CN114347464A - 3D printing photosensitive material taking green light as photocuring light source and 3D printer thereof - Google Patents

3D printing photosensitive material taking green light as photocuring light source and 3D printer thereof Download PDF

Info

Publication number
CN114347464A
CN114347464A CN202210077568.8A CN202210077568A CN114347464A CN 114347464 A CN114347464 A CN 114347464A CN 202210077568 A CN202210077568 A CN 202210077568A CN 114347464 A CN114347464 A CN 114347464A
Authority
CN
China
Prior art keywords
printing
green light
light
photosensitive
curing
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
Application number
CN202210077568.8A
Other languages
Chinese (zh)
Inventor
王钢
马传哲
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Sun Yat Sen University
Original Assignee
Sun Yat Sen University
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Sun Yat Sen University filed Critical Sun Yat Sen University
Publication of CN114347464A publication Critical patent/CN114347464A/en
Pending legal-status Critical Current

Links

Images

Classifications

    • BPERFORMING OPERATIONS; TRANSPORTING
    • B29WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29CSHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C64/00Additive manufacturing, i.e. manufacturing of three-dimensional [3D] objects by additive deposition, additive agglomeration or additive layering, e.g. by 3D printing, stereolithography or selective laser sintering
    • B29C64/10Processes of additive manufacturing
    • B29C64/106Processes of additive manufacturing using only liquids or viscous materials, e.g. depositing a continuous bead of viscous material
    • B29C64/124Processes of additive manufacturing using only liquids or viscous materials, e.g. depositing a continuous bead of viscous material using layers of liquid which are selectively solidified
    • B29C64/129Processes of additive manufacturing using only liquids or viscous materials, e.g. depositing a continuous bead of viscous material using layers of liquid which are selectively solidified characterised by the energy source therefor, e.g. by global irradiation combined with a mask
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B28WORKING CEMENT, CLAY, OR STONE
    • B28BSHAPING CLAY OR OTHER CERAMIC COMPOSITIONS; SHAPING SLAG; SHAPING MIXTURES CONTAINING CEMENTITIOUS MATERIAL, e.g. PLASTER
    • B28B1/00Producing shaped prefabricated articles from the material
    • B28B1/001Rapid manufacturing of 3D objects by additive depositing, agglomerating or laminating of material
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B33ADDITIVE MANUFACTURING TECHNOLOGY
    • B33YADDITIVE 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
    • B33Y10/00Processes of additive manufacturing

Landscapes

  • Engineering & Computer Science (AREA)
  • Chemical & Material Sciences (AREA)
  • Manufacturing & Machinery (AREA)
  • Materials Engineering (AREA)
  • Mechanical Engineering (AREA)
  • Ceramic Engineering (AREA)
  • Physics & Mathematics (AREA)
  • Optics & Photonics (AREA)

Abstract

The invention discloses a 3D printing photosensitive material taking green light as a photocuring light source, which at least comprises a green light photoinitiation system, wherein the green light photoinitiation system is a Norrish type I photosensitizer and a Norrish type II photosensitizer which have light absorption initiation capability in a green light wavelength range, and the green light photoinitiation system comprises a curcumin compound/onium salt system, a boron difluoride curcumin compound/onium salt system, a ferrocene-containing conjugated indene diketone compound/onium salt/azomethylpyrrolidone system, a benzylidene ketone compound/onium salt system and a benzylidene ketone compound/amine system. The method has the beneficial effects that on one hand, by adopting the principle that the longer the wavelength, the lower the light refractive index is, and the longer the wavelength, the stronger the light penetrating capacity is, the curing depth of the 3D printing material can be obviously improved, and the interlayer cracking problem is avoided, especially the 3D printing material with high refractive index, such as 3D printing photosensitive ceramic slurry and the like; on the other hand, by adopting the principle that the longer the wavelength is, the lower the light refractive index is, the curing width of the 3D printing material can be obviously reduced, and the curing and printing precision is improved, especially for the 3D printing material with high refractive index, such as 3D printing photosensitive ceramic slurry and the like.

