CN104830159A - Preparation method and application of photo-curing color paste containing graphene - Google Patents
Preparation method and application of photo-curing color paste containing graphene Download PDFInfo
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- CN104830159A CN104830159A CN201410787873.1A CN201410787873A CN104830159A CN 104830159 A CN104830159 A CN 104830159A CN 201410787873 A CN201410787873 A CN 201410787873A CN 104830159 A CN104830159 A CN 104830159A
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- photosensitive resin
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 32
- 229910021389 graphene Inorganic materials 0.000 title claims abstract description 32
- 238000002360 preparation method Methods 0.000 title claims abstract description 8
- 238000000016 photochemical curing Methods 0.000 title abstract description 5
- 229920005989 resin Polymers 0.000 claims abstract description 38
- 239000011347 resin Substances 0.000 claims abstract description 38
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 13
- 239000012752 auxiliary agent Substances 0.000 claims abstract description 5
- 239000002904 solvent Substances 0.000 claims abstract description 3
- 230000004048 modification Effects 0.000 claims abstract 2
- 238000012986 modification Methods 0.000 claims abstract 2
- 239000000203 mixture Substances 0.000 claims description 27
- 239000006185 dispersion Substances 0.000 claims description 14
- 238000007711 solidification Methods 0.000 claims description 10
- 230000008023 solidification Effects 0.000 claims description 10
- KWOLFJPFCHCOCG-UHFFFAOYSA-N Acetophenone Chemical compound CC(=O)C1=CC=CC=C1 KWOLFJPFCHCOCG-UHFFFAOYSA-N 0.000 claims description 8
- 239000013530 defoamer Substances 0.000 claims description 7
- YIKSHDNOAYSSPX-UHFFFAOYSA-N 1-propan-2-ylthioxanthen-9-one Chemical compound S1C2=CC=CC=C2C(=O)C2=C1C=CC=C2C(C)C YIKSHDNOAYSSPX-UHFFFAOYSA-N 0.000 claims description 6
- 230000001804 emulsifying effect Effects 0.000 claims description 5
- -1 hexanediyl ester Chemical class 0.000 claims description 5
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 claims description 4
- RWCCWEUUXYIKHB-UHFFFAOYSA-N benzophenone Chemical group C=1C=CC=CC=1C(=O)C1=CC=CC=C1 RWCCWEUUXYIKHB-UHFFFAOYSA-N 0.000 claims description 4
- 239000012965 benzophenone Substances 0.000 claims description 4
- UHESRSKEBRADOO-UHFFFAOYSA-N ethyl carbamate;prop-2-enoic acid Chemical compound OC(=O)C=C.CCOC(N)=O UHESRSKEBRADOO-UHFFFAOYSA-N 0.000 claims description 4
- 150000002576 ketones Chemical class 0.000 claims description 4
- PSGCQDPCAWOCSH-UHFFFAOYSA-N (4,7,7-trimethyl-3-bicyclo[2.2.1]heptanyl) prop-2-enoate Chemical compound C1CC2(C)C(OC(=O)C=C)CC1C2(C)C PSGCQDPCAWOCSH-UHFFFAOYSA-N 0.000 claims description 3
- NSFGOWGWLHAJPC-UHFFFAOYSA-N COCOC.C(C=C)(=O)O Chemical compound COCOC.C(C=C)(=O)O NSFGOWGWLHAJPC-UHFFFAOYSA-N 0.000 claims description 3
- UFRPKKYHEVFXQS-UHFFFAOYSA-N OC1(CCCCC1)ON=C(C(C1=CC=CC=C1)=O)C1=CC=CC=C1 Chemical compound OC1(CCCCC1)ON=C(C(C1=CC=CC=C1)=O)C1=CC=CC=C1 UFRPKKYHEVFXQS-UHFFFAOYSA-N 0.000 claims description 3
- 239000002202 Polyethylene glycol Substances 0.000 claims description 3
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 claims description 3
- DAKWPKUUDNSNPN-UHFFFAOYSA-N Trimethylolpropane triacrylate Chemical compound C=CC(=O)OCC(CC)(COC(=O)C=C)COC(=O)C=C DAKWPKUUDNSNPN-UHFFFAOYSA-N 0.000 claims description 3
- 125000004386 diacrylate group Chemical group 0.000 claims description 3
- 239000003822 epoxy resin Substances 0.000 claims description 3
- 229920000647 polyepoxide Polymers 0.000 claims description 3
- 229920001223 polyethylene glycol Polymers 0.000 claims description 3
- 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 3
