CN110330268A - A kind of 3D printing Si for DLP rapid shaping3N4The light-cured resin of ceramics - Google Patents
A kind of 3D printing Si for DLP rapid shaping3N4The light-cured resin of ceramics Download PDFInfo
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- CN110330268A CN110330268A CN201910634249.0A CN201910634249A CN110330268A CN 110330268 A CN110330268 A CN 110330268A CN 201910634249 A CN201910634249 A CN 201910634249A CN 110330268 A CN110330268 A CN 110330268A
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- light
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- 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
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B26/00—Compositions of mortars, concrete or artificial stone, containing only organic binders, e.g. polymer or resin concrete
- C04B26/02—Macromolecular compounds
- C04B26/10—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
- C04B26/18—Polyesters; Polycarbonates
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- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B2111/00—Mortars, concrete or artificial stone or mixtures to prepare them, characterised by specific function, property or use
- C04B2111/00034—Physico-chemical characteristics of the mixtures
- C04B2111/00181—Mixtures specially adapted for three-dimensional printing (3DP), stereo-lithography or prototyping
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Ceramic Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Structural Engineering (AREA)
- Organic Chemistry (AREA)
Abstract
The present invention proposes a kind of 3D printing Si for DLP rapid shaping3N4The light-cured resin of ceramics, by weight percentage, the light-cured resin includes the first prepolymer of 15-20%, the second prepolymer of 15-20%, the tough agent of 5-15%, the photoinitiator of 0.5-4%, the Si of 50-64.5%3N4Powder.Above-mentioned light-cured resin uses the first prepolymer and the second prepolymer with higher functionality that the light-cured resin is had compared with high reaction activity, the crosslink density of the thin layer formed after above-mentioned light-cured resin solidifies thus can be improved, to promote the curability of visible light wave range；The dosage of each component is limited to the stain resistance and wearability for being conducive to improve the thin layer that the resin is formed after photocuring within the above range simultaneously；Resin according to the present invention can use ordinary white light source photocuring, realize Si3N4The 3D printing effect of ceramics.
Description
Technical field
The present invention relates to 3D printing technique field more particularly to a kind of 3D printing Si for DLP rapid shaping3N4Ceramics
Light-cured resin, in particular to it is a kind of using visible light wave range carry out photocuring resin, can be used for Si3N4Ceramics
Rapid shaping.
Background technique
The design and exploitation of advanced ceramics develop since automotive field, and gradually to high-performance field earliest.At this stage
Advanced ceramics are developed and apply in aerospace, Homeland Defense, the energy and field of biomedicine.Ceramic need through
Cross four material powder processing, body preparation molding, solid articles sintering and final working process key links.Wherein, ceramic
The molding of product is a time-consuming and process costly.Saving prepare material, shorten the process-cycle, reduce manufacturing cost and
Realize that product mass production is advanced ceramics problem encountered.To solve advanced ceramics problems faced, no mould ceramics molding system
The technology of making is come into being.Wherein DLP Introduction To Stereolithography can be used for the stereo shaping of ceramics, have high efficiency, without mould
Change and can complicate etc. advantages, relative to other 3D printing forming techniques, is based on DLP (digital light processing) photocureable rapid shaping
The ceramic member of technology synthesis has the intensity closest to conventional sintering ceramics after sintering, in the doctor that dentistry and knitting are applied
In the preparation of, MEMS (MEMS), sensor, piezoelectric element and photonic crystal, there is very high practicability and sexual valence
Than.
Due to Si3N4Ceramics are high with intensity, fusing point is high, chemical property is stable, corrosion resistance is excellent and thermal coefficient is low
The features such as, it is widely used in forming tool, sizing die, wire drawing die, cutting tool, high temperature extrusion die, scissors, golf
Club head, Engine Push Rod, connecting rod, bearing, cylinder liner, piston cap, refractory material, casting gate, melting platinum and germanium crucible with
And gear division corona, base station, planting body, orthopaedics joint ball head and Invasive lumbar fusion device etc., there is the very big market space.
Si is formed using the method for photocuring 3D printing3N4The report of ceramics has had much, as number of patent application is
201710048156.0 application for a patent for invention discloses a kind of 3D printing based on Stereolithography and prepares silicon nitride ceramics
Method, the application for a patent for invention that number of patent application is 201810615646.9 disclose a kind of 3D printing artificial tooth ceramic material and system
Preparation Method.But these generally realize Si using UV light in the prior art3N4Ceramics 3D printing, due to use UV ray machine or
Ultraviolet laser is as light source, higher cost, results in ceramics at present 3D printer is expensive and be unfavorable for promoting, and therefore, opens
It issues and uses the cured resin of visible light wave range, improve the speed of photosensitized reaction into key to solve this problem.
