CN106647167A - Matte photosensitive resin for photocuring quick molding and preparation method thereof - Google Patents
Matte photosensitive resin for photocuring quick molding and preparation method thereof Download PDFInfo
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- CN106647167A CN106647167A CN201610870589.XA CN201610870589A CN106647167A CN 106647167 A CN106647167 A CN 106647167A CN 201610870589 A CN201610870589 A CN 201610870589A CN 106647167 A CN106647167 A CN 106647167A
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- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/004—Photosensitive materials
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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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Abstract
The invention discloses matte photosensitive resin for photocuring quick molding and a preparation method thereof. The resin is prepared from the following raw materials in parts by weight: 5-45 parts of urethane acrylate, 5-45 parts of epoxy resin, 10-25 parts of reactive diluent, 1-8 parts of cationic photoinitiator, 1-8 parts of free radical photoinitiator, 1-10 parts of micron silicon dioxide, 1-10 parts of polyethylene wax powder and 1-3 parts of nonionic surfactant. The photosensitive resin has an excellent matte effect due to the addition of micron silicon dioxide and polyethylene wax powder after photocuring quick molding, and clear printing textures on the surface of a molded part manufactured by photocuring quick molding cannot be observed due to the introduction of the matte effect, so that the surface quality of the molded part can be remarkably improved. Therefore, the manufactured three-dimensional solid has better mechanical performance, the shrinkage and warpage situation of the molded part can be reduced, the printing accuracy can be improved, and the practicality is stronger.
Description
Technical field
The invention belongs to 3D printing technique field, and in particular to a kind of photocureable rapid shaping with sub- light photosensitive resin and its
Preparation method.
Background technology
3D printing technique, also known as rapid shaping technique, is based on mathematical model file, with powdery metal or modeling
Material etc. can jointing material, come the technology of constructed object by way of successively printing.3D printing technique is got in current manufacturing industry
More to have competitiveness, therefore it is referred to as " there is the manufacturing technology of industrial revolution meaning ".3D printing technique includes fusion sediment
Shaping, selective laser sintering, photocureable rapid shaping（Stereolithography solidifies rapid shaping）Etc. technology.Wherein, photocuring is fast
Rapid-result type is by light（Ultraviolet light, laser etc.）According to the shape point by point scanning of two-dimensional section on resin liquid level, resin solidification is made,
Resin after solidification just forms an X-Y scheme, so successively scans, solidification, and complete 3D solid is finally obtained.
In photocureable rapid shaping, photosensitive resin will be determined as the basis that moulding material is whole technology, the quality of photosensitive resin
The precision of drip molding and its mechanical property and hot property.
In recent years, there are many universities and scientific research institutions in China in the research for carrying out photocureable rapid shaping photosensitive resin.Specially
Sharp CN200910040526.1 discloses a kind of stereolithography rapid shaping photosensitive resin and its preparation method and application, is related to
Stereolithography rapid shaping photosensitive resin includes epoxy resin, acrylate, radical initiator, cationic initiator and dilution
Agent.Its epoxy resin is phenolic resin or the cycloaliphatic epoxy resin with own ring, the diluent be epoxy resin diluent,
Acrylate diluent or their mixture.Patent CN200910095846.7 discloses a kind of rapid moulding injection mold and uses
UV curing photosensitive resin, it mainly has epoxy acrylate, epoxy resin, two-tube energy single group body or trifunctional monomer to live
Property diluent etc. is into being grouped into.On the basis of above patent, it is ultraviolet that patent CN201110177676.4 provides a kind of high accuracy
Laser curing rapid shaping photosensitive resin, its contain the cation type ultraviolet photo-curing higher cycloaliphatic epoxy resin of activity and
Oxetane compound, can produce with high-precision part.It is presently used for the photosensitive resin of photocureable rapid shaping
Mainly it is made up of epoxy resin, urethane acrylate etc., focuses principally on the lifting of the aspects such as mechanical property, is more enriched
The photosensitive resin with special-effect or performance need further exploitation.
