CN108690327A - A kind of 3D printing UV curing photosensitive resin and preparation method thereof - Google Patents
A kind of 3D printing UV curing photosensitive resin and preparation method thereof Download PDFInfo
- Publication number
- CN108690327A CN108690327A CN201810531543.4A CN201810531543A CN108690327A CN 108690327 A CN108690327 A CN 108690327A CN 201810531543 A CN201810531543 A CN 201810531543A CN 108690327 A CN108690327 A CN 108690327A
- Authority
- CN
- China
- Prior art keywords
- photosensitive resin
- printing
- curing
- curing photosensitive
- aliphatic epoxy
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 229920005989 resin Polymers 0.000 title claims abstract description 66
- 239000011347 resin Substances 0.000 title claims abstract description 66
- 238000010146 3D printing Methods 0.000 title claims abstract description 45
- 238000003848 UV Light-Curing Methods 0.000 title claims abstract description 31
- 238000002360 preparation method Methods 0.000 title claims abstract description 21
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 40
- 239000004844 aliphatic epoxy resin Substances 0.000 claims abstract description 22
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 22
- 239000003085 diluting agent Substances 0.000 claims abstract description 22
- 239000002270 dispersing agent Substances 0.000 claims abstract description 22
- 239000000377 silicon dioxide Substances 0.000 claims abstract description 20
- CYIGRWUIQAVBFG-UHFFFAOYSA-N 1,2-bis(2-ethenoxyethoxy)ethane Chemical class C=COCCOCCOCCOC=C CYIGRWUIQAVBFG-UHFFFAOYSA-N 0.000 claims abstract description 12
- 125000001931 aliphatic group Chemical group 0.000 claims abstract description 12
- 229910021389 graphene Inorganic materials 0.000 claims abstract description 6
- 238000003756 stirring Methods 0.000 claims description 30
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical class [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 29
- 238000006243 chemical reaction Methods 0.000 claims description 27
- 239000000203 mixture Substances 0.000 claims description 12
- 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 11
- KCTAWXVAICEBSD-UHFFFAOYSA-N prop-2-enoyloxy prop-2-eneperoxoate Chemical compound C=CC(=O)OOOC(=O)C=C KCTAWXVAICEBSD-UHFFFAOYSA-N 0.000 claims description 11
- 229920001400 block copolymer Polymers 0.000 claims description 6
- 238000000034 method Methods 0.000 claims description 6
- 150000003254 radicals Chemical class 0.000 claims description 4
- VILCJCGEZXAXTO-UHFFFAOYSA-N 2,2,2-tetramine Chemical group NCCNCCNCCN VILCJCGEZXAXTO-UHFFFAOYSA-N 0.000 claims description 3
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical group NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 claims description 3
- PDQAZBWRQCGBEV-UHFFFAOYSA-N Ethylenethiourea Chemical compound S=C1NCCN1 PDQAZBWRQCGBEV-UHFFFAOYSA-N 0.000 claims description 3
- HTKFORQRBXIQHD-UHFFFAOYSA-N allylthiourea Chemical compound NC(=S)NCC=C HTKFORQRBXIQHD-UHFFFAOYSA-N 0.000 claims description 3
- 229960001748 allylthiourea Drugs 0.000 claims description 3
- 238000005576 amination reaction Methods 0.000 claims description 3
- 150000001732 carboxylic acid derivatives Chemical class 0.000 claims description 3
- 150000001768 cations Chemical class 0.000 claims description 3
- VOZRXNHHFUQHIL-UHFFFAOYSA-N glycidyl methacrylate Chemical compound CC(=C)C(=O)OCC1CO1 VOZRXNHHFUQHIL-UHFFFAOYSA-N 0.000 claims description 3
- 239000003999 initiator Substances 0.000 claims description 3
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 claims description 3
- 229960001124 trientine Drugs 0.000 claims description 3
- LCZVSXRMYJUNFX-UHFFFAOYSA-N 2-[2-(2-hydroxypropoxy)propoxy]propan-1-ol Chemical compound CC(O)COC(C)COC(C)CO LCZVSXRMYJUNFX-UHFFFAOYSA-N 0.000 claims description 2
- FIHBHSQYSYVZQE-UHFFFAOYSA-N 6-prop-2-enoyloxyhexyl prop-2-enoate Chemical group 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 1
- 229910019142 PO4 Inorganic materials 0.000 claims 1
- XBDQKXXYIPTUBI-UHFFFAOYSA-M Propionate Chemical compound CCC([O-])=O XBDQKXXYIPTUBI-UHFFFAOYSA-M 0.000 claims 1
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 claims 1
- 239000007983 Tris buffer Substances 0.000 claims 1
- ZRXADTFMGYNRKV-UHFFFAOYSA-N [S].C1=CC=CC2=CC=CC=C21 Chemical group [S].C1=CC=CC2=CC=CC=C21 ZRXADTFMGYNRKV-UHFFFAOYSA-N 0.000 claims 1
- 230000002378 acidificating effect Effects 0.000 claims 1
