040 coloring Methods 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 238000011038 discontinuous diafiltration by volume reduction Methods 0.000 description 2
- 239000000758 substrate Substances 0.000 description 2
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 239000004851 dental resin Substances 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
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- 238000009776 industrial production Methods 0.000 description 1
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Landscapes
- Dental Preparations (AREA)
Abstract
The invention provides a light-cured 3D printing resin for dentistry and a preparation method thereof, which belong to the technical field of light-cured dentistry resins, wherein the light-cured 3D printing resin for dentistry consists of the following components: the component A is an acrylic monomer; a free radical photoinitiator; a living polymerization-dedicated reagent; the acrylic ester monomer is one of methyl methacrylate, hydroxypropyl methacrylate, isooctyl acrylate and tert-butyl acrylate; component B is a functional monomer; difunctional reactive diluents; the functional monomer is one of N-isopropyl acrylamide, 1-perylene methyl methacrylate, 4-vinyl pyridine and glycidyl methacrylate; the photo-curing 3D printing resin has high printing precision, high toughness and excellent mechanical property, has dormant active end groups, and can be activated again under external stimulus to realize the partial self-repair of damaged parts.
Description
Technical Field
The invention relates to the technical field of photo-curing dental resin, in particular to photo-curing 3D printing resin for dentistry and a preparation method thereof.
Background
The 3D printing technology, also called additive manufacturing technology, is a technology for manufacturing a three-dimensional product by adding materials layer by a 3D printing apparatus according to a designed 3D model. 3D printing integrates the front edge technology in the fields of digital modeling technology, electromechanical control technology, information technology, material science, chemistry and the like, and is one of the rapid prototyping technologies. The photo-curing 3D printing technology is widely applied in dentistry by virtue of the characteristics of good molding surface quality, high dimensional accuracy, capability of realizing finer and finer parts and the like. Along with the continuous improvement of market individuation and customization demands, the technology combining digitization and technology of photo-curing 3D printing has a wide application prospect in the dental industry. Compared with the traditional mode, the 3D printing is more accurate, and the period and the cost can be greatly reduced.
The dental curing resin is a dental restoration material with wide application and convenient use, and can be cured by light irradiation or self-curing under the condition of no light source or energy source; can be used as dental filling resin and pile core resin, and can be widely used for bonding. However, compared with the increasingly mature photo-curing 3D printing equipment, the type of the photo-curing resin used in a matched way is relatively single, and the photo-curing resin has no wide product applicability. For oral medical treatment, in addition to curing shrinkage factors of an initiator and a resin, factors of toxicity and reaction completeness, photo-curing reaction completeness and fast curing are considered, and good resin transparency, biocompatibility and repairability are required for the 3D printing photo-curing resin for dental use. Based on the above, development of a novel photo-curing resin is needed, which can be widely applied to the photo-curing 3D printing requirement in the oral field, has high printing precision, good toughness and mechanical property, and good compatibility with human body, and also has good self-repairing property.
Disclosure of Invention
In view of the above, the invention provides a photo-curing 3D printing resin for dentistry and a preparation method thereof, wherein the photo-curing 3D printing resin has high printing precision, high toughness, small volume reduction rate and excellent mechanical property, has dormant active end groups, and can be activated again under external stimulus to realize partial self-repair of damaged parts.
In order to solve the technical problems, the invention provides a light-cured 3D printing resin for dentistry, which comprises the following components in parts by weight:
Component A
100-200 Parts of acrylic monomer;
1-2 parts of a free radical photoinitiator;
1-2 parts of a special active polymerization reagent;
the acrylic ester monomer is one of methyl methacrylate, hydroxypropyl methacrylate, isooctyl acrylate and tert-butyl acrylate;
Component B
20-80 Parts of functional monomer;
2-8 parts of difunctional reactive diluent;
the functional monomer is one of N-isopropyl acrylamide, 1-perylene methyl methacrylate, 4-vinyl pyridine and glycidyl methacrylate.