- GJZFGDYLJLCGHT-UHFFFAOYSA-N 1,2-diethylthioxanthen-9-one Chemical compound C1=CC=C2C(=O)C3=C(CC)C(CC)=CC=C3SC2=C1 GJZFGDYLJLCGHT-UHFFFAOYSA-N 0.000 claims description 2
- UYEDESPZQLZMCL-UHFFFAOYSA-N 1,2-dimethylthioxanthen-9-one Chemical compound C1=CC=C2C(=O)C3=C(C)C(C)=CC=C3SC2=C1 UYEDESPZQLZMCL-UHFFFAOYSA-N 0.000 claims description 2
- LJRSZGKUUZPHEB-UHFFFAOYSA-N 2-[2-(2-prop-2-enoyloxypropoxy)propoxy]propyl prop-2-enoate Chemical compound C=CC(=O)OC(C)COC(C)COC(C)COC(=O)C=C LJRSZGKUUZPHEB-UHFFFAOYSA-N 0.000 claims description 2
- HDMIWIXLPFMCFC-UHFFFAOYSA-N 2-chloro-2h-thiopyrano[3,2-b]chromen-10-one Chemical class O1C2=CC=CC=C2C(=O)C2=C1C=CC(Cl)S2 HDMIWIXLPFMCFC-UHFFFAOYSA-N 0.000 claims description 2
- 239000004721 Polyphenylene oxide Substances 0.000 claims description 2
- 239000005864 Sulphur Substances 0.000 claims description 2
- 239000002253 acid Substances 0.000 claims description 2
- 238000005660 chlorination reaction Methods 0.000 claims description 2
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 claims description 2
- AUONHKJOIZSQGR-UHFFFAOYSA-N oxophosphane Chemical compound P=O AUONHKJOIZSQGR-UHFFFAOYSA-N 0.000 claims description 2
- LYXOWKPVTCPORE-UHFFFAOYSA-N phenyl-(4-phenylphenyl)methanone Chemical compound C=1C=C(C=2C=CC=CC=2)C=CC=1C(=O)C1=CC=CC=C1 LYXOWKPVTCPORE-UHFFFAOYSA-N 0.000 claims description 2
- 229920000728 polyester Polymers 0.000 claims description 2
- 229920000570 polyether Polymers 0.000 claims description 2
- YRHRIQCWCFGUEQ-UHFFFAOYSA-N thioxanthen-9-one Chemical compound C1=CC=C2C(=O)C3=CC=CC=C3SC2=C1 YRHRIQCWCFGUEQ-UHFFFAOYSA-N 0.000 claims description 2
- 238000002156 mixing Methods 0.000 abstract description 8
- 239000000463 material Substances 0.000 abstract description 6
- 238000000034 method Methods 0.000 abstract description 6
- 238000010146 3D printing Methods 0.000 abstract description 5
- 238000007639 printing Methods 0.000 abstract description 4
- 238000001723 curing Methods 0.000 abstract description 3
- 239000003085 diluting agent Substances 0.000 abstract description 2
- 239000006229 carbon black Substances 0.000 description 3
- 230000007423 decrease Effects 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 238000004154 testing of material Methods 0.000 description 3
- 238000010521 absorption reaction Methods 0.000 description 2
- 239000012141 concentrate Substances 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 238000007493 shaping process Methods 0.000 description 2
- MDDUHVRJJAFRAU-YZNNVMRBSA-N tert-butyl-[(1r,3s,5z)-3-[tert-butyl(dimethyl)silyl]oxy-5-(2-diphenylphosphorylethylidene)-4-methylidenecyclohexyl]oxy-dimethylsilane Chemical compound C1[C@@H](O[Si](C)(C)C(C)(C)C)C[C@H](O[Si](C)(C)C(C)(C)C)C(=C)\C1=C/CP(=O)(C=1C=CC=CC=1)C1=CC=CC=C1 MDDUHVRJJAFRAU-YZNNVMRBSA-N 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 239000000956 alloy Substances 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 229940042596 viscoat Drugs 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Abstract
The invention provides a black photo-curing color paste containing graphene, a preparation method thereof, and an application thereof in 3D-printing photosensitive resin. The black photo-curing color paste includes: graphene, photosensitive resin, an active diluent, a photo-initiation agent and an auxiliary agent. The preparation method is free of use of a volatile solvent. In the method, by means of high-speed shear, the graphene is dispersed in the photosensitive resin to obtain a color paste, and by blending the color paste with any 3D-printing photosensitive resin, a black printing model can be obtained. The black photo-curing color paste is excellent in texture and appearance, is free of influence on printing speed and curing thickness of a 3D printer, can satisfy use requirements of the 3D printer, and meanwhile has a significant modification function on the original 3D printing material.