- WBJINCZRORDGAQ-UHFFFAOYSA-N formic acid ethyl ester Natural products CCOC=O WBJINCZRORDGAQ-UHFFFAOYSA-N 0.000 claims 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 claims 1
- 239000010452 phosphate Substances 0.000 claims 1
- 239000000243 solution Substances 0.000 claims 1
- LJRSZGKUUZPHEB-UHFFFAOYSA-N 2-[2-(2-prop-2-enoyloxypropoxy)propoxy]propyl prop-2-enoate Chemical class C=CC(=O)OC(C)COC(C)COC(C)COC(=O)C=C LJRSZGKUUZPHEB-UHFFFAOYSA-N 0.000 abstract description 9
- 239000004593 Epoxy Substances 0.000 abstract description 9
- 150000001252 acrylic acid derivatives Chemical class 0.000 abstract description 9
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 16
- 230000000052 comparative effect Effects 0.000 description 14
- 239000000463 material Substances 0.000 description 11
- 150000001336 alkenes Chemical class 0.000 description 10
- 238000001723 curing Methods 0.000 description 10
- 238000005516 engineering process Methods 0.000 description 6
- 238000000016 photochemical curing Methods 0.000 description 6
- 230000000694 effects Effects 0.000 description 3
- 238000007711 solidification Methods 0.000 description 3
- 230000008023 solidification Effects 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- VALXVSHDOMUUIC-UHFFFAOYSA-N 2-methylprop-2-enoic acid;phosphoric acid Chemical group OP(O)(O)=O.CC(=C)C(O)=O VALXVSHDOMUUIC-UHFFFAOYSA-N 0.000 description 2
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 2
- OKKRPWIIYQTPQF-UHFFFAOYSA-N Trimethylolpropane trimethacrylate Chemical compound CC(=C)C(=O)OCC(CC)(COC(=O)C(C)=C)COC(=O)C(C)=C OKKRPWIIYQTPQF-UHFFFAOYSA-N 0.000 description 2
- -1 allyl ester Chemical class 0.000 description 2
- 125000003277 amino group Chemical group 0.000 description 2
- 230000008602 contraction Effects 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 125000003700 epoxy group Chemical group 0.000 description 2
- 150000002148 esters Chemical class 0.000 description 2
- MTZQAGJQAFMTAQ-UHFFFAOYSA-N ethyl benzoate Chemical compound CCOC(=O)C1=CC=CC=C1 MTZQAGJQAFMTAQ-UHFFFAOYSA-N 0.000 description 2
- 239000003365 glass fiber Substances 0.000 description 2
- 238000001459 lithography Methods 0.000 description 2
- PSZYNBSKGUBXEH-UHFFFAOYSA-N naphthalene-1-sulfonic acid Chemical group C1=CC=C2C(S(=O)(=O)O)=CC=CC2=C1 PSZYNBSKGUBXEH-UHFFFAOYSA-N 0.000 description 2
- 239000004575 stone Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 239000000805 composite resin Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- XYIBRDXRRQCHLP-UHFFFAOYSA-N ethyl acetoacetate Chemical compound CCOC(=O)CC(C)=O XYIBRDXRRQCHLP-UHFFFAOYSA-N 0.000 description 1
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 1
- 230000005764 inhibitory process Effects 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N o-dimethylbenzene Natural products CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- 238000007639 printing Methods 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000011343 solid material Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L63/00—Compositions of epoxy resins; Compositions of derivatives of epoxy resins
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B33—ADDITIVE MANUFACTURING TECHNOLOGY
- B33Y—ADDITIVE MANUFACTURING, i.e. MANUFACTURING OF THREE-DIMENSIONAL [3-D] OBJECTS BY ADDITIVE DEPOSITION, ADDITIVE AGGLOMERATION OR ADDITIVE LAYERING, e.g. BY 3-D PRINTING, STEREOLITHOGRAPHY OR SELECTIVE LASER SINTERING
- B33Y70/00—Materials specially adapted for additive manufacturing
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L63/00—Compositions of epoxy resins; Compositions of derivatives of epoxy resins
- C08L63/10—Epoxy resins modified by unsaturated compounds
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Materials Engineering (AREA)
- Epoxy Resins (AREA)
Abstract
The present invention discloses a kind of 3D printing UV curing photosensitive resin and preparation method thereof, and the photosensitive resin includes each component of following mass percentage:The aliphatic epoxy resin of 25~45wt.%, 10~25wt.% aliphatic epoxy acrylates, 1~6wt.% silica, 2~10wt.%N, N- mesitylenic acid ethyl esters, 0.5~6wt.% tripropylene glycol diacrylates, 5~15wt.% triethylene glycol divinyl ethers, 0.05~4wt.% modified graphenes, 0.05~5wt.% photoinitiators, 5~30wt.% reactive diluents, 0.1~5wt.% dispersants, 0.1~3wt.% accelerating agents.The photosensitive resin may be directly applied to 3D printing and complicated product be made, and good toughness, viscosity is low, and forming is fast, has ensured the Quick-forming of 3D printing product, meets industrial use and requires.
