CN104804151A - Preparation method of light-cured resin material for three-dimensional printing - Google Patents
Preparation method of light-cured resin material for three-dimensional printing Download PDFInfo
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- CN104804151A CN104804151A CN201510225132.9A CN201510225132A CN104804151A CN 104804151 A CN104804151 A CN 104804151A CN 201510225132 A CN201510225132 A CN 201510225132A CN 104804151 A CN104804151 A CN 104804151A
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Abstract
The invention discloses a preparation method of a light-cured resin material for three-dimensional printing. The preparation method comprises the following steps of firstly, synthesizing epoxy acrylate resin; secondly, mixing the epoxy acrylate resin with a reactive diluent according to a certain mixture ratio to obtain a homogeneous and stable composite organic solution; thirdly, adding a photoinitiator with a certain proportion in the composite organic solution, heating and fully stirring to be dissolved to obtain the light-cured resin material for the three-dimensional printing. The preparation method has the advantage of lower cost, simple process, short curing time and easiness for realization.
Description
Technical field
The present invention relates to a kind of preparation method of 3D printing photocurable resin material, be specifically related to the preparation of light-cured resin and the solidification process under light trigger effect thereof.
Background technology
3D printing technique is one of modern popular new and high technology, and the accuracy of its height and the diversity of printable scope make 3D be printed in production to emerge rapidly.Photocuring 3D printing technique is the photopolymerization principle work based on liquid photosensitive resin, and in print procedure, injection of material is carried out together with solidification.Photocuring 3D printing technique, in environmental protection and convenience, prints than traditional melt extruded formula 3D and has more advantages.The problem such as deficient for domestic photo-curing material formula, technical industry is shapeless, researcher has done a large amount of research work in this field, be intended to synthesize a kind of photo-curing material meeting 3D print conditions, and gives its corresponding physicochemical property.
Current existing photo-curing material concentrates on free radical type ray curing type resin mostly, but the curing speed of the type material is relatively slow, is applied in 3D print job and needs to expend the longer time; And mechanical strength of resin is relatively low after solidification, these two factors become the bottleneck of many existing formulas.
The people such as Lai Wenzhong are that main raw material and cis-butenedioic anhydride, epifluorohydrin and vinylformic acid react with turps, synthesize a kind of novel TMA epoxy acrylic resin.A kind of UV curing photosensitive resin is formed through adding photosensitizers, active initiator etc.This photosensitive resin is 1.4 minutes film-formings under UV-irradiation, and have excellent water-fast, oil resistant, chemically-resistant acid attack and strong adhesion, feature that glossiness is good.But because its set time is long, cause the whole manufacture working hour tediously long, the advantage making 3D print is had a greatly reduced quality.
Photocuring material 3D prints higher to the requirement of material property, ensures printed material flowing at a certain temperature evenly; Fast as far as possible on set time, and the products solidifying shrinking percentage after curing molding must not more than 2%.In addition for the requirement of many functional 3D printed materials also other correlated performances of demand fulfillment, and most domestic formula mainly has problems in the basic demand of material property, causing cannot use of large-scale production, thus causes the phenomenon that photocuring 3D printing technique remains where one is.
Summary of the invention
For above-mentioned deficiency, the present invention is from synthesizing epoxy acrylic resin, and the proportioning for light trigger and thinner proposes to be strict with, and makes resin reach the effect of rapid solidification under high voltage mercury lamp light source.