Summary of the invention
In order to solve the problems in the existing technology, the invention proposes a kind of 3D printings for DLP rapid shaping
Si3N4The light-cured resin of ceramics is realized to overcome the shortcomings of that 3D printing in the prior art need to solidify ceramic slurry using UV
Common DLP white light source or mobile phone liquid crystal screen can do the 3D printing of light source.
To achieve the goals above, the invention proposes a kind of 3D printing Si for DLP rapid shaping3N4The light of ceramics
Solidified resin, by weight percentage, the light-cured resin include the first prepolymer of 15-20%, and the second of 15-20% is pre-
Polymers, the tough agent of 5-15%, the photoinitiator of 0.5-4%, the Si of 50-64.5%3N4Powder.
Preferably, first prepolymer is the aliphatic polyurethane acrylic polymer of degree of functionality 9-10.
Preferably, second prepolymer is ethoxyquin trimethylolpropane trimethacrylate.
Preferably, the tough agent is acryloyl morpholine.
Preferably, the photoinitiator is (4- hydroxy phenyl) methylbenzyl sulphur hexafluoro antimonate and 2- diazonium -1-
The mixture of naphthols -5- sulfonic acid chloride, wherein the mass percent of the two are as follows: (4- hydroxy phenyl) methylbenzyl sulphur hexafluoro-antimonic acid
Salt: 2- diazonium -1- naphthols -5- sulfonic acid chloride=3:1-1:4.
Preferably, the Si3N4Powder uses grain size for the silicon nitride ceramic of 500-5000nm.
The beneficial effect of the program of the present invention is the above-mentioned 3D printing Si for DLP rapid shaping3N4The light of ceramics is solid
The photoinitiator that change resin uses is (4- hydroxy phenyl) methylbenzyl sulphur hexafluoro antimonate and 2- diazonium -1- naphthols -5- sulphur
The mixture of acyl chlorides makes resin solidification wavelength in 200-480nm, avoids using the UV light of 365nm or 405nm that carry out light solid
The problem of change, makes it possible common DLP projector or mobile phone light source as 3D printer light source.The light-cured resin uses
The first prepolymer and the second prepolymer with higher functionality have the light-cured resin compared with high reaction activity, thus energy
The crosslink density of the thin layer formed after above-mentioned light-cured resin solidifies is enough improved, to promote the curability of visible light wave range；Institute
State acryloyl morpholine and aliphatic polyurethane acrylic polymer reactivity with higher and bonding force, thus the component
Flexibility, wearability and the service life for being conducive to resin after enhancing solidifies is added；In addition, the dosage of each component is limited to
State the stain resistance for being conducive to improve the thin layer that the resin is formed after photocuring simultaneously in range and wearability.In summary because
Element makes resin according to the present invention be different from other reported resins, and common white light can be used in resin according to the present invention
Light source photocuring realizes Si3N4The 3D printing effect of ceramics.
Specific embodiment
A specific embodiment of the invention is further described below with reference to embodiment.
The main object of the present invention is to solve current photocuring Si3N4In the 3D printing of ceramics, use 365nm's or 405nm
Come the problem of carrying out photocuring, above-mentioned photocuring mode results in ceramics at present 3D printer is expensive to be unfavorable for pushing away UV light
Extensively.Light-cured resin according to the present invention is solidified using visible light wave range, and solidification wavelength improves light in 200-480nm
The speed of quick reaction makes it possible common DLP projector or mobile phone light source as 3D printer light source.
Embodiment 1
3D printing Si according to the present invention for DLP rapid shaping3N4The light-cured resin of ceramics, by weight percentage
Than meter, including 15% the first prepolymer, 15% the second prepolymer, 6% tough agent, 4% photoinitiator, 60%
Si3N4Powder.
Wherein first prepolymer is the aliphatic polyurethane acrylic polymer of degree of functionality 9-10；Second pre-polymerization
Object is ethoxyquin trimethylolpropane trimethacrylate；The tough agent is acryloyl morpholine；The photoinitiator is (4- hydroxyl
Phenyl) methylbenzyl sulphur hexafluoro antimonate and 2- diazonium -1- naphthols -5- sulfonic acid chloride mixture, wherein both quality hundred
Divide ratio are as follows: (4- hydroxy phenyl) methylbenzyl sulphur hexafluoro antimonate: 2- diazonium -1- naphthols -5- sulfonic acid chloride=3:7；It is described
Si3N4Powder uses grain size for the silicon nitride ceramic of 2000nm.