Description
Technical field
The invention belongs to the technical fields of 3D printing material, and in particular to a kind of 3D printing UV curing photosensitive resin
And preparation method thereof.
Background technology
3D printing is the new technology developed in recent decades, is received by more and more people.Photocuring is quick
Forming technique (SLA) is to develop earliest, most ripe technology in 3D printing field.Introduction To Stereolithography is also known as cubic light
Lithography or Stereo Lithography.Its course of work is that under the control of the computer, UV laser beam is with the profile of each layering cross section
Data are that foundation is successively scanned the photosensitive resin in feed reservoir, and the region that ultraviolet light passes through, photosensitive resin absorbs luminous energy
Photopolymerization occurs to cure, forms a thin cross-sectional layers.After the completion of one layer of solidification, computer controls movable workbench one
The height of a thickness (0.1mm) understands the uncured liquid photosensitive resin of layer overlay again on the cured resin surface of last layer,
The solidification process of last layer is repeated, new cured layer can be firmly bonded in preceding layer.It so repeats, layer upon layer, most end form
At entire product model.But, the photosensitive resin performance used in photocuring is to influence the matter of utmost importance of SLA technology development.Gao Xing
Energy photosensitive resin is the developing research direction of current 3D printing technique.
Due to processing technologys such as photosensitive resin need not heat, high pressures, but preset model is formed by being layering, because
This can have that matter is crisp, defect of poor mechanical property is to limit its large-scale application.How the toughness of photosensitive resin to be increased, one
It is directly 3D printing technique application problem to be solved.ZL201410074336.2 discloses free radical and causes allyl ester resin
Composite glass fiber photosensitive resin, obtained photo-curing material have good intensity and rigidity, but content of glass fiber
It is excessively high to make disperseing uneven in its resin, and hard and crisp also it is unfavorable for large-scale promotion;201610237237.0 disclosing
Prepolymer resin is the 3D printing material that is prepared of raw material, and the cure shrinkage of material is small, forming precision is high, but cures speed
Degree is slow, and toughness is relatively low.
In order to improve 3D printing photosensitive resin material flexibility, expand the application field of photosensitive resin material, exploitation is solid
Change speed it is fast, shrinking percentage is small, the 3D printing of color inhibition, good toughness with photosensitive resin material become era development inevitable requirement.
Invention content
For this purpose, technical problem to be solved by the present invention lies in overcoming, existing photo-curing material viscosity is high, curing rate is slow
Etc. technical bottlenecks, develop that a kind of curing rate is fast, shrinking percentage is small, the 3D printing of good toughness UV curing photosensitive resin material
And preparation method thereof.
The purpose of the present invention is what is be achieved through the following technical solutions:
The present invention provides a kind of 3D printing UV curing photosensitive resin, the photosensitive resin includes following weight hundred
Divide the component of content:
Preferably, the light source of the photosensitive resin is the ultraviolet light of 200~500nm of wavelength.
Preferably, the modified graphene is modified to graphene oxide with triethylene tetramine and ethylenediamine, makes it
The modified graphene obtained after amination.Epoxy group in the amino group and aliphatic epoxy resin of the modified graphene
Between there is stronger chemical bond, this effect can improve the calorifics and mechanical property of photosensitive resin.
Preferably, the photoinitiator is selected from one or both of cation light initiator, free radical photo-initiation
Mixture.
Preferably, the reactive diluent is 1,6- hexanediyl esters, glycidyl methacrylate, 3 third
The arbitrary proportion mixture of one or more of glycol diglycidyl ester, trimethylolpropane trimethacrylate.
Preferably, the dispersant is naphthalene sulfonic acids base, amino modified block copolymer, polybasic carboxylic acid based block copolymer
One or more of arbitrary proportion mixture.
Preferably, the accelerating agent is methacrylic acid phosphoric acid ester, ethylene thiourea, one kind in Allyl thiourea or several
The arbitrary proportion mixture of kind.