Technical solution of the present invention and step as follows:
(1) take a certain amount of epoxy resin, be dissolved in toluene solvant, stir and make solution be dilution shape, pour there-necked flask into and be placed on 85 DEG C of oil baths and heat and stir, make it fully dissolve.Accurately measured amounts vinylformic acid is placed in beaker in addition, and add initiator N, N-xylidene(s), hydroquinone of polymerization retarder are made into acrylic system, after abundant stirring, aforesaid propylene acid system is dropwise instilled in the epoxy resin of 85 DEG C, stablize reaction 1 hour, be then progressively warming up to 95 DEG C, then react 1 hour; Reaction terminates after product and carries out suction filtration, is cooled to room temperature, obtains light yellow clear colloidal liquid, i.e. epoxy acrylic resin; Its epoxy resin and acrylic acid mass ratio are 2.8 ~ 3.4:1, and the mass ratio of initiator N, N-xylidene(s) and hydroquinone of polymerization retarder is 3.5 ~ 4.5:1, and the mass ratio of initiator and epoxy resin is 1:13 ~ 17;
(2) epoxy acrylic resin is taken, add reactive thinner NVP and Viscoat 295, make system be stirred well to dilution shape, in order to make resin possess better can ejection and mobility, by reactive thinner, viscosity is adjusted to 10
-14about centipoise, simultaneously or can slight heating in water bath, make to mix between each material;
(3) light trigger benzoin dimethylether and benzophenone (wherein the mass ratio of epoxy acrylic resin, benzoin dimethylether, benzophenone is 2.7 ~ 3.3:0.95 ~ 1.05:1) is added in the solution obtained to step (2), be placed in water-bath rising temperature for dissolving, abundant stirring, treat that solid particulate matter all dissolves, stop stirring, be cooled to room temperature, namely obtain light-cured resin.Under high voltage mercury lamp light source, irradiate about 1s Ke Da solidify completely.
Preparation 3D printing light-cured resin of the present invention, method is simple, is easy to realize, and cost is lower.
Accompanying drawing explanation
Fig. 1 is the liquid colloidal resin before photocuring.
Fig. 2 is after high voltage mercury lamp radiation, the light-cured resin after solidification.
Specific embodiments
Below introduce the embodiment of the preparation method of a kind of 3D printing of the present invention photocurable resin material, but it is noted that enforcement of the present invention is not limited to following embodiment.
Embodiment 1
Electronic balance measures 25.94g epoxy resin, is dissolved in toluene solvant, stirs and makes solution be dilution shape, pours there-necked flask into and is placed on 85 DEG C of oil baths and heats and stir;
Measure 7.95g vinylformic acid and be placed in beaker, weigh initiator N, N-xylidene(s) 0.69g, hydroquinone of polymerization retarder 0.153g, add the two in vinylformic acid and be made into acrylic system, fully stir;
Aforesaid propylene acid system is dropwise dripped in the epoxy resin of 85 DEG C, accelerates stirring velocity, stablize reaction 1 hour, after be progressively warming up to 95 DEG C, then react 1 hour.Reaction terminates rear suction filtration, is cooled to room temperature, obtains light yellow clear colloidal liquid, i.e. epoxy acrylic resin;
Take 3g epoxy acrylic resin, add 2.25gN-vinyl pyrrolidone, 1.04g Viscoat 295, be stirred well to dilution shape, as shown in Figure 1;
In light-cured resin, add benzoin dimethylether 1.01g, benzophenone 1.04g, be placed in oil bath rising temperature for dissolving, fully stir, treat that solid particulate matter all dissolves, stop stirring, be cooled to room temperature, namely obtain light-cured resin;
By the light-cured resin uniform application that obtains on slide glass, under high voltage mercury lamp radiation, about 1s can reach and solidify completely, and the effect completely after solidification as shown in Figure 2.
Embodiment 2
Electronic balance measures 26.26g epoxy resin, is dissolved in toluene solvant, stirs and makes solution be dilution shape, pours there-necked flask into and is placed on 85 DEG C of oil bath heating, and place magnetic stir bar stirring;
Measure 8.19g vinylformic acid and be placed in beaker, weigh initiator N, N-xylidene(s) 0.88g, hydroquinone of polymerization retarder 0.173g, add the two in vinylformic acid and be made into acrylic system, fully stir;
Aforesaid propylene acid system is dropwise dripped in the epoxy resin of 85 DEG C, accelerates magnetic agitation speed, stablize reaction 1 hour, after be progressively warming up to 95 DEG C, stablize reaction 1 hour.Reaction terminates rear suction filtration, is cooled to room temperature, obtains light yellow clear colloidal liquid, i.e. epoxy acrylic resin;
Take 3g epoxy acrylic resin, add 2.05gN-vinyl pyrrolidone, 1.04g Viscoat 295, be stirred well to dilution shape;
In light-cured resin, add benzoin dimethylether 1.07g, benzophenone 1.10g, be placed in oil bath rising temperature for dissolving, fully stir, treat that solid particulate matter all dissolves, stop stirring, be cooled to room temperature, namely obtain light-cured resin;
By the light-cured resin uniform application that obtains on slide glass, under high voltage mercury lamp radiation, about 1s can reach and solidify completely.
