CN107815219A - A kind of preparation method of 3D printing photosensitive resin - Google Patents
A kind of preparation method of 3D printing photosensitive resin Download PDFInfo
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- CN107815219A CN107815219A CN201710837616.8A CN201710837616A CN107815219A CN 107815219 A CN107815219 A CN 107815219A CN 201710837616 A CN201710837616 A CN 201710837616A CN 107815219 A CN107815219 A CN 107815219A
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- photosensitive resin
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D163/00—Coating compositions based on epoxy resins; Coating compositions based on derivatives of epoxy resins
- C09D163/10—Epoxy resins modified by unsaturated compounds
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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
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- Life Sciences & Earth Sciences (AREA)
- Wood Science & Technology (AREA)
- Organic Chemistry (AREA)
- Manufacturing & Machinery (AREA)
- Photosensitive Polymer And Photoresist Processing (AREA)
- Materials For Photolithography (AREA)
Abstract
The invention provides a kind of preparation method of 3D printing photosensitive resin, by mass parts, by 10 30 parts of modified butadiene rubber；30 60 parts of epoxy acrylates；0.1 1 parts anti-2, along 6 nonadienols, 0.01 0.1 part of three (cyano group formula dialkylene) cerium, 0.01 0.1 part of four (trimethyl silene ether) titanium, 20 35 parts of diluents；14 parts of initiators；14 parts of accelerator, 10 20min are stirred, obtain photosensitive resin；By obtained photosensitive resin material coated on surface treated iron plate, iron plate is positioned in photo solidification machine and solidified, hardening time is 30 70s, and 3D printing photosensitive resin is made.
Description
Technical field
The present invention relates to the preparation method of the preparation method of photosensitive resin, especially 3D printing photosensitive resin.
Background technology
3D printer is also known as 3 D Printer, is a kind of new manufacture based on material stacking method, its is basic
Principle is " Layered manufacturing, successively adding ".Using laser beam, hot melt nozzle etc. mode by metal dust, ceramic powders, plastics,
The special materials such as cell tissue carry out successively accumulation and cohered, and final superposition shaping, produce entity products.First by powdering during work
Roller moves left and right, and will uniformly be laid on moulding cylinder for the powder in powder cylinder, then according to designed part model by printing
Head sprays this cross sectional shape on first layer powder, and then moulding cylinder moves down, and prints the second layer according still further to this step, passes through
Interlayer superposition makes part, and integrally each section is piled up to form product.
It for the material of photocureable rapid shaping is liquid photocurable resin that photosensitive resin, which is, or liquid photosensitive resin,
Mainly it is made up of oligomer, light trigger, diluent.Nearly 2 years, photosensitive resin had just been used for 3D printing emerging industry, photosensitive tree
Lipid 3D printing consumptive material is because its printing precision is high, and sharpness of border, surface is smooth, and interest in industry with paying attention to.
CN201310259101.6 discloses a kind of photosensitive resin for 3D printing and preparation method thereof, the photosensitive resin
By 35~40 parts of acrylate, 35~40 parts of epoxy resin, 20~30 parts of diluent, 0.1~5 part of defoamer, levelling agent 0.1~
1~10 part of 5 parts, 1~10 part of cationic initiators and free radical type Photoepolymerizationinitiater initiater are prepared.Light prepared by the present invention
Quick resin has the characteristics that shaping speed is fast, excitant is small, technique is simple and cost is cheap, may be directly applied to 3D printing and is made
Baroque product.
CN201410648958.1 belongs to 3D printing field of new materials, particularly belongs to photosensitive resin field.Percentage by weight
Than meter, the photosensitive resin includes following components：Acrylate 35~80%, radical initiator 0.5~10%, diluent 10
~55%.The photosensitive resin viscosity of the present invention is below 220cps, and viscosity is low, and shaping is fast, has ensured the Quick-forming of 3D products
Property, meet that industrial use requires.