The present invention also provides a kind of preparation method of 3D printing UV curing photosensitive resin, the method includes with
Lower step:
A, in a kettle, aliphatic epoxy resin, aliphatic epoxy acrylate, silica, N, N- diformazans is added
Yl benzoic acid ethyl ester, tripropylene glycol diacrylate, triethylene glycol divinyl ether, modified graphene and reactive diluent, uniformly
Stir 10~60min;
B, again in a kettle, dispersant, 5~50min of uniform stirring is added;
C, photoinitiator and accelerating agent are added in middle reaction kettle, temperature of reaction kettle is 40~80 DEG C, waits for that solution is transparent
Stop stirring after color.
Photosensitive resin prepared by the present invention may be directly applied to 3D printing and complicated product, good toughness, viscosity be made
Low, forming is fast, has ensured the Quick-forming of 3D printing product, meets industrial use and requires.
Compared with prior art, the present invention has following advantageous effect:
(1) present invention uses aliphatic epoxy resin, aliphatic epoxy acrylate, the N of low viscosity, N- dimethyl benzene first
Acetoacetic ester, tripropylene glycol diacrylate, triethylene glycol divinyl ether are oligomer, keep the photosensitive resin viscosity of the present invention low
In 300cps, viscosity is low, and molding is fast, has ensured the Quick-forming of 3D products;
(2) addition of modified graphene and silica makes the photo-curing material good toughness of the present invention, greatly increases use
Service life meets industrial use and requires;
(3) cubical contraction of photosensitive resin of the invention is extremely low so that 3D printing product in use will not be because
Occur compared with large deformation for contraction, it is most important for obtaining high-precision printed product, it is conducive to the holding of shape of product.
Specific implementation mode
With reference to specific embodiment, the present invention is described in detail.Following embodiment will be helpful to the technology of this field
Personnel further understand the present invention, but the invention is not limited in any way.It should be pointed out that the ordinary skill of this field
For personnel, without departing from the inventive concept of the premise, various modifications and improvements can be made.These belong to the present invention
Protection domain.
Following embodiment provides a kind of 3D printing UV curing photosensitive resin, and the photosensitive resin includes following heavy
Measure the component of percentage composition:
The light source of the photosensitive resin is the ultraviolet light of 200~500nm of wavelength.
The modified graphene is modified to graphene oxide with triethylene tetramine and ethylenediamine, after making its amination
The modified graphene of acquisition.Have between epoxy group in the amino group and aliphatic epoxy resin of the modified graphene
Stronger chemical bond, this effect can improve the calorifics and mechanical property of photosensitive resin.
The photoinitiator is selected from the mixture of one or both of cation light initiator, free radical photo-initiation.
The reactive diluent is 1,6 hexanediol diacrylate, glycidyl methacrylate, tripropylene glycol two
The arbitrary proportion mixture of one or more of ethylene oxidic ester, trimethylolpropane trimethacrylate.
The dispersant is one in naphthalene sulfonic acids base, amino modified block copolymer, polybasic carboxylic acid based block copolymer
Kind or several arbitrary proportion mixtures.
The accelerating agent is appointing for one or more of methacrylic acid phosphoric acid ester, ethylene thiourea, Allyl thiourea
Meaning scalemic thereof.
Embodiment 1
A kind of 3D printing UV curing photosensitive resin is present embodiments provided, component and mass percent are:
The aliphatic epoxy resin of 45wt.%, 25wt.% aliphatic epoxy acrylates, 6wt.% silica, 2wt.%N, N-
Mesitylenic acid ethyl ester, 1.9wt.% tripropylene glycol diacrylates, 5wt.% triethylene glycol divinyl ethers, 3wt.% are modified
Graphene, 5wt.% photoinitiators, 5wt.% reactive diluents, 0.1wt.% dispersants, 2wt.% accelerating agents.
Preparation method:
A, in the reaction kettle equipped with blender, thermometer, condenser and charging spout, aliphatic epoxy resin, fat is added
Fat race epoxy acrylate, silica, N, N- mesitylenic acids ethyl ester, tripropylene glycol diacrylate, triethylene glycol diethyl
Alkene ether, modified graphene and reactive diluent, uniform stirring 60min;
B, in a kettle, dispersant, uniform stirring 50min is added;
C, toward addition photoinitiator and accelerating agent inside reaction kettle, temperature of reaction kettle is 80 DEG C, waits for the transparent color of solution
Stop stirring afterwards.
The ultraviolet light that light source for curing the photosensitive resin is wavelength 500nm.
Embodiment 2
A kind of 3D printing UV curing photosensitive resin is present embodiments provided, component and mass percent are:
The aliphatic epoxy resin of 25wt.%, 25wt.% aliphatic epoxy acrylates, 1wt.% silica, 10wt.%N, N-
Mesitylenic acid ethyl ester, 0.5wt.% tripropylene glycol diacrylates, 15wt.% triethylene glycol divinyl ethers, 4wt.% change
Property graphene, 5wt.% photoinitiators, 6.5wt.% reactive diluents, 5wt.% dispersants, 3wt.% accelerating agents.