Description
Technical field
The invention belongs to mill base Material Field, photosensitive resin mixture being specifically related to a kind of graphene-containing and preparation method thereof, can be used for 3D and print.
Background technology
Photosensitive resin is used to mainly contain as the 3D printing technique of printed material: stereolithography rapid shaping (Stereolithography, SLA), DLP projection formula 3 D-printing technique (Digital Light Processing, and ultra-thin thickness photosensitive resin spray up n. technology (Connex500 system, Objet Geometries company) DLP).Its print procedure is determined in computer by three-dimensional model, then pays 3D printer, and print procedure adopts uviolizing liquid photosensitive resin, and in layer storehouse is shaping.
The photosensitive resin that 3D prints needs fast setting under the conditions of exposure of 3D printer, goes back the printing technique of demand fulfillment printer in addition, has certain mobility.These are basic demands that photosensitive resin can be used in 3D printer.At present, the domestic photosensitive resin kind for 3D printer is single, and color is dull, based on water white transparency, the light color such as faint yellow or white.
Black photosensitive resin mainly adopts the mill base containing carbon black, carbon black concentrates on 180 ~ 260nm scope to ultraviolet absorption, this wider range, and carbon black absorbs in a large number and reflects UV line, laser curing velocity is declined greatly, is difficult to the requirement meeting the low power exposure that 3D prints.
Graphene UV absorption peak concentrates on 270nm, and particle is less, and has certain mechanics modified effect, the black color paste prepared with Graphene is liquid, can easily with 3D printed photosensitive resin alloy, on laser curing velocity impact little, the 3D printed material of black can be obtained.
Summary of the invention
The present invention prepares the black light solidification mill base containing Graphene, and made an addition in 3D printing resin, obtain the 3D printed photosensitive resin of black, mill base has good dispersiveness in 3D printed photosensitive resin, do not affect print speed, have certain modifying function to resin simultaneously.
(1) Graphene 0.5 ~ 10%
(2) photosensitive resin 10 ~ 60%
(3) reactive thinner 20 ~ 70%
(4) light trigger 1 ~ 12%
(5) auxiliary agent 0.2 ~ 3%
Described (2) photosensitive resin is made up of the mixture of one or several in urethane acrylate, epoxy acrylate, polyester acrylate, polyether acrylate, epoxy resin;
Described (3) reactive thinner is by one or several the mixture in tri (propylene glycol) diacrylate, hexanediyl ester, Viscoat 295, polyethyleneglycol diacrylate, isobornyl acrylate, ring TriMethylolPropane(TMP) methylal acrylate.
Described (4) light trigger is the mixture of one or more in acetophenone derivs, fragrant ketone, triaryl phosphofluoric acid sulfosalt, triaryl sulphur hexafluoro antimonate, Ciba Irgacure 784.Described acetophenone derivs is 1-hydroxy cyclohexylphenyl benzoylformaldoxime, α, alpha-alpha-dimethyl-alpha-hydroxyacetophenone, p-isopropyl phenyl-2-hydroxyl dimethyl acetone-1; Described fragrant ketone is benzophenone, diphenyl antimony chloride ketone, acrylated benzophenone, 4-phenyl benzophenone, 2-chlorination thioxanthone, isopropyl thioxanthone, dimethyl thioxanthone, diethyl thioxanthone, two chlorothiaxanthenones, 2; 4,6-trimethylbenzoy-dipheny phosphine oxide.
Described (5) auxiliary agent is made up of one or several in dispersion agent, defoamer and flow agent.
Black light containing Graphene should solidify mill base, it is characterized in that preparation process does not need to use solvent, Graphene directly shears dispersion in reactive thinner or photosensitive resin, and its step is as follows:
Graphene is directly added in reactive thinner, at 0 ~ 10 DEG C, mix and blend 20 ~ 30min under 200 ~ 500rpm speed conditions, then add dispersion agent, with the high-speed emulsifying machine with roto-stator devices, high speed shear 5 ~ 60min under 3000 ~ 20000rpm rotating speed, stops high speed shear.Add photosensitive resin and defoamer, 200 ~ 500rpm mix and blend, 5 ~ 30min, with the high speed dispersor being furnished with zig-zag dispersion impeller, under 1000 ~ 8000rpm rotating speed, shear 10 ~ 30min.Finally add light trigger, 200 ~ 500rpm mixes 5 ~ 20min, obtains black color paste.
The resin stretched strength and modulus of 3D printed photosensitive that with the addition of Graphene black color paste obviously rises, and flexural strength and modulus decline, and cure shrinkage obviously declines.