Existing photosensitive resin due to matrix arrange in pairs or groups with formula design etc. reason cause curing efficiency is low, part performance is poor,
Printed material low intensity, excitant are big and the deficiencies of cost is high.Therefore, comprehensive curing efficiency, the product for improving 3D printing material
Performance, intensity etc., and the cost for reducing 3D printing material is that current industry breaks through difficult point.
The content of the invention
Present invention aims at solve above-mentioned technical problem present in prior art, there is provided 3D printing photosensitive resin, its
It is characterised by following steps：
1st, the preparation of modified butadiene rubber：
By initiator of (CH3) 3CLi, hexamethylene be solvent, butadiene carries out anionic polymerisation, and with oxirane and methanol
End-blocking, temperature are 40-60 DEG C, time 1-5h, obtain the polybutadiene telechelic polymer with terminal hydroxy group, then exist with acrylic acid
At 130-150 DEG C, it is that catalyst carries out esterification 2-8h with N- hydroxyl -5- ENBs -2,3- dicarboximide, is modified
Butadiene rubber；
2nd, the preparation of 3D printing photosensitive resin
By mass parts, by 10-30 part modified butadiene rubber；30-60 part epoxy acrylates；0.1-1 parts trans- 2, along 6- nonyls two
Enol, 0.01-0.1 parts three (cyano group formula dialkylene) cerium, 0.01-0.1 parts four-(trimethyl silene ether) titanium, the dilution of 20-35 parts
Agent；1-4 part initiators；1-4 part accelerator, 10-20min is stirred, obtains photosensitive resin；Obtained photosensitive resin material is coated
On surface treated iron plate, iron plate is positioned in photo solidification machine and solidified, hardening time 30-70s, 3D is made
Printed photosensitive resin.
In mass ratio, (CH3) 3CLi：Hexamethylene：Butadiene：Oxirane：Methanol=(1.5-2.5)：30：(1.5-
2.5)：(1.5-2.5)：1,
In mass ratio, polybutadiene telechelic polymer：Acrylic acid：N- hydroxyl -5- ENB -2,3- dicarboximide=1：
1：(0.03-0.05).
Diluent described in step 2 is in trihydroxy acrylate, 1,6- hexanediyl esters and styrene
It is any.
Initiator described in step 2 is appointing in 2,2- dimethoxy -2- phenyl acetophenones, UV-184 and UV-1173
It is a kind of.
Accelerator described in step 2 is methacrylic acid phosphoric acid ester.
The product of the present invention has the advantages that：
3D printing photosensitive resin of the present invention, its 3D printing photosensitive resin material produced have high intensity, low cost,
Rapid shaping, synthesis improve the performances such as intensity, the curing efficiency of 3D printing material.
Embodiment
Following instance is only to further illustrate the present invention, is not limitation the scope of protection of the invention.
Embodiment 1
1st, the preparation of modified butadiene rubber：
By initiator of (CH3) 3CLi, hexamethylene be solvent, butadiene carries out anionic polymerisation, and with oxirane and methanol
End-blocking, temperature are 50 DEG C, time 2h, obtain the polybutadiene telechelic polymer with terminal hydroxy group, then with acrylic acid at 138 DEG C
Under, it is that catalyst carries out esterification 5h with N- hydroxyl -5- ENBs -2,3- dicarboximide, obtains modified butadiene rubber；
2nd, the preparation of 3D printing photosensitive resin
By mass parts, by 20 parts of modified butadiene rubber；45 parts of epoxy acrylates；0.5 part trans- 2, suitable 6- nonadienols,
0.04 part of three (cyano group formula dialkylene) cerium, 0.07 part four-(trimethyl silene ether) titanium, 28 parts of diluents；3 parts of initiators；2.2 part
Accelerator, 14min is stirred, obtains photosensitive resin；Obtained photosensitive resin material is coated on surface treated iron plate,
Iron plate is positioned in photo solidification machine and solidified, hardening time 30-70s, 3D printing photosensitive resin is made.