In addition, photocureable rapid shaping is based on the manufacture being layering so that the 3D solid surface of shaping can
It was observed that clearly printing texture, poor surface quality limits the extensive application of photocuring technology.Now generally adopt solvent
Finishing method is improving surface quality but cumbersome, healthy on operator to have certain impact.
Sub- luminescent material refers to a kind of special, material with extremely tiny grainy surface.When a parallel ray beam
Material surface is irradiated to, if common smooth finish surface then only can occur mirror-reflection, the entrance people of the reflected meeting 100% of light
Eyes, if but then there is diffusing scattering in the rough surface of sub- luminescent material, now light because to all directions scattering not
Can be completely into the eyes of people, this allows people to feel that light is soft, produces and a kind of princely views and admires experience.Glossiness is to use number
Word represents the degree of the close minute surface of body surface, can be used to weigh the matt effect of material.The glossiness of traditional material is because of table
Face is bright and clean can to reach 100%, and sub- luminescent material glossiness is usually less than 50%.
In addition to special matt effect is obtained, the using of sub- luminescent material can cause the 3D solid being molded can be because uneven
Surface diffusing reflection clearly print texture without being observed, and then lifted surface quality, promote photocureable rapid shaping
Application of the technology in more areas, and avoid follow-up loaded down with trivial details surface treatment program.But, also it is not applied to so far
The photocureable rapid shaping report of sub- light photosensitive resin.
Comprehensive described above, exploitation in need is a kind of new, and the photocureable rapid shaping with matt effect is with photosensitive
Resin, while enriching photocureable rapid shaping with photosensitive resin types, can lift the surface quality of the 3D solid of shaping.
The content of the invention
It is an object of the invention to provide a kind of photocureable rapid shaping is with sub- light photosensitive resin, it is rapid-result soon to lift photocuring
Type surface quality of workpieces, mechanical property and printing precision, enrich the species of photocureable rapid shaping photosensitive resin, the Asia
Light photosensitive resin allows photocureable rapid shaping to manufacture the forming part with matt effect, with more preferably viewing and admiring body
Test, promote photocureable rapid shaping in the application of more areas.
It is a further object of the present invention to provide a kind of preparation method of photocureable rapid shaping with sub- light photosensitive resin, technique
Simply, it is with low cost, can quickly mass produce out the sub- light photosensitive resin for meeting photocureable rapid shaping requirement.
For achieving the above object, the present invention is employed the following technical solutions：
A kind of photocureable rapid shaping Asia light photosensitive resin, it is by made by the raw material of following portions by weight：Polyurethane third
Olefin(e) acid ester 5 ~ 45, epoxy resin 5 ~ 45, reactive diluent 10 ~ 25, cation-type photopolymerization initiators 1 ~ 8, free radical type light gather
Close initiator 1 ~ 8, micron silica 1 ~ 10, polyethylene wax powder 1 ~ 10, nonionic surfactant 1 ~ 3.
The micron silica is 1 with the ratio of the parts by weight of polyethylene wax powder:3~6:1, the micron silica
1 ~ 15 micron is with the particle diameter of polyethylene wax powder, index of refraction is 1.45 ~ 1.54.
The viscosity of photocureable rapid shaping Asia light photosensitive resin is 100 ~ 300 mPas（25℃）.
The epoxy resin is the one kind in aliphatic glycidyl ether epoxy resin, cycloaliphatic epoxy resin or its mixing
Thing.
The cycloaliphatic epoxy resin be 3,4- epoxy radicals -6- methylcyclohexyls formic acid -3 ', 4 '-epoxy radicals -6 '-methyl
Cyclohexylmethyl.
Reactive diluent is ethylene glycol diglycidylether diacrylate or the propylene of tripropyleneglycol diglycidyl ether two
One or two mixtures in acid esters.
The cation-type photopolymerization initiators be Diaryl iodonium hexafluorophosphate, Diaryl iodonium hexafluoro arsenate or
One or more mixture in triaryl sulphur hexafluorophosphate.
The free radical type Photoepolymerizationinitiater initiater is dimethoxybenzoin, chlorinated diphenyl ketone, 1- hydroxy-cyclohexyl benzene first
One or more mixture in ketone.