Common DLP can be used to project the 3D printer curing molding as light source for the light-cured resin, print products obtained therefrom
For resin/silicon nitride ceramics composite element, 6s can realize the solidification thickness of 40um, and gained slurry uniformity is good, place 120
Sedimentation layering, print surface roughness 0.25um, density 2.0g/cm do not occur for hour3, the Si of the light-cured resin 3D printing3N4
Ceramic idiosome has solid content high, and shaping speed is fast, advantage with high accuracy.
Embodiment 2
3D printing Si according to the present invention for DLP rapid shaping3N4The light-cured resin of ceramics, by weight percentage
Than meter, including 18% the first prepolymer, 18% the second prepolymer, 10% tough agent, 4% photoinitiator, 50%
Si3N4Powder.
Wherein first prepolymer is the aliphatic polyurethane acrylic polymer of degree of functionality 9-10；Second pre-polymerization
Object is ethoxyquin trimethylolpropane trimethacrylate；The tough agent is acryloyl morpholine；The photoinitiator is (4- hydroxyl
Phenyl) methylbenzyl sulphur hexafluoro antimonate and 2- diazonium -1- naphthols -5- sulfonic acid chloride mixture, wherein both quality hundred
Divide ratio are as follows: (4- hydroxy phenyl) methylbenzyl sulphur hexafluoro antimonate: 2- diazonium -1- naphthols -5- sulfonic acid chloride=1:4；It is described
Si3N4Powder uses grain size for the silicon nitride ceramic of 3000nm.
Common DLP can be used to project the 3D printer curing molding as light source for the light-cured resin, print products obtained therefrom
For resin/silicon nitride ceramics composite element, 10s can realize the solidification thickness of 100um, and gained slurry uniformity is good, place
Sedimentation layering, print surface roughness 1.00um, density 1.7g/cm does not occur within 90 hours3, the light-cured resin 3D printing
Si3N4Ceramic idiosome has shaping speed fast, advantage with high accuracy.
Embodiment 3
3D printing Si according to the present invention for DLP rapid shaping3N4The light-cured resin of ceramics, by weight percentage
Than meter, including 18% the first prepolymer, 18% the second prepolymer, 5% tough agent, 4% photoinitiator, 55%
Si3N4Powder.
Wherein first prepolymer is the aliphatic polyurethane acrylic polymer of degree of functionality 9-10；Second pre-polymerization
Object is ethoxyquin trimethylolpropane trimethacrylate；The tough agent is acryloyl morpholine；The photoinitiator is (4- hydroxyl
Phenyl) methylbenzyl sulphur hexafluoro antimonate and 2- diazonium -1- naphthols -5- sulfonic acid chloride mixture, wherein both quality hundred
Divide ratio are as follows: (4- hydroxy phenyl) methylbenzyl sulphur hexafluoro antimonate: 2- diazonium -1- naphthols -5- sulfonic acid chloride=3:1；It is described
Si3N4Powder uses grain size for the silicon nitride ceramic of 800nm.
Common DLP can be used to project the 3D printer curing molding as light source for the light-cured resin, print products obtained therefrom
For resin/silicon nitride ceramics composite element, 10s can realize the solidification thickness of 100um, and gained slurry uniformity is good, place
Sedimentation layering, print surface roughness 0.40um, density 2.0g/cm does not occur within 120 hours3, the light-cured resin 3D printing
Si3N4Ceramic idiosome has solid content high, and shaping speed is fast, advantage with high accuracy.
Embodiment 4
3D printing Si according to the present invention for DLP rapid shaping3N4The light-cured resin of ceramics, by weight percentage
Than meter, including 15% the first prepolymer, 15% the second prepolymer, 5% tough agent, 0.5% photoinitiator, 64.5%
Si3N4Powder.
Wherein first prepolymer is the aliphatic polyurethane acrylic polymer of degree of functionality 9-10；Second pre-polymerization
Object is ethoxyquin trimethylolpropane trimethacrylate；The tough agent is acryloyl morpholine；The photoinitiator is (4- hydroxyl
Phenyl) methylbenzyl sulphur hexafluoro antimonate and 2- diazonium -1- naphthols -5- sulfonic acid chloride mixture, wherein both quality hundred
Divide ratio are as follows: (4- hydroxy phenyl) methylbenzyl sulphur hexafluoro antimonate: 2- diazonium -1- naphthols -5- sulfonic acid chloride=1:3；It is described
Si3N4Powder uses grain size for the silicon nitride ceramic of 500nm.