In mass ratio, (CH3) 3CLi：Hexamethylene：Butadiene：Oxirane：Methanol=2：30：2：2：1,
In mass ratio, polybutadiene telechelic polymer：Acrylic acid：N- hydroxyl -5- ENB -2,3- dicarboximide=1：
1：0.05, production code member M-1.
Embodiment 2
1st, the preparation of modified butadiene rubber：
By initiator of (CH3) 3CLi, hexamethylene be solvent, butadiene carries out anionic polymerisation, and with oxirane and methanol
End-blocking, temperature are 40 DEG C, time 5h, obtain the polybutadiene telechelic polymer with terminal hydroxy group, then with acrylic acid at 130 DEG C
Under, it is that catalyst carries out esterification 2h with N- hydroxyl -5- ENBs -2,3- dicarboximide, obtains modified butadiene rubber；
In mass ratio, (CH3) 3CLi：Hexamethylene：Butadiene：Oxirane：Methanol=1.5：30：1.5：1.5：1, in mass ratio, gather
Butadiene telechelic polymer：Acrylic acid：N- hydroxyl -5- ENB -2,3- dicarboximide=1：1：0.03,
2nd, the preparation of 3D printing photosensitive resin
By mass parts, by 10 parts of modified butadiene rubber；30 parts of epoxy acrylates；0.1 part trans- 2, suitable 6- nonadienols,
0.01 part of three (cyano group formula dialkylene) cerium, 0.01 part four-(trimethyl silene ether) titanium, 20 parts of diluents；1 part of initiator；1 part of rush
Enter agent, stir 10min, obtain photosensitive resin；Obtained photosensitive resin material is coated on surface treated iron plate, will
Iron plate, which is positioned in photo solidification machine, to be solidified, hardening time 30s, and 3D printing photosensitive resin is made.Production code member M-2.
Embodiment 3
1st, the preparation of modified butadiene rubber：
By initiator of (CH3) 3CLi, hexamethylene be solvent, butadiene carries out anionic polymerisation, and with oxirane and methanol
End-blocking, temperature are 60 DEG C, time 5h, obtain the polybutadiene telechelic polymer with terminal hydroxy group, then with acrylic acid at 150 DEG C
Under, it is that catalyst carries out esterification 8h with N- hydroxyl -5- ENBs -2,3- dicarboximide, obtains modified butadiene rubber；
In mass ratio, (CH3) 3CLi：Hexamethylene：Butadiene：Oxirane：Methanol=2.5：30：2.5：2.5：1, in mass ratio, gather
Butadiene telechelic polymer：Acrylic acid：N- hydroxyl -5- ENB -2,3- dicarboximide=1：1：0.05；
2nd, the preparation of 3D printing photosensitive resin
By mass parts, by 30 parts of modified butadiene rubber；60 parts of epoxy acrylates；1 part trans- 2, suitable 6- nonadienols, 0.1 part
Three (cyano group formula dialkylene) ceriums, 0.1 part four-(trimethyl silene ether) titanium, 35 parts of diluents；4 parts of initiators；4 parts of accelerator, stir
20min is mixed, obtains photosensitive resin；By obtained photosensitive resin material coated on surface treated iron plate, iron plate is put
It is placed in photo solidification machine and is solidified, hardening time 70s, 3D printing photosensitive resin is made.
Comparative example 1
Trans- 2 are added without, along 6- nonadienols, other conditions are the same as embodiment 1.Production code member M-4.
Comparative example 2
0.1 part of three (cyano group formula dialkylene) cerium is added without, other conditions are the same as embodiment 1.Production code member M-5.
Comparative example 3
0.1 part four-(trimethyl silene ether) titanium is added without, other conditions are the same as embodiment 1.Production code member M-6.
Comparative example 4
Modified butadiene rubber is added without, adds unmodified butadiene rubber, other conditions are the same as embodiment 1.Production code member M-7.
Embodiment 4
The 3D printing photosensitive resin material that embodiment 1-3 and comparative example 1-4 are produced, carry out, impact strength J/M, stretching
Intensity MPa, elongation at break % detection, concrete outcome are shown in Table 1.