The nonionic surfactant is AEO, fatty acid methyl ester ethoxylate, polyoxyethylene
The mixture of one or more in sorbitan monostearate.
The preparation method of described washable ultraviolet laser solidification rapid shaping photosensitive resin, step is as follows：According to weight
Proportioning, first stirs micron silica, polyethylene wax powder and nonionic surfactant, is subsequently adding remaining poly- ammonia
Ester acrylate, epoxy resin, reactive diluent, cation-type photopolymerization initiators and free radical type Photoepolymerizationinitiater initiater, so
After be heated to 60 ~ 80 °C of stirrings and make faint yellow uniform liquid in 60 ~ 120 minutes.
The general principle of the present invention is as follows：Urethane acrylate, epoxy resin, reactive diluent and initiator composition is originally
Invent the bulk composition of the sub- light photosensitive resin.Wherein, polymerization of epoxy resins is ring-opening polymerisation, shrinks little, polyurethane propylene
Acid esters is polymerized to the polymerization that carbon-to-carbon double bond fracture becomes singly-bound, shrinks very big, but urethane acrylate is in Ultra-Violet Laser spoke
The solidification rate of epoxy resin is faster than according to lower solidification rate, thus sub- light photosensitive resin of the present invention uses epoxy resin
The compound resin constituted with urethane acrylate, while mechanical property is lifted, it is ensured that photosensitive resin is received in photocuring
Shrinkage is little, and formed precision is high, and with sufficiently high light sensitivity.Traditional reactive diluent such as acrylic acid of Glycerin three
The volatility such as ester, tripropylene glycol diacrylate are big, and excitant is big, there is certain pollution to working environment, select in the present invention
Bland glycidol ethers acrylate is used as reactive diluent, it is ensured that photosensitive tree is reduced while photocuring effect
Fat excitant, reduces the pollution to working environment.
Micron silica and polyethylene wax powder are used for realizing the matt effect of photosensitive resin.1 ~ 15 micron of particle diameter can be true
The 3D solid for protecting shaping has tiny granular surface to reach matt effect, and shading rate 1.45 ~ 1.54 is Jie Jin photosensitive
The shading rate of resin, to ensure the transparency of photosensitive resin Stereolithography is carried out.Wherein, micron silica and epoxy
Preferably, exclusive use is cannot well to move to material surface to realize matt effect to the compatibilities such as resin, polyethylene wax powder with
The compatibilities such as the epoxy resin of polarity are poor, and both use cooperatively can reach optimal matt effect.Non-ionic surface active
Agent is used in photosensitive resin effectively dispersion micron silica and polyethylene wax powder, and when preventing because of long-term placement precipitation is produced.
The present invention is had the advantage that with beneficial effect：
1st, the present invention is surprised to find that to add micron silica and polyethylene wax powder, and the photosensitive resin Jing photocurings are rapid-result soon
The 3D solid that type is obtained has good matt effect.
2nd, the present invention is surprised to find that the forming part table manufactured by photocureable rapid shaping using sub- light photosensitive resin
Face would not observe that and clearly print texture, significantly improve the surface quality of forming part.
3rd, photosensitive resin of the present invention, because the addition of micron silica and polyethylene wax powder causes photocuring rapid-result soon
The 3D solid of type has more preferable mechanical property, while the contraction warpage situation of forming part can also be reduced, improves and prints essence
Degree, practicality is higher.
4th, the preparation method of sub- light photosensitive resin of the present invention, it is easy to operate, process conditions and production equipment are required
It is relatively low, can realize that large-scale popularization produces, with wide market prospects, splendid market efficiency.
Specific embodiment
With reference to specific embodiment, the present invention will be further described.It should be understood that following examples are merely to illustrate this
Invention can make one not for the scope of the present invention, the person skilled in the art in the field is limited according to the content of foregoing invention
A little nonessential modifications and adaptations.