Claims (1)
1. prepare a method for 3D printing photocurable resin material, it is characterized in that comprising the steps:
(1) take a certain amount of epoxy resin, be dissolved in toluene solvant, stir and make solution be dilution shape, pour there-necked flask into and be placed on 85 DEG C of oil baths and heat and stir, make it fully dissolve; Accurately measured amounts vinylformic acid is placed in beaker in addition, and add initiator N, N-xylidene(s), hydroquinone of polymerization retarder are made into acrylic system, after abundant stirring, aforesaid propylene acid system is dropwise instilled in the epoxy resin of 85 DEG C, stablize reaction 1 hour, be then progressively warming up to 95 DEG C, then react 1 hour; Reaction terminates after product and carries out suction filtration, is cooled to room temperature, obtains light yellow clear colloidal liquid, i.e. epoxy acrylic resin; Its epoxy resin and acrylic acid mass ratio are 2.8 ~ 3.4: 1, and the mass ratio of initiator N, N-xylidene(s) and hydroquinone of polymerization retarder is 3.5 ~ 4.5: 1, and the mass ratio of initiator and epoxy resin is 1: 13 ~ 17;
(2) epoxy acrylic resin is taken, add reactive thinner NVP and Viscoat 295, make system be stirred well to dilution shape, in order to make resin possess better can ejection and mobility, by reactive thinner, system viscosity is adjusted to 10
-14about centipoise, simultaneously or can slight heating in water bath, make to mix between each material;
(3) light trigger benzoin dimethylether and benzophenone (wherein the mass ratio of epoxy acrylic resin, benzoin dimethylether, benzophenone is 2.7 ~ 3.3: 0.95 ~ 1.05: 1) is added in the solution obtained to step (2), be placed in water-bath rising temperature for dissolving, abundant stirring, treat that solid particulate matter all dissolves, stop stirring, be cooled to room temperature, namely obtain light-cured resin, under high voltage mercury lamp light source, irradiate about 1s Ke Da solidify completely.
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Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106084656A (en) * | 2016-06-13 | 2016-11-09 | 广西医科大学 | A kind of new modified materials printed for 3D |
| CN106167537A (en) * | 2016-07-29 | 2016-11-30 | 佛山市高明区诚睿基科技有限公司 | The photocurable resin material that a kind of 3D with self-cleaning antibacterial prints |
| CN106188427A (en) * | 2016-07-29 | 2016-12-07 | 佛山市高明区诚睿基科技有限公司 | The photocurable resin material that a kind of 3D prints |
| CN106221105A (en) * | 2016-07-29 | 2016-12-14 | 佛山市高明区诚睿基科技有限公司 | The photocurable resin material that a kind of anti-static type 3D prints |
| CN106608952A (en) * | 2016-11-30 | 2017-05-03 | 辽宁大学 | Flexible light-cured resin material for 3D printing and preparation method and application thereof |
| CN106750049A (en) * | 2016-11-30 | 2017-05-31 | 辽宁大学 | A kind of 3D printing rapid shaping photocurable resin material and its preparation method and application |
| CN106832149A (en) * | 2017-01-11 | 2017-06-13 | 杭州龙勤新材料科技有限公司 | A kind of easy to be release photosensitive resin for 3D printing and preparation method thereof |
| CN106867203A (en) * | 2017-03-07 | 2017-06-20 | 辽宁大学 | A kind of 3D printing resin toner and preparation method thereof |