Embodiment:
Embodiment 1: a kind of black light solidification mill base containing Graphene and preparation method thereof
0.5g Graphene (Changzhou No.6 Element Material Technology Co., Ltd.) is directly added in 45g reactive thinner TPGDA, at 0 DEG C, mix and blend 20min under 200rpm speed conditions, then 0.5g dispersion agent TEGO Dispers 685 is added, with the high-speed emulsifying machine of band roto-stator devices, high speed shear 10min under 10000rpm rotating speed, stops high speed shear.Add 50g urethane acrylate, 0.3g defoamer Tego Aire 920 and 0.3g flow agent TEGO Glide 130,200rpm mix and blend 5min, with the high speed dispersor being furnished with zig-zag dispersion impeller, under 8000rpm rotating speed, shear 15min.Finally add light trigger 1.6g isopropyl thioxanthone (ITX), 1.8g EDMAB (EDAB), mixing 5min, obtains black color paste.
Getting gained mill base 10g adds in 90g DLP type 3D printed photosensitive resin, at ambient temperature, with rotating speed 200rpm mixing 30min, obtains black 3D printed photosensitive resin.Gained black photosensitive resin is applied to ten dimension 10D125 type 3D printers (science and technology limited Company is tieed up in Beijing ten), directly prints the stretching of horizontal and vertical directions and the batten of crooked test with printer.
The testing of materials performance of horizontal direction is: Shao D hardness 79.2, flexural strength 8.43MPa, modulus in flexure 189MPa, amount of deflection 6.1%, tensile strength 21.4MPa, tensile modulus 666MPa, fracture rate elongation 5.1%.The testing of materials performance of vertical direction is: Shao D hardness 73.5, flexural strength 5.57MPa, modulus in flexure 116MPa, amount of deflection 5.9%, tensile strength 15.2MPa, tensile modulus 390MPa, fracture rate elongation 4.0%.
And not adding the original 3D printed photosensitive resin of Graphene black color paste, test performance is in the horizontal direction: Shao D hardness 82, flexural strength 22.9MPa, modulus in flexure 543MPa, amount of deflection 5.9%, tensile strength 19.7MPa, tensile modulus 587MPa, fracture rate elongation 4.1%.The testing of materials performance of vertical direction is: Shao D hardness 76, flexural strength 11.1MPa, modulus in flexure 151MPa, amount of deflection 6.3%, tensile strength 14.2MPa, tensile modulus 495MPa, fracture rate elongation 2.9%.
As can be seen here: the 3D printed photosensitive resin that with the addition of Graphene mill base, horizontal direction hardness slightly declines, and tensile strength and tensile modulus rise 8% and 13% respectively, and flexural strength and modulus decline 63% and 65% respectively, and fracture rate elongation rises 24%; Vertical direction hardness slightly declines, and tensile strength and tensile modulus rise 7% and 21% respectively, and flexural strength and modulus decline 50% and 23% respectively, and fracture rate elongation rises 38%, and the toughness of material totally rises.
In addition, after adding Graphene mill base, the shrinking percentage of 3D printed photosensitive resin drops to 5% by 9%.
Embodiment 2:
10g Graphene is directly added in 30g reactive thinner TPGDA and 21g Viscoat 295, at 5 DEG C, mix and blend 30min under 500rpm speed conditions, then 1.5g dispersion agent TEGO Dispers 685 is added, with the high-speed emulsifying machine of band roto-stator devices, high speed shear 5min under 20000rpm rotating speed, stops high speed shear.Add 15g epoxy resin and 15g urethane acrylate, 0.5g defoamer Tego Aire 900 and 0.5g flow agent TEGO Glide 100,500rpm mix and blend 10min, with the high speed dispersor being furnished with zig-zag dispersion impeller, under 2000rpm rotating speed, shear 30min.Finally add light trigger 2.5g Ciba Irgacure 784,1g 1-hydroxy cyclohexylphenyl benzoylformaldoxime, 2.5g 2,4,6-trimethylbenzoy-dipheny phosphine oxide, 200rpm mixing 20min, obtains black color paste.
Getting gained mill base 5g adds in 95g SLA type 3D printed photosensitive resin, at ambient temperature, with rotating speed 200rpm mixing 30min, obtains the black photosensitive resin being applicable to SLA type 3D printer.