Comparative example 1
A kind of photocureable rapid shaping Asia light photosensitive resin, it is by made by following raw materials：Urethane acrylate 5 ~ 45
Part, 5 ~ 45 parts of epoxy resin, reactive diluent（Ethylene glycol diglycidylether diacrylate or tripropylene glycol 2-glycidyl
Ether diacrylate）10 ~ 25 parts, 1 ~ 8 part of cation-type photopolymerization initiators, free radical type Photoepolymerizationinitiater initiater 1 ~ 8 part, micron
Silica 1 ~ 10 part, 1 ~ 10 part of polyethylene wax powder, 1 ~ 3 part of nonionic surfactant.
Above-mentioned solidification rapid shaping is as follows with the preparation method of sub- light photosensitive resin：
According to weight proportion, first micron silica, polyethylene wax powder and nonionic surfactant are stirred, Ran Houjia
Enter remaining urethane acrylate, epoxy resin, reactive diluent, cation-type photopolymerization initiators and free radical type light to gather
Initiator is closed, 60 ~ 80 °C of stirrings is then heated to and is well mixed within 60 ~ 120 minutes and obtains final product.
Comparative example 2
A kind of photocureable rapid shaping Asia light photosensitive resin, it is by made by following raw materials：45 parts of urethane acrylate,
Epoxy resin（3,4- epoxy radicals -6- methylcyclohexyls formic acid -3 ', 4 '-epoxy radicals -6 '-methylcyclohexyl methyl esters）30 parts, activity
Diluent（Tripropyleneglycol diglycidyl ether diacrylate）15 parts, cation-type photopolymerization initiators（Diaryl iodonium six
Fluorophosphate）2 parts, free radical type Photoepolymerizationinitiater initiater（Dimethoxybenzoin）1 part, 3 parts of micron silica, non-ionic surface
Activating agent（AEO）1 part.
Above-mentioned photocureable rapid shaping is as follows with the preparation method of sub- light photosensitive resin：
According to weight proportion, first micron silica and nonionic surfactant are stirred, be subsequently adding remaining poly-
Urethane acrylate, epoxy resin, reactive diluent, cation-type photopolymerization initiators and free radical type Photoepolymerizationinitiater initiater,
It is then heated to 60 °C of stirrings and makes faint yellow uniform liquid in 120 minutes.
Comparative example 3
A kind of photocureable rapid shaping Asia light photosensitive resin, it is by made by following raw materials：45 parts of urethane acrylate,
Epoxy resin（3,4- epoxy radicals -6- methylcyclohexyls formic acid -3 ', 4 '-epoxy radicals -6 '-methylcyclohexyl methyl esters）30 parts, activity
Diluent（Tripropyleneglycol diglycidyl ether diacrylate）15 parts, cation-type photopolymerization initiators（Diaryl iodonium six
Fluorophosphate）2 parts, free radical type Photoepolymerizationinitiater initiater（Dimethoxybenzoin）1 part, 3 parts of polyethylene wax powder, non-ionic surface live
Property agent（AEO）1 part.
Above-mentioned photocureable rapid shaping is as follows with the preparation method of sub- light photosensitive resin：
According to weight proportion, first polyethylene wax powder and nonionic surfactant are stirred, be subsequently adding remaining poly- ammonia
Ester acrylate, epoxy resin, reactive diluent, cation-type photopolymerization initiators and free radical type Photoepolymerizationinitiater initiater, so
After be heated to 80 °C of stirrings and make faint yellow uniform liquid in 60 minutes.
Embodiment 1
The photocureable rapid shaping of the present embodiment Asia light photosensitive resin, it is by made by following raw materials：Polyurethane acroleic acid
45 parts of ester, epoxy resin（3,4- epoxy radicals -6- methylcyclohexyls formic acid -3 ', 4 '-epoxy radicals -6 '-methylcyclohexyl methyl esters）30
Part, reactive diluent（Tripropyleneglycol diglycidyl ether diacrylate）15 parts, cation-type photopolymerization initiators（Diaryl
Iodine hexafluorophosphate）2 parts, free radical type Photoepolymerizationinitiater initiater（Dimethoxybenzoin）1 part, 3 parts of micron silica, poly- second
3 parts of alkene wax powder, nonionic surfactant（AEO）1 part.
