CN104312141B - Photosensitive resin and preparation method thereof - Google Patents
Photosensitive resin and preparation method thereof Download PDFInfo
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- CN104312141B CN104312141B CN201410648958.1A CN201410648958A CN104312141B CN 104312141 B CN104312141 B CN 104312141B CN 201410648958 A CN201410648958 A CN 201410648958A CN 104312141 B CN104312141 B CN 104312141B
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Abstract
The invention belongs to the field of novel 3D printing material, in particular to the field of photosensitive resin. The photosensitive resin is prepared from the following constituents in percentage by weight: 35-80% of acrylate, 0.5-10% of a radical initiator, and 10-55% of a thinner. The viscosity of the photosensitive resin disclosed by the invention is lower than 220 cps, so that the photosensitive resin is low in viscosity and quick in molding, can guarantee the quick molding property of the 3D product, and meets the requirements of industrialized use.
Description
Technical field
The invention belongs to 3D printing field of new, particularly belong to low viscous photosensitive resin field.
Background technology
3D printing (3Dprinting) technology also known as three-dimensional printing technology, be a kind of based on mathematical model file, fortune
With powdery metal or plastics etc. can jointing material, carry out the technology of constructed object by way of successively printing.It need not machinery
Processing or any mould, just directly can generate the part of any shape, thus greatly shorten producing from computer graphics data
The lead time of product, improve productivity ratio and reduce production cost.
DLP laser forming technology：Solidify liquid photopolymerization using high-resolution Digital Light Processor (DLP) projector
Thing, successively carry out photocuring, due to during every layer of solidification, by lamellar solidification as lantern slide, therefore speed is than same type
SLA stereolithography techniques speed is faster.This technology formed precision is high, in terms of material properties, details and surface smoothness
Can be equal to the durable plastic material part of injection mo(u)lding.
Upper light source molding refers to projector is positioned over above photosensitive resin, by the molding skill of photosensitive resin upper strata solidification
Art, compared to lower light source molding, upper light source molding can be with the bigger article of print volume, but it is wanted to the viscosity of photosensitive resin
Ask comparison high.In prior art, for upper light source molding photosensitive resin viscosity generally between 400-700cps, because of viscosity
Greatly, shaping speed is slow.
Content of the invention
Invention broadly provides the photosensitive resin that a kind of DLP technology for upper light source molding uses, reach low viscous
The use requirement of degree.
It is an object of the invention to provide a kind of photosensitive resin, by weight percentage, described photosensitive resin comprises following
Component：
Preferably, by weight percentage, described photosensitive resin comprises following components：
Preferably, the light source for solidifying described photosensitive resin is the ultraviolet light of wavelength 350～420nm.
Preferably, described acrylate be aromatic urethane acrylate, in aliphatic urethane acrylate extremely
Few one kind.
Preferably, described epoxy resin be epoxy acrylate, at least one in novolac epoxy resin.
Preferably, described radical initiator be dimethoxybenzoin, double (2,4, the 6- trimethylbenzoyl) oxygen of phenyl
In change phosphine, 2,4,6 (trimethylbenzoyl) diphenyl phosphine oxide, fluorinated diphenyl titanium cyclopentadienyl, benzophenone, chlorinated diphenyl ketone
At least one.
Preferably, described cationic initiator be diaryl hexafluorophosphoric acid iodine salt, triaryl hexafluorophosphoric acid iodine salt, 2,
At least one in 4- diethyl thioxanthone.
Preferably, described diluent is 1,6- hexanediyl ester, iso-bornyl acrylate, oxolane propylene
At least one in acid esters.
Another object of the present invention is to providing a kind of preparation method of photosensitive resin, this preparation method includes walking as follows
Suddenly：
(1) in the special glass there-necked flask equipped with agitator and condensing tube, sequentially add the acrylate 40 of formula ratio
～80 parts, 5～15 parts of epoxy resin, 0.5～8 part of radical initiator, 0.5～2 part of cationic initiator, diluent 10～50
Part, 0.5～2 part of tonyred, are allowed to uniformly mix, side mixing marginal not enters 0.5～3 part of aerosil；
(2) mixture obtaining step (1) is warming up to 50～70 DEG C, at the uniform velocity stirs 35～40min, obtains faint yellow equal
Even liquid, keeps in Dark Place, as low viscous photosensitive resin.