| CN110776604A (en) * | 2019-10-31 | 2020-02-11 | 东莞理工学院 | Light-cured wax resin for DLP (digital light processing) type 3D printing and preparation method thereof |
| CN111989209A (en) * | 2018-05-05 | 2020-11-24 | 清锋（北京）科技有限公司 | Material pool for photocuring 3D printing and manufacturing process thereof |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1699492A (en) * | 2005-07-11 | 2005-11-23 | 大连轻工业学院 | Photo-curable conductive adhesive and method for making same |
| CN101153127A (en) * | 2007-09-06 | 2008-04-02 | 湖南阳光新材料有限公司 | White composition capable of solidifying by ultraviolet light |
| US20120067759A1 (en) * | 2010-09-22 | 2012-03-22 | Michelman, Inc. | Energy curable overprint varnish and coated product |
| CN104312141A (en) * | 2014-11-14 | 2015-01-28 | 南京百川行远激光科技有限公司 | Photosensitive resin and preparation method thereof |
-
2015
- 2015-05-06 CN CN201510225132.9A patent/CN104804151A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1699492A (en) * | 2005-07-11 | 2005-11-23 | 大连轻工业学院 | Photo-curable conductive adhesive and method for making same |
| CN101153127A (en) * | 2007-09-06 | 2008-04-02 | 湖南阳光新材料有限公司 | White composition capable of solidifying by ultraviolet light |
| US20120067759A1 (en) * | 2010-09-22 | 2012-03-22 | Michelman, Inc. | Energy curable overprint varnish and coated product |
| CN104312141A (en) * | 2014-11-14 | 2015-01-28 | 南京百川行远激光科技有限公司 | Photosensitive resin and preparation method thereof |
Non-Patent Citations (3)
| Title |
|---|
| 何岷洪等: "3Ｄ打印光敏树脂的研究进展", 《功能高分子学报》 * |
| 常英等: "环氧丙烯酸光敏树脂的研制及应用", 《中国胶粘剂》 * |
| 朱林泉等: "《快速成型与快速制造技术》", 31 January 2003, 国防工业出版社 * |
Cited By (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106084656A (en) * | 2016-06-13 | 2016-11-09 | 广西医科大学 | A kind of new modified materials printed for 3D |
| CN106167537A (en) * | 2016-07-29 | 2016-11-30 | 佛山市高明区诚睿基科技有限公司 | The photocurable resin material that a kind of 3D with self-cleaning antibacterial prints |
| CN106188427A (en) * | 2016-07-29 | 2016-12-07 | 佛山市高明区诚睿基科技有限公司 | The photocurable resin material that a kind of 3D prints |
| CN106221105A (en) * | 2016-07-29 | 2016-12-14 | 佛山市高明区诚睿基科技有限公司 | The photocurable resin material that a kind of anti-static type 3D prints |
| CN106608952A (en) * | 2016-11-30 | 2017-05-03 | 辽宁大学 | Flexible light-cured resin material for 3D printing and preparation method and application thereof |
| CN106750049A (en) * | 2016-11-30 | 2017-05-31 | 辽宁大学 | A kind of 3D printing rapid shaping photocurable resin material and its preparation method and application |
| CN106832149A (en) * | 2017-01-11 | 2017-06-13 | 杭州龙勤新材料科技有限公司 | A kind of easy to be release photosensitive resin for 3D printing and preparation method thereof |
| CN106832149B (en) * | 2017-01-11 | 2019-01-08 | 杭州龙勤新材料科技有限公司 | A kind of easy release photosensitive resin and preparation method thereof for 3D printing |
| CN106867203A (en) * | 2017-03-07 | 2017-06-20 | 辽宁大学 | A kind of 3D printing resin toner and preparation method thereof |
| CN111989209A (en) * | 2018-05-05 | 2020-11-24 | 清锋（北京）科技有限公司 | Material pool for photocuring 3D printing and manufacturing process thereof |
| CN110776604A (en) * | 2019-10-31 | 2020-02-11 | 东莞理工学院 | Light-cured wax resin for DLP (digital light processing) type 3D printing and preparation method thereof |
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Application publication date: 20150729 |