Embodiment 3:
Direct and 20g hexanediyl ester, 25g Viscoat 295,10g polyethyleneglycol diacrylate, 10g isobornyl acrylate, 5g ring TriMethylolPropane(TMP) methylal acrylate reactive mixing diluents by 1g Graphene, at 10 DEG C, mix and blend 30min under 500rpm speed conditions, then 0.5g dispersion agent TEGO Dispers 685 is added, with the high-speed emulsifying machine of band roto-stator devices, high speed shear 10min under 5000rpm rotating speed, stops high speed shear.Add 15g epoxy acrylate, 0.7g defoamer Tego Aire 920 and 0.8g flow agent TEGO Glide 130,200rpm mix and blend 5min, with the high speed dispersor being furnished with zig-zag dispersion impeller, under 8000rpm rotating speed, shear 15min.Finally add light trigger 4g1-hydroxy cyclohexylphenyl benzoylformaldoxime, 5g 2; 4,6-trimethylbenzoy-dipheny phosphine oxide, 2g isopropyl thioxanthone (ITX), 1g EDMAB (EDAB); mixing 5min, obtains black color paste.
Getting gained mill base 5g adds in 95g DLP type 3D printed photosensitive resin, at ambient temperature, with rotating speed 200rpm mixing 30min, obtains black 3D printed photosensitive resin.
Claims (8)
1. containing Graphene black light solidification a mill base, it is characterized in that: each component and weight percent as follows:
(1) Graphene 0.5 ~ 10%;
(2) photosensitive resin 10 ~ 60%;
(3) reactive thinner 20 ~ 70%;
(4) light trigger 1 ~ 12%;
(5) auxiliary agent 0.2 ~ 3%.
2. the black light solidification mill base containing Graphene according to claim 1, is characterized in that: described (2) photosensitive resin is made up of the mixture of one or several in urethane acrylate, epoxy acrylate, polyester acrylate, polyether acrylate, epoxy resin.
3. the black light solidification mill base containing Graphene according to claim 1, is characterized in that: described (3) reactive thinner is by one or several the mixture in tri (propylene glycol) diacrylate, hexanediyl ester, Viscoat 295, polyethyleneglycol diacrylate, isobornyl acrylate, ring TriMethylolPropane(TMP) methylal acrylate.
4. the black light solidification mill base containing Graphene according to claim 1, is characterized in that: described (4) light trigger is the mixture of one or more in acetophenone derivs, fragrant ketone, triaryl phosphofluoric acid sulfosalt, triaryl sulphur hexafluoro antimonate, Ciba Irgacure 784;
Described acetophenone derivs is 1-hydroxy cyclohexylphenyl benzoylformaldoxime, α, alpha-alpha-dimethyl-alpha-hydroxyacetophenone, p-isopropyl phenyl-2-hydroxyl dimethyl acetone-1;
Described fragrant ketone is benzophenone, diphenyl antimony chloride ketone, acrylated benzophenone, 4-phenyl benzophenone, 2-chlorination thioxanthone, isopropyl thioxanthone, dimethyl thioxanthone, diethyl thioxanthone, two chlorothiaxanthenones, 2; 4,6-trimethylbenzoy-dipheny phosphine oxide.
5. the black light solidification mill base containing Graphene according to claim 1, is characterized in that: described (5) auxiliary agent is made up of one or several in dispersion agent, defoamer and flow agent.
6. the solidification of the black light containing the Graphene mill base described in any one of claim 1-5, it is characterized in that preparation process does not need to use solvent, Graphene directly shears dispersion in reactive thinner or photosensitive resin, and its step is as follows:
Graphene is directly added in reactive thinner, at 0 ~ 10 DEG C, mix and blend 20 ~ 30min under 200 ~ 500rpm speed conditions, then add dispersion agent, with the high-speed emulsifying machine with roto-stator devices, high speed shear 5 ~ 60min under 3000 ~ 20000rpm rotating speed, stops high speed shear; Add photosensitive resin and defoamer, 200 ~ 500rpm mix and blend, 5 ~ 30min, with the high speed dispersor being furnished with zig-zag dispersion impeller, under 1000 ~ 8000rpm rotating speed, shear 10 ~ 30min; Finally add light trigger, 200 ~ 500rpm mixes 5 ~ 20min.
7. the application in black 3D printed photosensitive resin prepared by the solidification of the black light containing the Graphene mill base according to any one of claim 1-5.
8. the application of the solidification mill base of the black light containing Graphene in other 3D printed photosensitive resin of modification according to any one of claim 1-5.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410787873.1A CN104830159A (en) | 2014-12-17 | 2014-12-17 | Preparation method and application of photo-curing color paste containing graphene |
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| CN201410787873.1A CN104830159A (en) | 2014-12-17 | 2014-12-17 | Preparation method and application of photo-curing color paste containing graphene |
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| CN104830159A true CN104830159A (en) | 2015-08-12 |
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