Description

3D printing photosensitive material taking green light as photocuring light source and 3D printer thereof
Technical Field
The invention relates to the field of 3D printing, in particular to a 3D printing photosensitive material taking green light as a photocuring light source and a 3D printer thereof.
Background
The photocuring type 3D printing method is a 3D printing method based on a photocuring (photopolymerization) method and has the characteristics of high speed, high efficiency and high precision. The existing light-curing type 3D printing method mostly adopts an ultraviolet light source, because almost all the existing commercial photoinitiators are used under ultraviolet light.
In the actual use process, the ultraviolet light source-based photocuring type 3D printing method has the problems of poor precision, easy delamination and low success rate. The 3D printing process is controlled by the shape and the range of light in the photocuring 3D printing process, and no matter the light-sensitive resin or the powder in various light-sensitive pastes has the light refractive index, so that the light is refracted in the 3D printing process to cause precision errors, the curing depth is reduced, and interlayer cracking is caused, particularly for a high-refractive-index light-sensitive material system, such as 3D printing of light-sensitive ceramic paste and the like.
This phenomenon has been supported by the theory at present. In the photo-curing type ceramic 3D printing method, the most obvious phenomenon of the photo-curing area is the variation of the curing depth and the additional curing width. The curing depth refers to the maximum curing thickness which can be reached by the photosensitive ceramic slurry in a certain time under illumination, the extra curing width refers to the curing width of the photosensitive ceramic slurry in a non-illumination area, and the extra curing width is generated due to the optical refractive index. There is a well established theoretical system for the phenomenon of photosensitive ceramics when cured.
Halloran et al, based on Jacob's equation and Beer-Lambert's law and other related formulas and studies, gave the relationship between the curing depth Cd and the curing width and energy.
Figure BDA0003484658820000021
wex=wcure-wbeam
Figure BDA0003484658820000022
In the formula, DdAnd DwSensitivity of the photosensitive ceramic slurry in the vertical and horizontal directions, respectively, E0Energy dose in the light time, EdAnd EwThe critical energy dose at which curing occurs in the vertical and horizontal directions, respectively. As in the course of the experiment, wexFrom the curing Width experiment, wcureTo cure the width, wbeamIs the slit width.
The existing light curing type 3D printing method based on the ultraviolet light source has the following defects: 1. the problem of interlayer cracking in the 3D printing process can occur due to low curing depth, especially due to the fact that a photosensitive system with high refractive index and high light absorption rate, such as photosensitive ceramic slurry, photosensitive metal slurry and the like; 2. curing and printing precision is poor, due to the existence of a light refraction phenomenon, a large amount of refraction light exists in a non-curing area, so that edge curing occurs, and the printing precision is reduced, especially for photosensitive systems with high refractive index and high light absorptivity, such as photosensitive ceramic slurry, photosensitive metal slurry and the like; 3. the curing depth and the curing precision conflict with each other, for example, the improvement of the light intensity is beneficial to improving the curing depth, but the edge curing is increased to reduce the precision; 4. in the existing method, for example, a method for increasing the accuracy by adding a light-absorbing dye is not suitable for photosensitive materials with high refractive index and high light absorption rate, because the curing depth of the photosensitive materials is poor, the addition of the light-absorbing dye for increasing the accuracy can further reduce the curing depth, and cause the problems of interlayer cracking and the like.
Disclosure of Invention
In view of the defects of the prior art, the invention aims to provide a 3D printing photosensitive material taking green light as a photocuring light source and a 3D printer thereof, which can solve the problems of low curing depth and poor curing precision of a photocuring 3D printing method under an ultraviolet light source.