Further, the component B also comprises 0.02-0.05 part by weight of an auxiliary agent.
Further, the auxiliary agent is one of curcumin, eosin Y, gardenia blue, fluorescent whitening powder and methylene blue.
Further, the free radical photoinitiator in the component A is one or more of diphenyl (2, 4, 6-trimethyl benzoyl) phosphine oxide, 1-hydroxy-cyclohexyl-phenyl ketone, p-chlorobenzophenone, ethyl p-dimethylaminobenzoate and 2, 4-diethyl thiazolone.
Further, the special active polymerization reagent in the component A is one or more of bromoisobutyric acid glycol ester and bromoisobutyric acid ethyl ester.
Further, the difunctional reactive diluent in the component B is one or more of 1, 4-butanediol diglycidyl ether, polypropylene glycol diglycidyl ether, neopentyl glycol diglycidyl ether, tripropylene glycol diacrylate, 1, 6-hexanediol diacrylate, neopentyl glycol diethoxy diacrylate and polyethylene glycol (400) dimethacrylate.
A method for preparing a photo-curing 3D printing resin for dentistry, comprising the steps of:
(1) Preparing a functional matrix resin prepolymer: weighing a proper amount of acrylate monomers, a free radical photoinitiator and an active polymerization special reagent, adding a proper amount of organic solvent into a glass reaction bottle, fully dissolving and uniformly mixing by ultrasonic, then placing into a photoreactor for polymerization reaction, and then obtaining a functional matrix resin prepolymer containing active end groups, and sealing in a dark place for later use;
(2) Preparing a photo-curing 3D printing resin raw material: and (3) taking the functional matrix resin prepolymer in the step (1), adding a proper amount of component B, and uniformly mixing and stirring.
The technical scheme of the invention has the following beneficial effects:
1. The photocuring 3D printing resin raw material for dentistry provided by the invention can be applied to various photocuring 3D printing technologies such as SLA, DLP, LCD, CLIP, MJP, two-photon 3D printing, holographic 3D printing and the like; high printing precision, high toughness, small volume reduction rate and excellent mechanical property.
2. The photo-curing 3D printing resin raw material for dentistry provided by the invention has the advantages of high printing precision, high toughness, excellent mechanical property, dormant active end groups, and the photo-curing 3D printing resin raw material can be activated again under external stimulus, so that the partial self-repairing of damaged parts is realized. In addition, the activated end group is also beneficial to secondary modification of the surface of the printing part, and is beneficial to surface modification, coloring and other post-treatments of the substrate.
3. The photocuring 3D printing resin raw material for dentistry provided by the invention has the advantages of simple preparation process, mild reaction conditions, easily available raw materials, wide application range in the market, contribution to industrial production and manufacturing and further reduction of production cost.
Drawings
Fig. 1 is a diagram showing the effect of a component obtained by printing a photo-cured 3D printing resin raw material by a 3D printer in an embodiment of the invention.
Detailed Description
In order to make the objects, technical solutions and advantages of the embodiments of the present invention more clear, the technical solutions of the embodiments of the present invention will be clearly and completely described below with reference to the accompanying drawings of the embodiments of the present invention. It will be apparent that the described embodiments are some, but not all, embodiments of the invention. All other embodiments, which are obtained by a person skilled in the art based on the described embodiments of the invention, fall within the scope of protection of the invention.
Example 1
The embodiment provides a light-cured 3D printing resin for dentistry, which comprises the following components in parts by weight:
Component A
100 Parts of acrylic monomer;
2 parts of a free radical photoinitiator;
a living polymerization special reagent 1;
wherein the acrylic monomer is methyl methacrylate.
Wherein the free radical photoinitiator is diphenyl (2, 4, 6-trimethylbenzoyl) phosphine oxide.