Preparation method:
A, in the reaction kettle equipped with blender, thermometer, condenser and charging spout, aliphatic epoxy resin, fat is added
Fat race epoxy acrylate, silica, N, N- mesitylenic acids ethyl ester, tripropylene glycol diacrylate, triethylene glycol diethyl
Alkene ether, modified graphene and reactive diluent, uniform stirring 60min;
B, in a kettle, dispersant, uniform stirring 5min is added;
C, toward addition photoinitiator and accelerating agent inside reaction kettle, temperature of reaction kettle is 40 DEG C, waits for the transparent color of solution
Stop stirring afterwards.
The ultraviolet light that light source for curing the photosensitive resin is wavelength 200nm.
Embodiment 3
A kind of 3D printing UV curing photosensitive resin is present embodiments provided, component and mass percent are:
The aliphatic epoxy resin of 35wt.%, 10wt.% aliphatic epoxy acrylates, 3.5wt.% silica, 6wt.%N, N-
Mesitylenic acid ethyl ester, 6wt.% tripropylene glycol diacrylates, 10wt.% triethylene glycol divinyl ethers, 0.05wt.% change
Property graphene, 0.05wt.% photoinitiators, 24.3wt.% reactive diluents, 5wt.% dispersants, 0.1wt.% accelerating agents.
Preparation method:
A, in the reaction kettle equipped with blender, thermometer, condenser and charging spout, aliphatic epoxy resin, fat is added
Fat race epoxy acrylate, silica, N, N- mesitylenic acids ethyl ester, tripropylene glycol diacrylate, triethylene glycol diethyl
Alkene ether, modified graphene and reactive diluent, uniform stirring 35min;
B, in a kettle, dispersant, uniform stirring 25min is added;
C, toward addition photoinitiator and accelerating agent inside reaction kettle, temperature of reaction kettle is 60 DEG C, waits for the transparent color of solution
Stop stirring afterwards.
The ultraviolet light that light source for curing the photosensitive resin is wavelength 300nm.
Embodiment 4
A kind of 3D printing UV curing photosensitive resin is present embodiments provided, component and mass percent are:
The aliphatic epoxy resin of 25wt.%, 20wt.% aliphatic epoxy acrylates, 2wt.% silica, 10wt.%N, N-
Mesitylenic acid ethyl ester, 3wt.% tripropylene glycol diacrylates, 5wt.% triethylene glycol divinyl ethers, 2wt.% are modified stone
Black alkene, 2.5wt.% photoinitiators, 30wt.% reactive diluents, 1.5wt.% dispersants, 0.5wt.% accelerating agents.
Preparation method:
A, in the reaction kettle equipped with blender, thermometer, condenser and charging spout, aliphatic epoxy resin, fat is added
Fat race epoxy acrylate, silica, N, N- mesitylenic acids ethyl ester, tripropylene glycol diacrylate, triethylene glycol diethyl
Alkene ether, modified graphene and reactive diluent, uniform stirring 40min;
B, in a kettle, dispersant, uniform stirring 15min is added;
C, toward addition photoinitiator and accelerating agent inside reaction kettle, temperature of reaction kettle is 50 DEG C, waits for the transparent color of solution
Stop stirring afterwards.
The ultraviolet light that light source for curing the photosensitive resin is wavelength 400nm.
Embodiment 5
A kind of 3D printing UV curing photosensitive resin is present embodiments provided, component and mass percent are:
The aliphatic epoxy resin of 30wt.%, 25wt.% aliphatic epoxy acrylates, 3wt.% silica, 8wt.%N, N-
Mesitylenic acid ethyl ester, 2wt.% tripropylene glycol diacrylates, 10wt.% triethylene glycol divinyl ethers, 3wt.% are modified
Graphene, 2wt.% photoinitiators, 12wt.% reactive diluents, 3wt.% dispersants, 2wt.% accelerating agents.
Preparation method:
A, in the reaction kettle equipped with blender, thermometer, condenser and charging spout, aliphatic epoxy resin, fat is added
Fat race epoxy acrylate, silica, N, N- mesitylenic acids ethyl ester, tripropylene glycol diacrylate, triethylene glycol diethyl
Alkene ether, modified graphene and reactive diluent, uniform stirring 30min;
B, in a kettle, dispersant, uniform stirring 20min is added;
C, toward addition photoinitiator and accelerating agent inside reaction kettle, temperature of reaction kettle is 60 DEG C, waits for the transparent color of solution
Stop stirring afterwards.
The ultraviolet light that light source for curing the photosensitive resin is wavelength 350nm.