In order to achieve the purpose, the technical scheme adopted by the invention is as follows:
A3D printing photosensitive material taking green light as a photocuring light source at least comprises a green light photoinitiation system, wherein the green light photoinitiation system is a Norrish type I photosensitizer and a Norrish type II photosensitizer which have light absorption initiation capability in a green light wavelength range, and comprises a curcumin compound/onium salt system, a boron difluoride curcumin compound/onium salt system, a ferrocene-containing conjugated indene dione compound/onium salt/azomethylpyrrolidone system, a benzylidene ketone compound/onium salt system and a benzylidene ketone compound/amine system.
It should be noted that the photosensitive material may be used to form one of 3D printing photosensitive resin, 3D printing photosensitive ceramic paste, 3D printing photosensitive metal paste, or 3D printing photosensitive casting wax paste.
The 3D printing photosensitive resin contains a green light photoinitiation system, a photosensitive acrylic resin and an auxiliary agent, and the weight ratio of the green light photoinitiation system to the photosensitive acrylic resin to the auxiliary agent is (0.1-5): (90-99.5): (0.4-5).
The 3D printing photosensitive ceramic slurry contains a green light photoinitiation system, photosensitive acrylic resin, ceramic powder and an auxiliary agent, wherein the weight ratio of the green light photoinitiation system to the photosensitive acrylic resin is (0.1-5): (9.5-54.5): (45-90): (0.4-5).
The 3D printing photosensitive metal paste comprises a green light photoinitiation system, photosensitive acrylic resin, metal powder and an auxiliary agent in the 3D printing photosensitive metal paste, wherein the weight ratio of the green light photoinitiation system to the photosensitive acrylic resin to the metal powder is (0.1-5): (9.5-30): (60-90): (0.4-5).
The photosensitive casting wax slurry for 3D printing comprises a green light photoinitiation system, photosensitive acrylic resin, wax powder and an auxiliary agent, wherein the weight ratio of the green light photoinitiation system to the photosensitive acrylic resin to the wax powder to the auxiliary agent is (0.1-5): (19.5-60): (30-80): (0.4-5).
The invention also provides a light-curing type 3D printer with the 3D printing photosensitive material taking green light as a light-curing light source, wherein the light-curing type 3D printer is one of an SLA-3D printer, a DLP-3D printer or an LCD-3D printer.
It should be noted that the light-curing type 3D printer includes a green LED chip and a green laser light source, wherein the wavelength range of the green light source is 492-577 nm.
As an application of the invention, the invention also provides a photocuring 3D printer for 3D printing of photosensitive materials by taking green light as a photocuring light source, and the photocuring 3D printer can be applied to handheld production, ceramic forming, metal forming and wax mold forming.
The method has the beneficial effects that on one hand, by adopting the principle that the longer the wavelength, the lower the light refractive index is, and the longer the wavelength, the stronger the light penetrating capacity is, the curing depth of the 3D printing material can be obviously improved, and the interlayer cracking problem is avoided, especially the 3D printing material with high refractive index, such as 3D printing photosensitive ceramic slurry and the like; on the other hand, by adopting the principle that the longer the wavelength is, the lower the light refractive index is, the curing width of the 3D printing material can be obviously reduced, and the curing and printing precision is improved, especially for the 3D printing material with high refractive index, such as 3D printing photosensitive ceramic slurry and the like.
Drawings
Fig. 1 is experimental data of curing width of 3D printing photosensitive ceramic paste under ultraviolet light and green light according to a preferred embodiment of the present invention.
Detailed Description
The present invention will be further described with reference to the accompanying drawings, and it should be noted that the present embodiment is based on the technical solution, and the detailed implementation and the specific operation process are provided, but the protection scope of the present invention is not limited to the present embodiment.