The photocureable rapid shaping of the present embodiment is as follows with the preparation method of sub- light photosensitive resin：
According to weight proportion, first micron silica, polyethylene wax powder and nonionic surfactant are stirred, Ran Houjia
Enter remaining urethane acrylate, epoxy resin, reactive diluent, cation-type photopolymerization initiators and free radical type light to gather
Initiator is closed, 70 °C of stirrings is then heated to and is made faint yellow uniform liquid in 100 minutes.
Embodiment 2
The photocureable rapid shaping of the present embodiment Asia light photosensitive resin, it is by made by following raw materials：Polyurethane acroleic acid
5 parts of ester, epoxy resin（Aliphatic glycidyl ether epoxy resin）45 parts, reactive diluent（Ethylene glycol diglycidylether two
Acrylate）20 parts, cation-type photopolymerization initiators（Triaryl sulphur hexafluorophosphate）1.0 parts, free radical type photopolymerization
Initiator（Chlorinated diphenyl ketone）8 parts, 10 parts of micron silica, 1 part of polyethylene wax powder, nonionic surfactant（Polyoxy
Ethene sorbitan monostearate）2 parts.
The photocureable rapid shaping of the present embodiment is as follows with the preparation method of sub- light photosensitive resin：
According to weight proportion, first micron silica, polyethylene wax powder and nonionic surfactant are stirred, Ran Houjia
Enter remaining urethane acrylate, epoxy resin, reactive diluent, cation-type photopolymerization initiators and free radical type light to gather
Initiator is closed, 80 °C of stirrings is then heated to and is made faint yellow uniform liquid in 60 minutes.
Embodiment 3
The photocureable rapid shaping of the present embodiment Asia light photosensitive resin, it is by made by following raw materials：Polyurethane acroleic acid
40 parts of ester, epoxy resin（Aliphatic glycidyl ether epoxy resin）20 parts, reactive diluent（Ethylene glycol diglycidylether two
Acrylate and tripropyleneglycol diglycidyl ether diacrylate）18 parts, cation-type photopolymerization initiators（Diaryl iodonium
Hexafluorophosphate）1 part, free radical type Photoepolymerizationinitiater initiater（1- hydroxy cyclohexyl phenylketones）8 parts, it is 6 parts of micron silica, poly-
1 part of ethene wax powder, nonionic surfactant（Fatty acid methyl ester ethoxylate and polyoxyethylene sorbitol acid anhydride monostearate
Ester）2 parts.
The photocureable rapid shaping of the present embodiment is as follows with the preparation method of sub- light photosensitive resin：
According to weight proportion, first micron silica, polyethylene wax powder and nonionic surfactant are stirred, Ran Houjia
Enter remaining urethane acrylate, epoxy resin, reactive diluent, cation-type photopolymerization initiators and free radical type light to gather
Initiator is closed, 70 °C of stirrings is then heated to and is made faint yellow uniform liquid in 90 minutes.
Embodiment 4
The photocureable rapid shaping of the present embodiment Asia light photosensitive resin, it is by made by following raw materials：Polyurethane acroleic acid
42 parts of ester, epoxy resin（3,4- epoxy radicals -6- methylcyclohexyls formic acid -3 ', 4 '-epoxy radicals -6 '-methylcyclohexyl methyl esters）28
Part, reactive diluent（Ethylene glycol diglycidylether diacrylate）10 parts, cation-type photopolymerization initiators（Diaryl iodonium
Hexafluoro arsenate and triaryl sulphur hexafluorophosphate）2 parts, free radical type Photoepolymerizationinitiater initiater（Dimethoxybenzoin and chlorine
Change benzophenone）4 parts, 6 parts of micron silica, 5 parts of polyethylene wax powder, nonionic surfactant（Aliphatic alcohol polyethenoxy
Ether and fatty acid methyl ester ethoxylate）3 parts.
The photocureable rapid shaping of the present embodiment preparation method of sub- light photosensitive resin is with embodiment 2.