Wherein the special active polymerization reagent is bromoisobutyric acid glycol ester.
Component B
20 Parts of functional monomer;
2 parts of difunctional reactive diluent;
0.02 parts of auxiliary agent;
Wherein the functional monomer is N-isopropyl acrylamide.
Wherein the auxiliary agent is eosin Y.
Wherein the difunctional reactive diluent is tripropylene glycol diacrylate.
The preparation of the photo-curing 3D printing resin for dentistry comprises the following steps:
(1) Preparing a functional matrix resin prepolymer: placing the acrylic ester monomer, the free radical photoinitiator and the active polymerization special reagent in a glass reaction bottle, adding a proper amount of organic solvent, namely dimethylformamide, carrying out ultrasonic treatment to fully dissolve and uniformly mix the acrylic ester monomer, the free radical photoinitiator and the active polymerization special reagent, then placing the mixture in a photoreactor to carry out polymerization reaction for 3 hours, then obtaining a functional matrix resin prepolymer containing active end groups, and sealing the prepolymer in a dark place for standby;
(2) Preparing a photo-curing 3D printing resin raw material: taking 80 parts of the functional matrix resin prepolymer in the step (1), adding the component B, and uniformly mixing and stirring.
And placing the prepared photocuring 3D printing resin raw material in a trough of a DLP 3D printer, setting printing parameters, wherein the thickness of the layer is 500 mu m, the curing time of the layer is 18s, irradiating the system under a light source with the wavelength of 405nm, and then obtaining the printed part.
Example 2
The embodiment provides a light-cured 3D printing resin for dentistry, which comprises the following components in parts by weight:
Component A
200 Parts of acrylic monomer;
1.5 parts of a free radical photoinitiator;
a living polymerization special reagent 1;
Wherein the acrylic acid ester monomer is tert-butyl acrylate.
Wherein the free radical photoinitiator is diphenyl (2, 4, 6-trimethylbenzoyl) phosphine oxide.
Wherein the special active polymerization reagent is bromoisobutyric acid glycol ester.
Component B
40 Parts of functional monomer;
4 parts of difunctional reactive diluent;
0.02 part of auxiliary agent
Wherein the functional monomer is 4-vinyl pyridine.
Wherein the auxiliary agent is eosin Y.
Wherein the difunctional reactive diluent is polyethylene glycol (400) dimethacrylate.
The preparation of the photo-curing 3D printing resin for dentistry comprises the following steps:
(1) Preparing a functional matrix resin prepolymer: placing the acrylic ester monomer, the free radical photoinitiator and the active polymerization special reagent in a glass reaction bottle in parts by weight, adding a proper amount of organic solvent, namely dimethylformamide, carrying out ultrasonic treatment to fully dissolve and uniformly mix the acrylic ester monomer, the free radical photoinitiator and the active polymerization special reagent, then placing the mixture in a photoreactor to carry out polymerization reaction, continuously cooling the system by a small fan, reacting for 3 hours, then obtaining a functional matrix resin prepolymer containing active end groups, and sealing the prepolymer in a dark place for standby;
(2) Preparing a photo-curing 3D printing resin raw material: taking 60 parts of the functional matrix resin prepolymer in the step (1), adding the component B, and uniformly mixing and stirring.
And placing the prepared photocuring 3D printing resin raw material in a trough of a DLP 3D printer, setting printing parameters, wherein the thickness of the layer is 500 mu m, the curing time of the layer is 18s, irradiating the system under a light source with the wavelength of 405nm, and then obtaining the printed part.
Example 3
The embodiment provides a light-cured 3D printing resin for dentistry, which comprises the following components in parts by weight:
Component A
150 Parts of acrylic monomer;
1.5 parts of a free radical photoinitiator;
a living polymerization special reagent 1;
Wherein the acrylic acid ester monomer is tert-butyl acrylate.
Wherein the free radical photoinitiator is 1-hydroxy-cyclohexyl-phenyl ketone.