Using above-mentioned photosensitive resin and preparation method thereof, the present invention has advantages below：
(1) the photosensitive resin viscosity of the present invention is below 220cps, and viscosity is low, and molding is fast, has ensured the quick of 3D product
Formability；
(2) bending moduluses of the photosensitive resin of the present invention and stretch moduluses all reach more than 2500Mpa, and photosensitive resin is in bullet
Property the limit in opposing flexural deformation stress big, intensity is high, is deformed that ability relative property is little, and mechanical strength is big, greatly increases and makes
With the life-span, meet requirement useful industrially；
(3) cubical contraction of the photosensitive resin of the present invention all 1.0% about it is achieved that extremely low cubical contraction,
3D printing product will not be occurred in use compared with large deformation, for obtaining high-precision printed product because of contraction
Most important, beneficial to the holding of shape of product；
(4) photosensitive resin of present invention preparation has the advantages that shaping speed is fast, mechanical strength is high, dimensional stability, this
Outer preparation process is simple, easy to utilize.
Specific embodiment
The present invention is expanded on further below by way of specific embodiment, but is not limited to following embodiments.
First, specific embodiment
Embodiment 1
1st, configure photosensitive resin raw material according to the following ratio
2nd, preparation method
(1) in the special glass there-necked flask equipped with agitator and condensing tube, sequentially add 35 parts of urethane acrylate,
Double 10 parts of (2,4,6- trimethylbenzoyl) phosphine oxide of phenyl, 55 parts of 1,6 hexanediol diacrylate are allowed to uniformly mix；
(2) mixture obtaining step (1) is warming up to 60 DEG C, at the uniform velocity stirs 35min, obtains faint yellow uniform liquid,
Sealing preserve, as low viscous photosensitive resin.
Light source for solidifying described photosensitive resin is the ultraviolet light of wavelength 350nm.
Embodiment 2
1st, configure photosensitive resin raw material according to the following ratio
2nd, preparation method
(1) in the special glass there-necked flask equipped with agitator and condensing tube, sequentially add aliphatic polyurethane acrylic acid
30 parts of ester, 30 parts of aromatic urethane acrylate, 0.5 part of 2,4,6 (trimethylbenzoyl) diphenyl phosphine oxide, isoborneol
39.5 parts of base acrylate is allowed to uniformly mix；
(2) mixture obtaining step (1) is warming up to 50 DEG C, at the uniform velocity stirs 40min, obtains faint yellow uniform liquid,
Sealing preserve, as low viscous photosensitive resin.
Light source for solidifying described photosensitive resin is the ultraviolet light of wavelength 370nm.
Embodiment 3
1st, configure photosensitive resin raw material according to the following ratio
2nd, preparation method
(1) in the special glass there-necked flask equipped with agitator and condensing tube, sequentially add 15 parts of urethane acrylate,
25 parts of aromatic urethane acrylate, 1 part of 2,4,6 (trimethylbenzoyl) diphenyl phosphine oxide, fluorinated diphenyl titanium cyclopentadienyl 2
Part, 2 parts of triaryl hexafluorophosphoric acid iodine salt, 25 parts of iso-bornyl acrylate, 30 parts of oxolane acrylate are allowed to uniform
Mixing；
(2) mixture obtaining step (1) is warming up to 70 DEG C, at the uniform velocity stirs 37min, obtains faint yellow uniform liquid,
Sealing preserve, as low viscous photosensitive resin.
Light source for solidifying described photosensitive resin is the ultraviolet light of wavelength 420nm.
Embodiment 4
1st, configure photosensitive resin raw material according to the following ratio
2nd, preparation method
(1) in the special glass there-necked flask equipped with agitator and condensing tube, sequentially add aliphatic polyurethane acrylic acid
Double 2 parts of (2,4,6- trimethylbenzoyl) phosphine oxide of 80 parts of ester, phenyl, 2 parts of fluorinated diphenyl titanium cyclopentadienyl, 3 parts of benzophenone, two
3 parts of aryl hexafluorophosphoric acid iodine salt, 3 parts of iso-bornyl acrylate, 4 parts of oxolane acrylate, 1,6-HD dipropyl
3 parts of olefin(e) acid ester is allowed to uniformly mix；
(2) mixture obtaining step (1) is warming up to 55 DEG C, at the uniform velocity stirs 35min, obtains faint yellow uniform liquid,
Sealing preserve, as low viscous photosensitive resin.