Common DLP can be used to project the 3D printer curing molding as light source for the light-cured resin, print products obtained therefrom
For resin/silicon nitride ceramics composite element, 10s can realize the solidification thickness of 50um, and gained slurry uniformity is good, place
Sedimentation layering, print surface roughness 0.25um, density 2.1g/cm does not occur within 120 hours3, the light-cured resin 3D printing
Si3N4Ceramic idiosome has solid content high, and shaping speed is fast, advantage with high accuracy.
Claims (6)
1. a kind of 3D printing Si for DLP rapid shaping3N4The light-cured resin of ceramics, it is characterised in that: by weight percentage
Meter, the light-cured resin include the first prepolymer of 15-20%, the second prepolymer of 15-20%, the tough agent of 5-15%,
The photoinitiator of 0.5-4%, the Si of 50-64.5%3N4Powder.
2. the 3D printing Si according to claim 1 for DLP rapid shaping3N4The light-cured resin of ceramics, feature exist
In: first prepolymer is the aliphatic polyurethane acrylic polymer of degree of functionality 9-10.
3. the 3D printing Si according to claim 1 for DLP rapid shaping3N4The light-cured resin of ceramics, feature exist
In: second prepolymer is ethoxyquin trimethylolpropane trimethacrylate.
4. the 3D printing Si according to claim 1 for DLP rapid shaping3N4The light-cured resin of ceramics, feature exist
In: the tough agent is acryloyl morpholine.
5. the 3D printing Si according to claim 1 for DLP rapid shaping3N4The light-cured resin of ceramics, feature exist
In: the photoinitiator is (4- hydroxy phenyl) methylbenzyl sulphur hexafluoro antimonate and 2- diazonium -1- naphthols -5- sulfonic acid chloride
Mixture, wherein the mass percent of the two are as follows: (4- hydroxy phenyl) methylbenzyl sulphur hexafluoro antimonate: 2- diazonium -1- naphthalene
Phenol -5- sulfonic acid chloride=3:1-1:4.
6. the 3D printing Si according to claim 1 for DLP rapid shaping3N4The light-cured resin of ceramics, feature exist
In: the Si3N4Powder uses grain size for the silicon nitride ceramic of 500-5000nm.
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| CN107722193A (en) * | 2017-10-18 | 2018-02-23 | 中山大简科技有限公司 | A kind of high rigidity photosensitive resin composition for photocuring rapid prototyping |
| CN108218440A (en) * | 2017-12-29 | 2018-06-29 | 深圳长朗智能科技有限公司 | Light-cured resin based composite ceramic material and ceramic idiosome degreasing method |
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| CN108751951A (en) * | 2018-06-14 | 2018-11-06 | 长沙鹏登生物陶瓷有限公司 | A kind of 3D printing artificial tooth ceramic material and preparation method |
| CN108976352A (en) * | 2017-06-05 | 2018-12-11 | 惠展电子材料（上海）有限公司 | A kind of 3D printing Photocurable composition based on acrylic resin |
| CN109541889A (en) * | 2018-12-19 | 2019-03-29 | 江苏艾森半导体材料股份有限公司 | Negative photoresist for semiconductor packaging process |
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2019
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Patent Citations (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS62221474A (en) * | 1986-03-24 | 1987-09-29 | Kansai Paint Co Ltd | Method for painting wooden base material |
| CN105259736A (en) * | 2015-11-10 | 2016-01-20 | 上海移石新材料科技有限公司 | Photosensitive resin for 3D printer and preparation method of photosensitive resin |
| CN105566860A (en) * | 2015-12-11 | 2016-05-11 | 上海联泰科技股份有限公司 | Ceramic material for 3D (three-dimensional) light curing forming printing and preparation method thereof |
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| CN107722193A (en) * | 2017-10-18 | 2018-02-23 | 中山大简科技有限公司 | A kind of high rigidity photosensitive resin composition for photocuring rapid prototyping |
| CN108218440A (en) * | 2017-12-29 | 2018-06-29 | 深圳长朗智能科技有限公司 | Light-cured resin based composite ceramic material and ceramic idiosome degreasing method |
| CN108727550A (en) * | 2018-04-23 | 2018-11-02 | 浙江锐胜新材料有限公司 | A kind of photosensitive resin and its application |
| CN108751951A (en) * | 2018-06-14 | 2018-11-06 | 长沙鹏登生物陶瓷有限公司 | A kind of 3D printing artificial tooth ceramic material and preparation method |
| CN109541889A (en) * | 2018-12-19 | 2019-03-29 | 江苏艾森半导体材料股份有限公司 | Negative photoresist for semiconductor packaging process |
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Application publication date: 20191015 |