Wherein the special active polymerization reagent is bromoisobutyric acid glycol ester.
Component B
80 Parts of functional monomer;
2 parts of difunctional reactive diluent;
0.05 part of auxiliary agent
Wherein the functional monomer is 4-vinyl pyridine.
Wherein the auxiliary agent is methylene blue.
Wherein the difunctional reactive diluent is polyethylene glycol (400) dimethacrylate.
The preparation of the photo-curing 3D printing resin for dentistry comprises the following steps:
(1) Preparing a functional matrix resin prepolymer: placing the acrylic ester monomer, the free radical photoinitiator and the active polymerization special reagent in a glass reaction bottle in parts by weight, adding a proper amount of organic solvent, namely dimethylformamide, carrying out ultrasonic treatment to fully dissolve and uniformly mix the acrylic ester monomer, the free radical photoinitiator and the active polymerization special reagent, then placing the mixture in a photoreactor to carry out polymerization reaction, continuously cooling the system by a small fan, reacting for 3 hours, then obtaining a functional matrix resin prepolymer containing active end groups, and sealing the prepolymer in a dark place for standby;
(2) Preparing a photo-curing 3D printing resin raw material: and (3) taking the functional matrix resin prepolymer in the step (1), adding the component B, and uniformly mixing and stirring.
And placing the prepared photocuring 3D printing resin raw material in a trough of a DLP 3D printer, setting printing parameters, wherein the thickness of the layer is 500 mu m, the curing time of the layer is 18s, irradiating the system under a light source with the wavelength of 405nm, and then obtaining the printed part.
Example 4
The embodiment provides a light-cured 3D printing resin for dentistry, which comprises the following components in parts by weight:
Component A
200 Parts of acrylic monomer;
2 parts of a free radical photoinitiator;
a living polymerization-dedicated reagent 2;
Wherein the acrylic acid ester monomer is tert-butyl acrylate.
Wherein the free radical photoinitiator is diphenyl (2, 4, 6-trimethylbenzoyl) phosphine oxide.
Wherein the special active polymerization reagent is bromoisobutyric acid glycol ester.
Component B
20 Parts of functional monomer
2 Parts of difunctional reactive diluent;
0.03 min of auxiliary agent
Wherein the functional monomer is 4-vinyl pyridine.
Wherein the auxiliary agent is methylene blue.
Wherein the difunctional reactive diluent is polyethylene glycol (400) dimethacrylate.
The preparation of the photo-curing 3D printing resin for dentistry comprises the following steps:
(1) Preparing a functional matrix resin prepolymer: placing the acrylic ester monomer, the free radical photoinitiator and the active polymerization special reagent in a glass reaction bottle, adding a proper amount of organic solvent, namely dimethylformamide, carrying out ultrasonic treatment to fully dissolve and uniformly mix the acrylic ester monomer, the free radical photoinitiator and the active polymerization special reagent, then placing the mixture in a photoreactor to carry out polymerization reaction for 3 hours, then obtaining a functional matrix resin prepolymer containing active end groups, and sealing the prepolymer in a dark place for standby;
(2) Preparing a photo-curing 3D printing resin raw material: taking 80 parts of the functional matrix resin prepolymer in the step (1), adding the component B, and uniformly mixing and stirring.
And placing the prepared photocuring 3D printing resin raw material in a trough of a DLP 3D printer, setting printing parameters, wherein the thickness of the layer is 200 mu m, the curing time of the layer is 12s, irradiating the system under a light source with the wavelength of 405nm, and then obtaining the printed part.
Example 5
The embodiment provides a light-cured 3D printing resin for dentistry, which comprises the following components in parts by weight:
Component A
180 Parts of acrylic monomer;
1 part of a free radical photoinitiator;
a living polymerization special reagent 1;
wherein the acrylic monomer is methyl methacrylate.