Table 1：The 3D printing photosensitive resin material impact strength J/M that different process is produced, tensile strength MPa, fracture are stretched
Long rate % testing results
Claims (6)
1. a kind of preparation method of 3D printing photosensitive resin, it is characterised in that comprise the following steps：
By mass parts, by 10-30 part modified butadiene rubber；30-60 part epoxy acrylates；0.1-1 parts trans- 2, along 6- nonyls two
Enol, 0.01-0.1 parts three (cyano group formula dialkylene) cerium, 0.01-0.1 parts four-(trimethyl silene ether) titanium, the dilution of 20-35 parts
Agent；1-4 part initiators；1-4 part accelerator, 10-20min is stirred, obtains photosensitive resin；Obtained photosensitive resin material is coated
On surface treated iron plate, iron plate is positioned in photo solidification machine and solidified, hardening time 30-70s, 3D is made
Printed photosensitive resin.
A kind of 2. preparation method of 3D printing photosensitive resin described in claim 1, it is characterised in that the modified butadiene rubber
The preparation method of glue comprises the following steps：
By initiator of (CH3) 3CLi, hexamethylene be solvent, butadiene carries out anionic polymerisation, and with oxirane and methanol
End-blocking, temperature are 40-60 DEG C, time 1-5h, obtain the polybutadiene telechelic polymer with terminal hydroxy group, then exist with acrylic acid
At 130-150 DEG C, it is that catalyst carries out esterification 2-8h with N- hydroxyl -5- ENBs -2,3- dicarboximide, is modified
Butadiene rubber.
A kind of 3. preparation method of 3D printing photosensitive resin described in claim 1, it is characterised in that in mass ratio, (CH3)
3CLi：Hexamethylene：Butadiene：Oxirane：Methanol=(1.5-2.5)：30：(1.5-2.5)：(1.5-2.5)：1.
A kind of 4. preparation method of 3D printing photosensitive resin described in claim 1, it is characterised in that in mass ratio, polybutadiene
Alkene telechelic polymer：Acrylic acid：N- hydroxyl -5- ENB -2,3- dicarboximide=1：1：(0.03-0.05).
5. the preparation method of a kind of 3D printing photosensitive resin described in claim 1, it is characterised in that described initiator is
Any of 2,2- dimethoxy -2- phenyl acetophenones, UV-184 and UV-1173.
6. the preparation method of a kind of 3D printing photosensitive resin described in claim 1, it is characterised in that described accelerator is first
Base acrylated phosphate.
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| Application Number | Priority Date | Filing Date | Title |
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| CN201710837616.8A CN107815219A (en) | 2017-09-18 | 2017-09-18 | A kind of preparation method of 3D printing photosensitive resin |
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| CN201710837616.8A CN107815219A (en) | 2017-09-18 | 2017-09-18 | A kind of preparation method of 3D printing photosensitive resin |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113176705A (en) * | 2020-01-27 | 2021-07-27 | 株式会社田村制作所 | Photosensitive resin composition |
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| 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 |
| CN104765251A (en) * | 2014-11-06 | 2015-07-08 | 青岛科技大学 | High-toughness photosensitive resin for 3D printing and preparation method thereof. |
| CN105199178A (en) * | 2015-09-21 | 2015-12-30 | 江苏科技大学 | Three-dimensional printing photosensitive resin material containing modified butadiene rubber and preparation method |
-
2017
- 2017-09-18 CN CN201710837616.8A patent/CN107815219A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104765251A (en) * | 2014-11-06 | 2015-07-08 | 青岛科技大学 | High-toughness photosensitive resin for 3D printing and preparation method thereof. |
| 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 |
| CN105199178A (en) * | 2015-09-21 | 2015-12-30 | 江苏科技大学 | Three-dimensional printing photosensitive resin material containing modified butadiene rubber and preparation method |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113176705A (en) * | 2020-01-27 | 2021-07-27 | 株式会社田村制作所 | Photosensitive resin composition |
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Application publication date: 20180320 |
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