Light source for solidifying described photosensitive resin is the ultraviolet light of wavelength 400nm.
Embodiment 5
1st, configure photosensitive resin raw material according to the following ratio
2nd, preparation method
(1) in the special glass there-necked flask equipped with agitator and condensing tube, sequentially add aliphatic polyurethane acrylic acid
30 parts of ester, 42 parts of urethane acrylate, phenyl double 2 parts of (2,4,6- trimethylbenzoyl) phosphine oxide, 2,4,6 (trimethyls
Benzoyl) 2 parts of diphenyl phosphine oxide, fluorinated diphenyl titanium cyclopentadienyl 2 parts, 2 parts of chlorinated diphenyl ketone, iso-bornyl acrylate 10
Part, 10 parts of 1,6- hexanediyl ester, are allowed to uniformly mix；
(2) mixture obtaining step (1) is warming up to 58 DEG C, at the uniform velocity stirs 38min, obtains faint yellow uniform liquid,
Sealing preserve, as low viscous photosensitive resin.
Light source for solidifying described photosensitive resin is the ultraviolet light of wavelength 390nm.
Embodiment 6
1st, configure photosensitive resin raw material according to the following ratio
2nd, preparation method
(1) in the special glass there-necked flask equipped with agitator and condensing tube, sequentially add 35 parts of urethane acrylate,
5 parts of epoxy acrylate, 3 parts of fluorinated diphenyl titanium cyclopentadienyl, 0.5 part of benzophenone, 55 parts of oxolane acrylate, tonyred
0.5 part is allowed to uniformly mix, and side mixing marginal not enters 1 part of aerosil；
(2) mixture obtaining step (1) is warming up to 50 DEG C, at the uniform velocity stirs 35min, obtains faint yellow uniform liquid,
Sealing preserve, as low viscous photosensitive resin.
Light source for solidifying described photosensitive resin is the ultraviolet light of wavelength 420nm.
Embodiment 7
1st, configure photosensitive resin raw material according to the following ratio
2nd, preparation method
(1) in the special glass there-necked flask equipped with agitator and condensing tube, sequentially add 30 parts of urethane acrylate,
30 parts of aliphatic urethane acrylate, 10 parts of novolac epoxy resin, 4 parts of diaryl hexafluorophosphoric acid iodine salt, chlorinated diphenyl first
2 parts of ketone, 20 parts of 1,6- hexanediyl ester, 1 part of tonyred are allowed to uniformly mix, and side mixing marginal not enters 3 parts of gas phase two
Silicon oxide；
(2) mixture obtaining step (1) is warming up to 55 DEG C, at the uniform velocity stirs 38min, obtains faint yellow uniform liquid,
Sealing preserve, as low viscous photosensitive resin.
Light source for solidifying described photosensitive resin is the ultraviolet light of wavelength 350nm.
Embodiment 8
1st, configure photosensitive resin raw material according to the following ratio
2nd, preparation method
(1) in the special glass there-necked flask equipped with agitator and condensing tube, sequentially add aromatic urethane acrylic acid
Double (the 2,4,6- of 80 parts of ester, 3 parts of epoxy acrylate, 3 parts of novolac epoxy resin, 1 part of triaryl hexafluorophosphoric acid iodine salt, phenyl
Trimethylbenzoyl) 1 part of phosphine oxide, 1 part of dimethoxybenzoin, 10 parts of iso-bornyl acrylate, 0.5 part of tonyred be allowed to
Uniformly mix, side mixing marginal not enters 0.5 part of aerosil；
(2) mixture obtaining step (1) is warming up to 70 DEG C, at the uniform velocity stirs 34min, sealing preserve, obtains faint yellow
Uniform liquid, as low viscous photosensitive resin.
Light source for solidifying described photosensitive resin is the ultraviolet light of wavelength 410nm.