Wherein the free radical photoinitiator is diphenyl (2, 4, 6-trimethylbenzoyl) phosphine oxide.
Wherein the special active polymerization reagent is bromoisobutyric acid ethyl ester.
Component B
60 Parts of functional monomer;
8 parts of difunctional reactive diluent;
0.02 parts of auxiliary agent;
Wherein the functional monomer is N-isopropyl acrylamide.
Wherein the auxiliary agent is eosin Y.
Wherein the difunctional reactive diluent is tripropylene glycol diacrylate.
The preparation of the photo-curing 3D printing resin for dentistry comprises the following steps:
(1) Preparing a functional matrix resin prepolymer: placing the acrylic ester monomer, the free radical photoinitiator and the active polymerization special reagent in a glass reaction bottle, adding a proper amount of organic solvent, namely dimethylacetamide, carrying out ultrasonic treatment to fully dissolve and uniformly mix the materials, then placing the materials in a photoreactor to carry out polymerization reaction for 3 hours, then obtaining a functional matrix resin prepolymer containing active end groups, and sealing the prepolymer in a dark place for standby;
(2) Preparing a photo-curing 3D printing resin raw material: and (3) taking the functional matrix resin prepolymer in the step (1), adding the component B, and uniformly mixing and stirring.
And placing the prepared photocuring 3D printing resin raw material in a trough of a DLP 3D printer, setting printing parameters, wherein the thickness of the layer is 500 mu m, the curing time of the layer is 18s, irradiating the system under a light source with the wavelength of 405nm, and then obtaining the printed part.
Example 6
The embodiment provides a light-cured 3D printing resin for dentistry, which comprises the following components in parts by weight:
Component A
160 Parts of acrylic monomer;
1.5 parts of a free radical photoinitiator;
1.5 parts of a reagent special for living polymerization;
wherein the acrylic ester monomer is isooctyl acrylate.
Wherein the free radical photoinitiator is p-chlorobenzophenone.
Wherein the special active polymerization reagent is bromoisobutyric acid ethyl ester.
Component B
60 Parts of functional monomer;
6 parts of difunctional reactive diluent;
0.04 parts of auxiliary agent;
wherein the functional monomer is glycidyl methacrylate.
Wherein the auxiliary agent is curcumin.
Wherein the difunctional reactive diluent is a mixture of 1, 4-butanediol diglycidyl ether and polypropylene glycol diglycidyl ether.
The preparation of the photo-curing 3D printing resin for dentistry comprises the following steps:
(1) Preparing a functional matrix resin prepolymer: placing the acrylic ester monomer, the free radical photoinitiator and the active polymerization special reagent in a glass reaction bottle, adding a proper amount of organic solvent, namely dimethylacetamide, carrying out ultrasonic treatment to fully dissolve and uniformly mix the materials, then placing the materials in a photoreactor to carry out polymerization reaction for 3 hours, then obtaining a functional matrix resin prepolymer containing active end groups, and sealing the prepolymer in a dark place for standby;
(2) Preparing a photo-curing 3D printing resin raw material: and (3) taking the functional matrix resin prepolymer in the step (1), adding the component B, and uniformly mixing and stirring.
And placing the prepared photocuring 3D printing resin raw material in a trough of a DLP 3D printer, setting printing parameters, wherein the thickness of the layer is 500 mu m, the curing time of the layer is 18s, irradiating the system under a light source with the wavelength of 405nm, and then obtaining the printed part.
Experimental example 1
The printed parts obtained in examples 1 to 6 were taken and scored on the surface of the parts by a knife, and then placed under a light source having a wavelength of 405nm for one hour, and the scratch was found to be significantly reduced or disappeared.
Experimental example 2
The printed parts obtained in examples 1 to 6 were taken and coated with a layer of polyethylene glycol (400) dimethacrylate on the surface, and then irradiated with a light source having a wavelength of 405nm for 20 minutes, and the coated parts were rinsed to find that the polyethylene glycol (400) dimethacrylate had been linked to the part surface.