Embodiment 6
A kind of 3D printing UV curing photosensitive resin is present embodiments provided, component and mass percent are:
The aliphatic epoxy resin of 45wt.%, 20wt.% aliphatic epoxy acrylates, 3wt.% silica, 6wt.%N, N-
Mesitylenic acid ethyl ester, 2wt.% tripropylene glycol diacrylates, 5wt.% triethylene glycol divinyl ethers, 3wt.% are modified stone
Black alkene, 2wt.% photoinitiators, 10wt.% reactive diluents, 2wt.% dispersants, 2wt.% accelerating agents.
Preparation method:
A, in the reaction kettle equipped with blender, thermometer, condenser and charging spout, aliphatic epoxy resin, fat is added
Fat race epoxy acrylate, silica, N, N- mesitylenic acids ethyl ester, tripropylene glycol diacrylate, triethylene glycol diethyl
Alkene ether, modified graphene and reactive diluent, uniform stirring 40min;
B, in a kettle, dispersant, uniform stirring 30min is added;
C, toward addition photoinitiator and accelerating agent inside reaction kettle, temperature of reaction kettle is 70 DEG C, waits for the transparent color of solution
Stop stirring afterwards.
The ultraviolet light that light source for curing the photosensitive resin is wavelength 450nm.
Embodiment 7
A kind of 3D printing UV curing photosensitive resin is present embodiments provided, component and mass percent are:
The aliphatic epoxy resin of 40wt.%, 25wt.% aliphatic epoxy acrylates, 5wt.% silica, 5wt.%N, N-
Mesitylenic acid ethyl ester, 4wt.% tripropylene glycol diacrylates, 10wt.% triethylene glycol divinyl ethers, 2wt.% are modified
Graphene, 2wt.% photoinitiators, 5wt.% reactive diluents, 1wt.% dispersants, 1wt.% accelerating agents.
Preparation method:
A, in the reaction kettle equipped with blender, thermometer, condenser and charging spout, aliphatic epoxy resin, fat is added
Fat race epoxy acrylate, silica, N, N- mesitylenic acids ethyl ester, tripropylene glycol diacrylate, triethylene glycol diethyl
Alkene ether, modified graphene and reactive diluent, uniform stirring 35min;
B, in a kettle, dispersant, uniform stirring 15min is added;
C, toward addition photoinitiator and accelerating agent inside reaction kettle, temperature of reaction kettle is 50 DEG C, waits for the transparent color of solution
Stop stirring afterwards.
The ultraviolet light that light source for curing the photosensitive resin is wavelength 250nm.
Embodiment 8
A kind of 3D printing UV curing photosensitive resin is present embodiments provided, component and mass percent are:
The aliphatic epoxy resin of 30wt.%, 25wt.% aliphatic epoxy acrylates, 5wt.% silica, 5wt.%N, N-
Mesitylenic acid ethyl ester, 4wt.% tripropylene glycol diacrylates, 10wt.% triethylene glycol divinyl ethers, 2wt.% are modified
Graphene, 2wt.% photoinitiators, 15wt.% reactive diluents, 1wt.% dispersants, 1wt.% accelerating agents.
Preparation method:
A, in the reaction kettle equipped with blender, thermometer, condenser and charging spout, aliphatic epoxy resin, fat is added
Fat race epoxy acrylate, silica, N, N- mesitylenic acids ethyl ester, tripropylene glycol diacrylate, triethylene glycol diethyl
Alkene ether, modified graphene and reactive diluent, uniform stirring 20min;
B, in a kettle, dispersant, uniform stirring 20min is added;
C, toward addition photoinitiator and accelerating agent inside reaction kettle, temperature of reaction kettle is 50 DEG C, waits for the transparent color of solution
Stop stirring afterwards.
The ultraviolet light that light source for curing the photosensitive resin is wavelength 500nm.
The each component mass percentage of 3D printing UV curing photosensitive resin described in embodiment 1-8 such as 1 institute of table
Show.
The mass percentage of each component in 1 embodiment of table
Comparative example 1
This comparative example provides a kind of 3D printing UV curing photosensitive resin, and component and content are as shown in table 2,
Preparation method is same as Example 1.
Comparative example 2
This comparative example provides a kind of 3D printing UV curing photosensitive resin, and component and content are as shown in table 2,
Preparation method is same as Example 2.
Comparative example 3-4
Comparative example 3-4 provides a kind of 3D printing UV curing photosensitive resin, and component and content are as shown in table 2,
Preparation method is same as Example 3.
Comparative example 5
This comparative example provides a kind of 3D printing UV curing photosensitive resin, and component and content are as shown in table 2,
Preparation method is same as Example 1.
Comparative example 6
This comparative example provides a kind of 3D printing UV curing photosensitive resin, and component and content are as shown in table 2,
Preparation method is same as Example 6.