Embodiment 9
1st, configure photosensitive resin raw material according to the following ratio
2nd, preparation method
(1) in the special glass there-necked flask equipped with agitator and condensing tube, sequentially add 49 parts of urethane acrylate,
11 parts of novolac epoxy resin, 0.5 part of 2,4,6 (trimethylbenzoyl) diphenyl phosphine oxide, 2,4- diethyl thioxanthone 0.5
Part, 0.5 part of benzophenone, 20 parts of iso-bornyl acrylate, 15 parts of 1,6 hexanediol diacrylate, 2 parts of tonyred are allowed to
Uniformly mix, side mixing marginal not enters 1.5 parts of aerosil；
(2) mixture obtaining step (1) is warming up to 65 DEG C, at the uniform velocity stirs 36min, obtains faint yellow uniform liquid,
Sealing preserve, as low viscous photosensitive resin.
Light source for solidifying described photosensitive resin is the ultraviolet light of wavelength 390nm.
Embodiment 10
1st, configure photosensitive resin raw material according to the following ratio
2nd, preparation method
(1) in the special glass there-necked flask equipped with agitator and condensing tube, sequentially add 20 parts of aliphatic acrylate,
26 parts of aromatic urethane acrylate, 15 parts of epoxy acrylate, 2 parts of triaryl hexafluorophosphoric acid iodine salt, diaryl hexafluoro
2 parts of phosphoric acid iodine salt, 1 part of 2,4- diethyl thioxanthone, 30 parts of oxolane acrylate, 1.5 parts of tonyred are allowed to uniform
Mixing, side mixing marginal not enters 2.5 parts of aerosil；
(2) mixture obtaining step (1) is warming up to 69 DEG C, at the uniform velocity stirs 39min, obtains faint yellow uniform liquid,
Sealing preserve, as low viscous photosensitive resin.
Light source for solidifying described photosensitive resin is the ultraviolet light of wavelength 370nm.
Embodiment 11
1st, configure photosensitive resin raw material according to the following ratio
2nd, preparation method
(1) in the special glass there-necked flask equipped with agitator and condensing tube, sequentially add aromatic urethane acrylic acid
30 parts of ester, 40 parts of urethane acrylate, 4 parts of epoxy acrylate, 4 parts of novolac epoxy resin, diaryl iodonium hexafluorophosphate
3 parts of salt, 2 parts of fluorinated diphenyl titanium cyclopentadienyl, 0.5 part of dimethoxybenzoin, 15 parts of oxolane acrylate, 1 part of tonyred are allowed to
Uniformly mix, side mixing marginal not enters 0.5 part of aerosil；
(2) mixture obtaining step (1) is warming up to 56 DEG C, at the uniform velocity stirs 35min, obtains faint yellow uniform liquid,
Sealing preserve, as low viscous photosensitive resin.
Light source for solidifying described photosensitive resin is the ultraviolet light of wavelength 380nm.
Embodiment 12
1st, configure photosensitive resin raw material according to the following ratio
2nd, preparation method
(1) in the special glass there-necked flask equipped with agitator and condensing tube, sequentially add 10 parts of urethane acrylate,
10 parts of aliphatic urethane acrylate, 20 parts of aromatic urethane acrylate, 6.5 parts of novolac epoxy resin, 2,4,6 (three
Methyl benzoyl) 3 parts of diphenyl phosphine oxide, 4 parts of benzophenone, 1 part of chlorinated diphenyl ketone, 2,4- diethyl thioxanthone
0.5 part, 40 parts of iso-bornyl acrylate, 2 parts of tonyred be allowed to uniformly mix, side mixing marginal not enters 3 parts of gas phase titanium dioxide
Silicon；
(2) mixture obtaining step (1) is warming up to 54 DEG C, at the uniform velocity stirs 40min, obtains faint yellow uniform liquid,
Sealing preserve, as low viscous photosensitive resin.
Light source for solidifying described photosensitive resin is the ultraviolet light of wavelength 360nm.
Embodiment 13
1st, configure photosensitive resin raw material according to the following ratio
2nd, preparation method
(1) in the special glass there-necked flask equipped with agitator and condensing tube, sequentially add aliphatic polyurethane acrylic acid
Double 2 parts of (2,4,6- trimethylbenzoyl) phosphine oxide of 52 parts of ester, 3 parts of epoxy acrylate, 4 parts of novolac epoxy resin, phenyl,
3 parts of 2,4,6 (trimethylbenzoyl) diphenyl phosphine oxide, fluorinated diphenyl titanium cyclopentadienyl 1 part, 1 part of 2,4- diethyl thioxanthone,
1 part of dimethoxybenzoin, 2 parts of benzophenone, 2 parts of chlorinated diphenyl ketone, 13 parts of iso-bornyl acrylate, oxolane propylene
12 parts of acid esters, 2 parts of tonyred are allowed to uniformly mix, and side mixing marginal not enters 2 parts of aerosil；
(2) mixture obtaining step (1) is warming up to 64 DEG C, at the uniform velocity stirs 36min, obtains faint yellow uniform liquid,
Sealing preserve, as low viscous photosensitive resin.