The invention relates to a 3D printing photosensitive material taking green light as a photocuring light source, which at least comprises a green light photoinitiation system, wherein the green light photoinitiation system is a Norrish type I photosensitizer and a Norrish type II photosensitizer which have light absorption initiation capability in a green light wavelength range, and the Norrish type I photosensitizer and the Norrish type II photosensitizer comprise a curcumin compound/onium salt system, a boron difluoride curcumin compound/onium salt system, a ferrocene-containing conjugated indene dione compound/onium salt/azomethylpyrrolidone system, a benzylidene ketone compound/onium salt system and a benzylidene ketone compound/amine system.
Further, the photosensitive material can be used for forming one of 3D printing photosensitive resin, 3D printing photosensitive ceramic slurry, 3D printing photosensitive metal slurry or 3D printing photosensitive casting wax slurry.
Further, the 3D printing photosensitive resin comprises a green light photoinitiation system, a photosensitive acrylic resin and an auxiliary agent, wherein the weight ratio of the green light photoinitiation system to the photosensitive acrylic resin to the auxiliary agent is (0.1-5): (90-99.5): (0.4-5).
Further, the 3D printing photosensitive ceramic slurry contains a green light photoinitiation system, photosensitive acrylic resin, ceramic powder and an auxiliary agent, wherein the weight ratio of the green light photoinitiation system to the photosensitive acrylic resin to the ceramic powder is (0.1-5): (9.5-54.5): (45-90): (0.4-5).
Further, the 3D printing photosensitive metal paste comprises a green light photoinitiation system, photosensitive acrylic resin, metal powder and an auxiliary agent in the 3D printing photosensitive metal paste, wherein the weight ratio of the green light photoinitiation system to the photosensitive acrylic resin to the metal powder is (0.1-5): (9.5-30): (60-90): (0.4-5).
Furthermore, in the 3D printing photosensitive casting wax slurry, a green light photoinitiation system, photosensitive acrylic resin, wax powder and an auxiliary agent are added, wherein the weight ratio of the green light photoinitiation system to the photosensitive acrylic resin to the wax powder is (0.1-5): (19.5-60): (30-80): (0.4-5).
The invention also provides a light-curing type 3D printer with the 3D printing photosensitive material taking green light as a light-curing light source, wherein the light-curing type 3D printer is one of an SLA-3D printer, a DLP-3D printer or an LCD-3D printer.
Furthermore, the light-curing type 3D printer comprises a green LED chip and a green laser light source, wherein the wavelength range of the green light source is 492-577 nm.
As an application of the invention, the invention also provides a photocuring 3D printer for 3D printing of photosensitive materials by taking green light as a photocuring light source, and the photocuring 3D printer can be applied to handheld production, ceramic forming, metal forming and wax mold forming.
It should be noted that, the following further illustrates the advantages of the technical solution of the present invention through different models of 3D printers.
Example one
The present embodiment discloses an SLA type 3D printer and a 3D printing method, which are implemented by using an SLA-3D printer with green light as a light source, which is a 520nm green laser light source.
The embodiment also discloses a 3D printing photosensitive resin, which uses phenothiazine curcumin/iodonium salt as a green light photoinitiation system, the content is 0.5g/1.5g, the composition of the photosensitive resin is that epoxy acrylic resin/difunctional polyurethane acrylic resin/tripropylene glycol diacrylate are 35g/25g/35g, and the composition of a defoaming agent/an adhesion promoter is 1g/2g.
Figure BDA0003484658820000071
The molar extinction coefficient of phenothiazine curcumin at 520nm is 169900M-1cm-1
In this embodiment, the curing depth of the 3D printing photosensitive resin at 500mJ was 53 mm.
In the embodiment, the optical power density of the green SLA-3D printer is 500mW/cm during working2The focal plane spot size was 0.15mm, the layer thickness was 0.05mm (precision manufacturing)/0.5 mm (rapid manufacturing), the molding accuracy was 0.01mm (precision manufacturing)/0.1 mm (rapid manufacturing), and the scanning speed was 10 m/s.