The mass percentage of each component in 2 embodiment of table
Comparative example 7
This comparative example provides a kind of 3D printing UV curing photosensitive resin, component and content and 3 base of embodiment
This is identical, the difference is that only:Using unmodified graphene oxide in this comparative example.
Preparation method is same as Example 6.
Compliance test result:
Photo-curing material prepared by embodiment and comparative example is placed in 3D printer and carries out printing test, to 3D printing light
The performance of solidification solid material and shaped article is tested, and test result is as shown in table 3:
Table 3
There are many concrete application approach of the present invention, the above is only a preferred embodiment of the present invention.More than it should be pointed out that
Embodiment is merely to illustrate the present invention, and the protection domain being not intended to restrict the invention.For the common skill of the art
For art personnel, without departing from the principle of the present invention, several improvement can also be made, these improvement also should be regarded as this hair
Bright protection domain.
Claims (8)
1. a kind of 3D printing UV curing photosensitive resin, which is characterized in that the photosensitive resin includes following weight percent
The component of content:
2. 3D printing UV curing photosensitive resin as described in claim 1, which is characterized in that the light of the photosensitive resin
Source is the ultraviolet light of 200~500nm of wavelength.
3. 3D printing UV curing photosensitive resin as described in claim 1, which is characterized in that the modified graphene is
Graphene oxide is modified with triethylene tetramine and ethylenediamine, makes the modified graphene obtained after its amination.
4. 3D printing UV curing photosensitive resin as described in claim 1, which is characterized in that the photoinitiator is selected from
The mixture of one or both of cation light initiator, free radical photo-initiation.
5. 3D printing UV curing photosensitive resin as described in claim 1, which is characterized in that the reactive diluent is
1,6 hexanediol diacrylate, glycidyl methacrylate, tripropylene glycol 2-glycidyl ester, trimethylolpropane tris
The arbitrary proportion mixture of one or more of acrylate.
6. 3D printing UV curing photosensitive resin as described in claim 1, which is characterized in that the dispersant is naphthalene sulphur
The arbitrary proportion mixture of one or more of acidic group, amino modified block copolymer, polybasic carboxylic acid based block copolymer.
7. 3D printing UV curing photosensitive resin as described in claim 1, which is characterized in that the accelerating agent is methyl
The arbitrary proportion mixture of one or more of acrylated phosphate, ethylene thiourea, Allyl thiourea.
8. a kind of preparation method of such as claim 1-7 any one of them 3D printing UV curing photosensitive resins, special
Sign is, the described method comprises the following steps:
A, in a kettle, aliphatic epoxy resin, aliphatic epoxy acrylate, silica, N, N- dimethyl benzenes is added
Ethyl formate, tripropylene glycol diacrylate, triethylene glycol divinyl ether, modified graphene and reactive diluent, uniform stirring
10~60min;
B, again in a kettle, dispersant, 5~50min of uniform stirring is added;
C, photoinitiator and accelerating agent are added in a kettle, temperature of reaction kettle is 40~80 DEG C, after the transparent color of solution
Stop stirring.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810531543.4A CN108690327A (en) | 2018-05-29 | 2018-05-29 | A kind of 3D printing UV curing photosensitive resin and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810531543.4A CN108690327A (en) | 2018-05-29 | 2018-05-29 | A kind of 3D printing UV curing photosensitive resin and preparation method thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN108690327A true CN108690327A (en) | 2018-10-23 |
Family
ID=63849260
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201810531543.4A Pending CN108690327A (en) | 2018-05-29 | 2018-05-29 | A kind of 3D printing UV curing photosensitive resin and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN108690327A (en) |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109867755A (en) * | 2019-02-22 | 2019-06-11 | 苏州轻金三维科技有限公司 | A kind of photosensitive resin preparation method suitable for 3 D-printing |
| CN109867756A (en) * | 2019-02-22 | 2019-06-11 | 苏州轻金三维科技有限公司 | A kind of 3 D-printing blue light curing photosensitive resin and preparation method thereof |
| CN112062896A (en) * | 2020-08-25 | 2020-12-11 | 南方科技大学 | Energy-absorbing 3D printing material, preparation method thereof and energy-absorbing device |
| CN112574366A (en) * | 2020-12-22 | 2021-03-30 | 杜晖 | Photosensitive resin, transparent mold for injection molding of photosensitive resin and injection molding method |