Light source for solidifying described photosensitive resin is the ultraviolet light of wavelength 350nm.
2nd, performance test
Shore hardness
By the photosensitive resin sample of embodiment 1-13 gained under the conditions of 23 ± 5 DEG C, measured with shore D type hardness tester.
Viscosity test
By the photosensitive resin sample of embodiment 1-13 gained under the conditions of 25 DEG C, glued with Bookfield DV- II+Pro type
Degree measures.
Photosensitive property is tested
The photosensitive property of photosensitive resin is the important indicator characterizing photocuring characteristic, including critical solidification amount EcDeep with transmission
Degree Dp.EcRefer to that the photosensitive resin of unit area under transmission depth reaches the minimum solidification energy needed for gel state；DpThen table
Levy the relation of cured thickness and luminous energy.
By the prepared photosensitive resin sample of embodiment 1-13 under the conditions of different laser scanning speeds and energy exposure, often
Individual embodiment makes different samples respectively, then tests the thickness of these samples respectively.With different thickness in each embodiment
Degree and energy make working curve, then the slope of curve is Dp, curve and X-axis intersection point are Ec.
Shrinkage factor is tested
Use specific weight determine method, proportion during the photosensitive resin sample liquid that first test above-described embodiment 1-13 is obtained, calculating side
Formula is as follows：
γ=G/V, wherein, γ represents proportion (unit g/cm3), (unit g), V represent volume (unit to G representation quality
cm3).
Again with the sample proportion after same procedure test solidification, calculation is as follows：
γ '=G'/V'
Then shrinkage factor H=(γ '-γ)/γ × 100%
3rd, test result analysis
The sample that above-described embodiment 1-13 is obtained measures shore hardness, viscosity, boundary's solidification amount E respectivelyc, transmission depth Dp、
Bending moduluses, stretch moduluses, shrinkage factor, the data recording is as follows：
The experimental result that the sample that table 1 embodiment 1-13 is obtained records
Embodiment 1-5 is the formula of photosensitive resin is experimental result when acrylate, radical initiator, diluent.
As it can be seen from table 1 embodiment 1-5 be obtained the bending moduluses of photosensitive resin sample and stretch moduluses all reach 2500Mpa with
On, shore hardness reaches more than 60 degree, and viscosity is no more than 220cps.It follows that the formula of photosensitive resin is only acrylic acid
Use requirement can be reached when ester, radical initiator, diluent.In elastic limit, opposing flexural deformation stress is big, and intensity is high,
Mechanical strength is big, and the 3D product obtaining resistance to external world is strong,；Shrinkage factor 1.0% about, is deformed ability relative property
Little；Viscosity is low, reaches low viscous use requirement.
Embodiment 6-13 is to add epoxy resin, cationic initiator, gas phase on the basis of embodiment 1-5 further
The photosensitive resin sample that silicon dioxide and tonyred are obtained, gained sample bent modulus and stretch moduluses all reach 2500Mpa with
On, no more than 220cps, shore hardness all reaches more than 60 degree to viscosity, has reached the hardness requirement of medium hardness plastic cement, and
Viscosity is low, and molding is fast, has ensured the formability of 3D product.
Critical solidification energy E of the photosensitive resin sample that embodiment 6-13 is obtainedcAverage than embodiment 1-5 somewhat increases
Greatly, in 10-12mJ/cm2Between, equally solidification light energy is required relatively low.Because ultraviolet light penetration capacity is strong, light energy is high,
Meet solidifying requirements with ultraviolet light, beneficial to curing molding.
Embodiment 6-13 be obtained photosensitive resin sample cubical contraction average 0.8% about, than embodiment 1-5's
Average low 0.2% about is it is achieved that extremely low cubical contraction is so that 3D printing product in use will not be because of contraction
And occur compared with large deformation, for obtaining, high-precision printed product is most important, beneficial to the holding of shape of product.