The photo-curing 3D printing method using green light as a light source disclosed in the embodiment can be used for small-sized handheld high-precision manufacturing and rapid manufacturing of large models.
Example two
The present embodiment discloses a DLP type 3D printer and a 3D printing method, the 3D printing method being implemented by using a DLP-3D printer having green light as a light source, which is a 520nm green laser light source.
The embodiment also discloses 3D printing photosensitive ceramic slurry, which uses triphenylamine curcumin/iodonium salt as a green light photoinitiation system, wherein the content of the triphenylamine curcumin/iodonium salt is 0.5g/1.5g, the photosensitive resin composition is acryloylmorpholine/hexa-functionality polyurethane acrylic resin/tripropylene glycol diacrylate is 5g/8g/7g, the zirconia nano powder is 75g, and the defoaming agent/dispersing agent is 1g/2g.
Figure BDA0003484658820000081
The molar extinction coefficient of triphenylamine curcumin at 520nm is 11998M-1cm-1
In this example, the curing depth of the 3D printing photosensitive ceramic paste at 500mJ was 1.00 mm.
In this embodiment, the light power density of the green DLP-3D printer is 10mW/cm during operation2The layer thickness was 0.05mm (precision manufacturing)/0.1 mm (rapid manufacturing), the molding accuracy was 0.05mm (precision manufacturing)/0.1 mm (rapid manufacturing), and the single layer exposure time was 20 seconds.
The photo-curing 3D printing method using green light as a light source disclosed in the embodiment can be used for high-precision and rapid manufacturing of zirconia ceramic components.
EXAMPLE III
The present embodiment discloses a DLP type 3D printer and a 3D printing method, the 3D printing method being implemented by using a DLP-3D printer having green light as a light source, which is a 520nm green laser light source.
The embodiment also discloses a 3D printing photosensitive metal paste, which uses triphenylamine curcumin/iodonium salt as a green light photoinitiation system, wherein the content is 0.5g/1.5g, the photosensitive resin composition is acryloyl morpholine/hexa-functionality polyurethane acrylic resin/propylene glycol diacrylate is 2g/9g/4g, the spherical tungsten nano powder is 80g, and the anti-settling agent/dispersant is 2g/1g.
In this embodiment, the curing depth of the 3D printing photosensitive metal paste at 500mJ is 0.86 mm.
In this embodiment, the light power density of the green DLP-3D printer is 10mW/cm during operation2The layer thickness was 0.05mm (precision manufacturing)/0.1 mm (rapid manufacturing), the molding accuracy was 0.01mm (precision manufacturing)/0.05 mm (rapid manufacturing), and the single layer exposure time was 20 seconds.
The photo-curing 3D printing method using green light as a light source disclosed by the embodiment can be used for high-precision and rapid manufacturing of metal tungsten parts.
Example four
The present embodiment discloses an SLA type 3D printer and a 3D printing method, which are implemented by using an SLA-3D printer with green light as a light source, which is a 520nm green laser light source.
The embodiment also discloses photosensitive casting wax slurry for 3D printing, wherein dimethylamino curcumin/iodonium salt is used as a green light photoinitiation system, the content is 0.5g/1.5g, the photosensitive resin comprises 25g/10g/10g of polyethylene glycol acrylate/1, 6-hexanediol diacrylate/tripropylene glycol diacrylate, 50g of polyethylene wax powder, and 2g/1g of a flatting agent/dispersant.
In this example, the curing depth of the 3D printing photosensitive metal paste at 500mJ was 62 mm.
In the embodiment, the optical power density of the green SLA-3D printer is 500mW/cm during working2The focal plane spot size was 0.15mm, the layer thickness was 0.05mm (precision manufacturing)/0.5 mm (rapid manufacturing), the molding accuracy was 0.01mm (precision manufacturing)/0.1 mm (rapid manufacturing), and the scanning speed was 10 m/s.
The photo-curing 3D printing method using green light as a light source disclosed by the embodiment can be used for high-precision and rapid manufacturing of the wax mould.
Various other changes and modifications to the above-described embodiments and concepts will become apparent to those skilled in the art from the above description, and all such changes and modifications are intended to be included within the scope of the present invention as defined in the appended claims.