Embodiment 5
The photocureable rapid shaping of the present embodiment Asia light photosensitive resin, it is by made by following raw materials：Polyurethane acroleic acid
38 parts of ester, epoxy resin（Aliphatic glycidyl ether epoxy resin and 3,4- epoxy radicals -6- methylcyclohexyls formic acid -3 ', 4 ' -
Epoxy radicals -6 '-methylcyclohexyl methyl esters）20 parts, reactive diluent（Tripropyleneglycol diglycidyl ether diacrylate）25 parts,
Cation-type photopolymerization initiators（Diaryl iodonium hexafluorophosphate and Diaryl iodonium hexafluoro arsenate）3.5 parts, free radical
Type Photoepolymerizationinitiater initiater（Dimethoxybenzoin and 1- hydroxy cyclohexyl phenylketones）5.5 parts, 4 parts of micron silica, polyethylene
3 parts of wax powder, nonionic surfactant（AEO）1 part.
The photocureable rapid shaping of the present embodiment preparation method of sub- light photosensitive resin is with embodiment 3.
Embodiment 6
The photocureable rapid shaping of the present embodiment Asia light photosensitive resin, it is by made by following raw materials：Polyurethane acroleic acid
32 parts of ester, epoxy resin（3,4- epoxy radicals -6- methylcyclohexyls formic acid -3 ', 4 '-epoxy radicals -6 '-methylcyclohexyl methyl esters）22
Part, reactive diluent（Ethylene glycol diglycidylether diacrylate and tripropyleneglycol diglycidyl ether diacrylate）23
Part, cation-type photopolymerization initiators（Triaryl sulphur hexafluorophosphate）5.6 parts, free radical type Photoepolymerizationinitiater initiater（Chlorination
Benzophenone）4.4 parts, 1 part of micron silica, 3 parts of polyethylene wax powder, nonionic surfactant（Polyoxyethylene sorbitol
Acid anhydride monostearate）3 parts.
The photocureable rapid shaping of the present embodiment preparation method of sub- light photosensitive resin is with embodiment 1.
Embodiment 7
The photocureable rapid shaping of the present embodiment Asia light photosensitive resin, it is by made by following raw materials：Polyurethane acroleic acid
45 parts of ester, epoxy resin（3,4- epoxy radicals -6- methylcyclohexyls formic acid -3 ', 4 '-epoxy radicals -6 '-methylcyclohexyl methyl esters）5
Part, reactive diluent（Tripropyleneglycol diglycidyl ether diacrylate）25 parts, cation-type photopolymerization initiators（Diaryl
Iodine hexafluoro arsenate）8 parts, free radical type Photoepolymerizationinitiater initiater（Dimethoxybenzoin）1 part, 4 parts of micron silica, poly- second
9 parts of alkene wax powder, nonionic surfactant（Fatty acid methyl ester ethoxylate）3 parts.
The photocureable rapid shaping of the present embodiment preparation method of sub- light photosensitive resin is with embodiment 3.
The unit of part is g in above-described embodiment 1 ~ 7 and comparative example 1 ~ 3.
In embodiment 1 ~ 7 and comparative example 1 ~ 3, the particle diameter of micron silica and polyethylene wax powder is 1 ~ 15 micron, folding
Light rate is 1.45 ~ 1.54.
Table 1 is real embodiment 1 ~ 7 and the material prescription of comparative example 1 ~ 3 and viscosity.
The embodiment 1 ~ 7 of table 1 and the material prescription of comparative example 1 ~ 3 and viscosity（Weight/part）
First, photocureable rapid shaping photosensitive resin curing molding mechanical property and shrinkage factor method of testing
Using U.S.'s Formlabs companies Form1 type 3D printers, the photocureable rapid shaping Asia light photosensitive resin for preparing is beaten
Print the sample batten for test.Specifically print conditions are：Shaping thickness is 0.10 mm, and sweep speed is 20 cm3/ h, its
The parameters such as his line width are molded using the parameter of system default.
Mechanics Performance Testing includes tensile property test, bending property test and impact strength test.Tensile property is tested
Carry out according to GB/T 1040, the sample batten size of printing is 150 × 10 × 4 mm, and draw speed is 50 mm/min；Bending
Performance test is carried out according to GB/T 9341, and the sample batten size of printing is 80 × 10 × 4 mm, and rate of bending is 2 mm/
Min, span is 64 mm；Simple beam impact strength is carried out according to GB/T 1043, and the sample batten size of printing is 80 × 6 × 4
Mm, notch depth is 1/3rd of sample thickness.Material comprehensive mechanical property test by test obtained by tensile strength,
The numerical value of elongation at break, bending modulus and impact strength is passed judgment on.