The photosensitive resin viscosity of present invention preparation is low, has that shaping speed is fast, mechanical strength is high, chi under ultraviolet light
The advantages of very little stability, preparation process is simple in addition, easy to utilize.
It will be apparent to those skilled in the art that can technical scheme as described above and design, make other various
Corresponding change and deformation, and all these change and deformation all should belong to the protection domain of the claims in the present invention
Within.
Claims (8)
1. a kind of photosensitive resin, including following weight percents：
Light source for solidifying described photosensitive resin is the ultraviolet light of wavelength 350～420nm；Described photosensitive resin is as 3D printing
Materials'use.
2. photosensitive resin according to claim 1, including following weight percents：
3. photosensitive resin according to claim 1 and 2 it is characterised in that：Described acrylate is aromatic urethane third
At least one in olefin(e) acid ester, aliphatic urethane acrylate.
4. photosensitive resin according to claim 1 and 2 it is characterised in that：Described epoxy resin is epoxy acrylate, phenol
At least one in formaldehyde epoxy resin.
5. photosensitive resin according to claim 1 and 2 it is characterised in that：Described radical initiator be phenyl double (2,4,
6- trimethylbenzoyl) phosphine oxide, 2,4,6 (trimethylbenzoyl) diphenyl phosphine oxide, fluorinated diphenyl titanium cyclopentadienyl, rest in peace
At least one in fragrant dimethyl ether, benzophenone, chlorinated diphenyl ketone, 2,4- diethyl thioxanthone.
6. photosensitive resin according to claim 1 and 2 it is characterised in that：Described cationic initiator is diaryl hexafluoro
At least one in phosphoric acid iodine salt, triaryl hexafluorophosphoric acid iodine salt.
7. photosensitive resin according to claim 1 and 2 it is characterised in that：Described diluent is 1,6-HD two propylene
At least one in acid esters, iso-bornyl acrylate, oxolane acrylate.
8. a kind of preparation method of photosensitive resin it is characterised in that：Comprise the following steps：
(1) in the special glass there-necked flask equipped with agitator and condensing tube, sequentially add the acrylate 40～80 of formula ratio
Part, epoxy resin 5～15,0.5～8 part of radical initiator, 0.5～2 part of cationic initiator, 10～50 parts of diluent, Soviet Union
0.5～2 part of DANHONG, is allowed to uniformly mix, and side mixing marginal not enters 0.5～3 part of aerosil；
(2) mixture obtaining step (1) is warming up to 50～70 DEG C, at the uniform velocity stirs 35～40min, obtains faint yellow uniform liquid
Body, keeps in Dark Place, as low viscous photosensitive resin.
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| CN106032425A (en) * | 2015-03-09 | 2016-10-19 | 优克材料科技股份有限公司 | Ceramic resin printing raw material for light cured three dimensional printing |
| CN104804151A (en) * | 2015-05-06 | 2015-07-29 | 华东理工大学 | Preparation method of light-cured resin material for three-dimensional printing |
| CN105199058B (en) * | 2015-09-30 | 2018-09-21 | 惠州市安品新材料有限公司 | A kind of 3D printing light curing resin composition and moulder prepared therefrom |
| CN106243635A (en) * | 2016-07-29 | 2016-12-21 | 华蓥友达精密模具制造有限公司 | A kind of 3D printed material with anti-mildew antibacterial functions |
| CN107936146A (en) * | 2017-06-05 | 2018-04-20 | 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 |
| CN107501442B (en) * | 2017-08-15 | 2022-06-17 | 宁波七诺新材料科技有限公司 | Photoinitiator composition initiated by visible light for 3D printing technology and application |
| CN107815219A (en) * | 2017-09-18 | 2018-03-20 | 江山海维科技有限公司 | A kind of preparation method of 3D printing photosensitive resin |
| CN108410162B (en) * | 2018-04-13 | 2021-06-08 | 广州有得新材料科技有限公司 | Photocuring 3D printing material and preparation method and application thereof |
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| CN103305132B (en) * | 2012-03-06 | 2015-03-25 | 上海佑威新材料科技有限公司 | Fast-curing structural adhesive and preparation method thereof |
| CN103396689A (en) * | 2013-08-01 | 2013-11-20 | 苏州市明大高分子科技材料有限公司 | LED-UV light source curable coating and preparation method |
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