| CN115926635A (en) * | 2022-12-02 | 2023-04-07 | 华侨大学 | Ultraviolet-heat dual curing adhesive and preparation method and application in 3D printing |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH07228644A (en) * | 1994-02-21 | 1995-08-29 | Teijin Seiki Co Ltd | Resin composition for optical three-dimensional modeling |
| CN106773532A (en) * | 2015-11-19 | 2017-05-31 | 芜湖启泽信息技术有限公司 | It is a kind of to be applied to photosensitive resin of 3D printing and preparation method thereof |
| CN106749942A (en) * | 2016-12-15 | 2017-05-31 | 深圳飞扬兴业科技有限公司 | A kind of 3D printing ultraviolet photocureable material and preparation method thereof |
| CN106977665A (en) * | 2017-03-30 | 2017-07-25 | 中北大学 | A kind of 3D printing photosensitive resin and preparation method thereof |
-
2018
- 2018-05-29 CN CN201810531543.4A patent/CN108690327A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH07228644A (en) * | 1994-02-21 | 1995-08-29 | Teijin Seiki Co Ltd | Resin composition for optical three-dimensional modeling |
| CN106773532A (en) * | 2015-11-19 | 2017-05-31 | 芜湖启泽信息技术有限公司 | It is a kind of to be applied to photosensitive resin of 3D printing and preparation method thereof |
| CN106749942A (en) * | 2016-12-15 | 2017-05-31 | 深圳飞扬兴业科技有限公司 | A kind of 3D printing ultraviolet photocureable material and preparation method thereof |
| CN106977665A (en) * | 2017-03-30 | 2017-07-25 | 中北大学 | A kind of 3D printing photosensitive resin and preparation method thereof |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109867755A (en) * | 2019-02-22 | 2019-06-11 | 苏州轻金三维科技有限公司 | A kind of photosensitive resin preparation method suitable for 3 D-printing |
| CN109867756A (en) * | 2019-02-22 | 2019-06-11 | 苏州轻金三维科技有限公司 | A kind of 3 D-printing blue light curing photosensitive resin and preparation method thereof |
| CN112062896A (en) * | 2020-08-25 | 2020-12-11 | 南方科技大学 | Energy-absorbing 3D printing material, preparation method thereof and energy-absorbing device |
| CN112574366A (en) * | 2020-12-22 | 2021-03-30 | 杜晖 | Photosensitive resin, transparent mold for injection molding of photosensitive resin and injection molding method |
| CN115926635A (en) * | 2022-12-02 | 2023-04-07 | 华侨大学 | Ultraviolet-heat dual curing adhesive and preparation method and application in 3D printing |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN108690327A (en) | A kind of 3D printing UV curing photosensitive resin and preparation method thereof | |
| CN104570603B (en) | A kind of ultraviolet light solidifies the preparation method and application of 3D printing photosensitive resin | |
| CN102436145B (en) | Stereolithographic rapid prototyping photosensitive resin and preparation method thereof | |
| CN104250422A (en) | Photosensitive resin used in 3D printing, and its preparation method | |
| CN105259736A (en) | Photosensitive resin for 3D printer and preparation method of photosensitive resin | |
| CN108948279A (en) | A kind of optical and thermal double cured resin composition and prepreg cloth and 3D printing method | |
| CN104804151A (en) | Preparation method of light-cured resin material for three-dimensional printing | |
| CN105837760A (en) | Polyimide photosensitive material for 3D printing | |
| CN106995583A (en) | A kind of method that photocuring quickly prepares fiber-reinforced resin matrix compound material | |
| KR101572518B1 (en) | manufacturing method of conductor using dual curing composition for 3D printing | |
| CN104371488A (en) | Quick bonding repair method of ultraviolet-curing composite material | |
| CN108102277B (en) | 3D printing light-cured resin | |
| CN105404095A (en) | Washable ultraviolet laser curing and rapid prototyping photosensitive resin and preparation method thereof | |
| CN106543649A (en) | One specific admixture type 3D printing light curing resin composition | |
| CN109438631B (en) | High-precision and high-thermal-deformation-temperature stereolithography 3D printing photosensitive resin and preparation method thereof | |
| CN101776844A (en) | Photocuring component used for three-dimensional imaging | |
| CN108515693A (en) | A kind of material pond and its manufacturing process for photocuring 3D printing | |
| CN107244127B (en) | A kind of preparation method of fiber reinforced polymer film | |
| CN106987092A (en) | Cation photocuring prepares the method and its resin combination of fiber-reinforced resin matrix compound material | |
| CN109988273A (en) | A kind of preparation method of long-wave ultraviolet curing resin composition for 3D printing | |
| CN105904726B (en) | A kind of method based on digitized projection technique construction polymer three-dimensional structure | |
| CN117402458A (en) | Prepreg resin for composite material, and preparation method and application thereof | |
| CN102952257A (en) | Method for preparing stereolithography rapid-prototyping photosensitive resin by adopting 1,4-cyclohexanedimethanol diglycidyl ether diacrylate as prepolymer | |
| CN108690328A (en) | A kind of photosensitive resin and preparation method thereof for 3D printing | |
| CN105400472A (en) | Space-time separated preparation method for UV adhesive |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20181023 |
|
| RJ01 | Rejection of invention patent application after publication |