Claims (9)

1. The 3D printing photosensitive material with green light as a photocuring light source is characterized by at least comprising a green light photoinitiation system, wherein the green light photoinitiation system is a Norrish type I photosensitizer and a Norrish type II photosensitizer which have light absorption initiation capability in a green light wavelength range, and comprises a curcumin compound/onium salt system, a boron difluoride curcumin compound/onium salt system, a ferrocene-containing conjugated indene diketone compound/onium salt/azomethylpyrrolidone system, a benzylidene ketone compound/onium salt system and a benzylidene ketone compound/amine system.
2. The photosensitive material for 3D printing with green light as light curing source of claim 1, wherein the photosensitive material can be used to compose one of 3D printing photosensitive resin, 3D printing photosensitive ceramic paste, 3D printing photosensitive metal paste or 3D printing photosensitive casting wax paste.
3. The photosensitive material for 3D printing with green light as a photocuring light source according to claim 2, wherein the photosensitive resin for 3D printing contains a green light photoinitiation system, a photosensitive acrylic resin and an auxiliary agent in a weight ratio of (0.1-5): (90-99.5): (0.4-5).
4. The 3D printing photosensitive material taking green light as a photocuring light source according to claim 2, wherein the 3D printing photosensitive ceramic slurry contains a green light photoinitiation system, photosensitive acrylic resin, ceramic powder and an auxiliary agent in a weight ratio of (0.1-5): (9.5-54.5): (45-90): (0.4-5).
5. The 3D printing photosensitive material taking green light as a photocuring light source according to claim 2, wherein the 3D printing photosensitive metal paste contains a green light photoinitiation system, photosensitive acrylic resin, metal powder and an auxiliary agent in the 3D printing photosensitive metal paste, and the weight ratio of the green light photoinitiation system to the photosensitive acrylic resin to the metal powder is (0.1-5): (9.5-30): (60-90): (0.4-5).
6. The 3D printing photosensitive material taking green light as a photocuring light source according to claim 2, wherein the green light photoinitiation system, the photosensitive acrylic resin, the wax powder and the auxiliary agent are contained in the 3D printing photosensitive casting wax slurry in a weight ratio of (0.1-5): (19.5-60): (30-80): (0.4-5).
7. A light curable 3D printer having the light sensitive material for 3D printing with green light as light curing source of claim 1, wherein the light curable 3D printer is one of SLA-3D printer, DLP-3D printer or LCD-3D printer.
8. The photo-curing type 3D printer for 3D printing of photosensitive material with green light as the photo-curing light source as claimed in claim 7, wherein the photo-curing type 3D printer comprises a green LED chip and a green laser light source, wherein the wavelength range of the green light source is 492-577 nm.
9. The photo-curing 3D printer of the 3D printing photosensitive material with green light as the photo-curing light source according to claim 7 or 8, wherein the photo-curing 3D printer can be applied to handheld production, ceramic forming, metal forming and wax mold forming.
CN202210077568.8A 2021-09-29 2022-01-24 3D printing photosensitive material taking green light as photocuring light source and 3D printer thereof Pending CN114347464A (en)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
CN202111153983.9A CN113895031A (en) 2021-09-29 2021-09-29 3D printing photosensitive material taking green light as photocuring light source and 3D printer thereof
CN2021111539839 2021-09-29