Examples 1-6 the raw materials for preparing the photo-cured 3D printing resin showed good mechanical properties and printing properties after 3D printing; when the method is used for 3D printing, the curing speed is relatively high, the time consumption is short, the printing precision is high, the toughness is high, and the mechanical property is excellent.
And as can be seen from experimental examples 1-2, the parts of the raw materials of the photo-cured 3D printing resin prepared in examples 1-5 after 3D printing show good self-repairing function, and the surfaces of the parts are easy to modify.
Namely, examples 1-6 prepare a photo-curing 3D printing resin raw material, the functional matrix resin prepolymer of which has dormant active end groups, and can be activated again under external stimulus to realize the partial self-repair of damaged parts. In addition, the activated end group is also beneficial to secondary modification of the surface of the printing part, and is beneficial to surface modification, coloring and other post-treatments of the substrate.
The preparation process of the raw materials for preparing the photo-curing 3D printing resin in the embodiments 1-6 is simple, the reaction condition is mild, the raw materials are easy to obtain, the industrialized production and manufacturing are facilitated, and the production cost is further reduced.
While the foregoing is directed to the preferred embodiments of the present invention, it will be appreciated by those skilled in the art that various modifications and adaptations can be made without departing from the principles of the present invention, and such modifications and adaptations are intended to be comprehended within the scope of the present invention.
Claims (3)
1. The photocuring 3D printing resin for dentistry is characterized by comprising the following components in parts by weight:
Component A
100-200 Parts of acrylic monomer;
1-2 parts of a free radical photoinitiator;
1-2 parts of a special active polymerization reagent;
the acrylic ester monomer is one of methyl methacrylate, hydroxypropyl methacrylate, isooctyl acrylate and tert-butyl acrylate;
Component B
20-80 Parts of functional monomer;
2-8 parts of difunctional reactive diluent;
The functional monomer is one of N-isopropyl acrylamide, 1-perylene methyl methacrylate, 4-vinyl pyridine and glycidyl methacrylate;
The component B also comprises 0.02-0.05 part by weight of an auxiliary agent;
The auxiliary agent is one of curcumin, eosin Y, gardenia blue, fluorescent whitening powder and methylene blue;
the free radical photoinitiator in the component A is one or more of diphenyl (2, 4, 6-trimethyl benzoyl) phosphine oxide, 1-hydroxy-cyclohexyl-phenyl ketone, p-chlorobenzophenone, ethyl p-dimethylaminobenzoate and 2, 4-diethyl thiazolone;
The special active polymerization reagent in the component A is one or more of bromoisobutyric acid glycol ester and bromoisobutyric acid ethyl ester.
2. The photocurable 3D printing resin for dentistry according to claim 1, wherein the difunctional reactive diluent in component B is one or more of 1, 4-butanediol diglycidyl ether, polypropylene glycol diglycidyl ether, neopentyl glycol diglycidyl ether, tripropylene glycol diacrylate, 1, 6-hexanediol diacrylate, neopentyl glycol diethoxy diacrylate, polyethylene glycol (400) dimethacrylate.
3. A method for preparing a photocurable 3D printing resin for dentistry according to any one of claims 1-2, comprising the steps of:
(1) Preparing a functional matrix resin prepolymer: weighing a proper amount of acrylate monomers, a free radical photoinitiator and an active polymerization special reagent, adding a proper amount of organic solvent into a glass reaction bottle, fully dissolving and uniformly mixing by ultrasonic, then placing into a photoreactor for polymerization reaction, and then obtaining a functional matrix resin prepolymer containing active end groups, and sealing in a dark place for later use;
(2) Preparing a photo-curing 3D printing resin raw material: and (3) taking the functional matrix resin prepolymer in the step (1), adding a proper amount of component B, and uniformly mixing and stirring.
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