Publications (1)

Publication Number Publication Date
CN114347464A true CN114347464A (en) 2022-04-15

Family

ID=79189433

Family Applications (2)

Application Number Title Priority Date Filing Date
CN202111153983.9A Pending CN113895031A (en) 2021-09-29 2021-09-29 3D printing photosensitive material taking green light as photocuring light source and 3D printer thereof
CN202210077568.8A Pending CN114347464A (en) 2021-09-29 2022-01-24 3D printing photosensitive material taking green light as photocuring light source and 3D printer thereof

Family Applications Before (1)

Application Number Title Priority Date Filing Date
CN202111153983.9A Pending CN113895031A (en) 2021-09-29 2021-09-29 3D printing photosensitive material taking green light as photocuring light source and 3D printer thereof

Country Status (1)

Country Link
CN (2) CN113895031A (en)

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN116444282A (en) * 2023-03-14 2023-07-18 北京遥感设备研究所 Fused quartz photocuring forming method based on introduction of ZrO2-B4C

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN107501442A (en) * 2017-08-15 2017-12-22 宁波七诺新材料科技有限公司 For 3D printing technique by visible light-initiated photoinitiator composite and application
CN108440688A (en) * 2018-01-31 2018-08-24 北京化工大学 Application of a kind of curcumin derivate in visible-light curing field
CN109232668A (en) * 2018-08-28 2019-01-18 安庆北化大科技园有限公司 A kind of ferrocene derivatives and combinations thereof can be used as photoredox catalyst in photopolymerization
CN110894191A (en) * 2019-11-26 2020-03-20 安庆北化大科技园有限公司 Phenothiazinyl conjugated benzylidene ketone photosensitizer and preparation method and application thereof
US20200282638A1 (en) * 2019-02-11 2020-09-10 Photocentric Limited Method of making 3d printed objects using two distinct light sources

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN107501442A (en) * 2017-08-15 2017-12-22 宁波七诺新材料科技有限公司 For 3D printing technique by visible light-initiated photoinitiator composite and application
CN108440688A (en) * 2018-01-31 2018-08-24 北京化工大学 Application of a kind of curcumin derivate in visible-light curing field
CN109232668A (en) * 2018-08-28 2019-01-18 安庆北化大科技园有限公司 A kind of ferrocene derivatives and combinations thereof can be used as photoredox catalyst in photopolymerization
US20200282638A1 (en) * 2019-02-11 2020-09-10 Photocentric Limited Method of making 3d printed objects using two distinct light sources
CN110894191A (en) * 2019-11-26 2020-03-20 安庆北化大科技园有限公司 Phenothiazinyl conjugated benzylidene ketone photosensitizer and preparation method and application thereof

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
甘志伟等: "绿光激光器引发光敏树脂光固化的研究" *

Also Published As

Publication number Publication date
CN113895031A (en) 2022-01-07

Similar Documents

Publication Publication Date Title
US12071566B2 (en) Antimony-free radiation curable compositions for additive fabrication, and applications thereof in investment casting processes
CN105924571B (en) Continuous photocurable three-dimensional printing materials
EP2396299B1 (en) Liquid radiation curable resin compositions for additive fabrication comprising a triaryl sulfonium borate cationic photoinitiator
RU2005116302A (en) IMPROVEMENT OF STABILITY OF PHOTO INITIATORS DURING STORAGE
CN114347464A (en) 3D printing photosensitive material taking green light as photocuring light source and 3D printer thereof
JP2887684B2 (en) Photocurable composition
US11780989B2 (en) Optically active build materials for 3D printing
JP5393239B2 (en) Processing method for optical three-dimensional object
US20240131780A1 (en) Additives for build materials and associated printed 3d articles
JP2008291172A (en) Curable composition and method for curing the same
CN1813220A (en) Low-viscous,radiation curable formulation,particularly for the stereolithographical production of earpieces
CN111526977B (en) Compositions and articles for additive manufacturing and methods of use thereof
JP5738367B2 (en) Optical three-dimensional model with low yellowness
JP2009046565A (en) Curable composition
WO2014196536A1 (en) Curing resin composition and three-dimensional formed article
JP7052397B2 (en) Composition for three-dimensional model, manufacturing device for three-dimensional model, and method for manufacturing three-dimensional model
JP6844664B2 (en) 3D model manufacturing method and 3D model manufacturing equipment
CN109293851B (en) Photo-curing resin composition and optical device prepared from same
JP2023140213A (en) Curable composition, storage container, and three-dimensional object producing method
CN115157666A (en) Evanescent wave-based dual-optical-path 3D printing method and device
CN113045706A (en) Low-tack photocurable resin composition and high-speed three-dimensional printing method
KR101655708B1 (en) Photopolymerizable composition
JP2022147319A (en) Inkjet active-energy-ray-curable composition, three-dimensional object producing method, and three-dimensional object producing apparatus

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: 20220415

RJ01 Rejection of invention patent application after publication