Shrinkage factor test is the sample batten developed width for extension test printed using slide measure accurate measurement
W2（Sample batten designs width W1=10 mm）, the absolute value of the difference of W2 and W1 and the ratio of W1 are shrinkage factor.Shrinkage factor is got over
It is little, show that printing precision is higher.
2nd, the photocureable rapid shaping method of testing of sub- light photosensitive resin curing molding glossiness
Glossiness test after photosensitive resin curing molding is carried out according to GB/T 8807-1988, and the sample length, width and height size of printing is
50 × 50 × 1 mm, is measured using bright luster instrument to sample glossiness.By sample horizontal setting on formation plate, minute surface
Glossometer adopts D65 light sources, and it is 45 ° that regulation is radiated at the incidence angle on sample, and retest three times, statistical test value is simultaneously calculated
Mean value, i.e., final sample glossiness.Table 2 is embodiment 1 ~ 7 and the sample mechanical property of comparative example 1 ~ 3, shrinkage factor and glossiness
Test result.
The embodiment 1 ~ 7 of table 2 and the sample mechanical property of comparative example 1 ~ 3, shrinkage factor and glossiness test result
As shown in Table 2, compared with comparative example 1, add in photosensitive resin after micron silica in comparative example 2, mechanical property
Have and significantly increase, shrinkage factor is also decreased obviously, add after polyethylene wax powder in comparative example 3, mechanical property is compared with comparative example 1
Improve, shrinkage factor is reduced, but effect is more or less the same with comparative example 2, and micron silica and polyethylene wax powder are common in embodiment 1
Addition（Micron silica is 1 with the ratio of the consumption of polyethylene wax powder:1）Afterwards, mechanical property exists after photosensitive resin curing molding
There are further lifting, tensile strength, elongation at break and breach under the collective effect of micron silica and polyethylene wax powder
Impact strength is all significantly increased compared with comparative example 2 and comparative example 3, and shrinkage factor also further declines, and printing precision is improved, practicality
It is higher.
It is the sample of 50 × 50 × 1 mm by comparative example 1 ~ 3 and the file printing of embodiment 1 ~ 7, tests according to above-mentioned glossiness
Method is tested sample translucency.As shown in Table 2, in comparative example 1, specimen surface is bright and clean, and glossiness is higher, reaches
92.3%.The addition of micron silica in comparative example 2 causes occur matt effect after photosensitive resin curing molding, under glossiness
It is down to 45.2%.The addition of polyethylene wax powder in comparative example 3 advantageously reduces glossiness, obtains the light with uneven surface
Quick resin forming part, now sample glossiness be reduced to 48.1%.Micron silica and polyethylene wax powder in embodiment 1
After common addition, sample glossiness has significantly further to be reduced, and glossiness is 35.6%.It can thus be seen that material glossiness
Because the addition of micron silica and polyethylene wax powder has obvious reduction, be conducive to the formation of material matt effect.
Embodiment 2-7 is the photocureable rapid shaping Asia light photosensitive resin prepared in compositional range of the present invention,
The sample of manufacture has obvious matt effect, and mechanical property is also significantly improved, and shrinkage factor is low, and printing precision is high, illustrates this
The bright sub- light photosensitive resin can be advantageously applied to Introduction To Stereolithography and receive, and be conducive to photocureable rapid shaping
Technology is promoted the use of.
The general principle and principal character and advantages of the present invention of the present invention has been shown and described above.The skill of the industry
Simply explanation of the art personnel it should be appreciated that the present invention is not restricted to the described embodiments, described in above-described embodiment and specification
The principle of the present invention, without departing from the spirit and scope of the present invention, the present invention also has various changes and modifications, these
Changes and improvements are both fallen within scope of the claimed invention.The claimed scope of the invention by appending claims and
Its equivalent thereof.
Claims (10)
1. a kind of photocureable rapid shaping is with sub- light photosensitive resin, it is characterised in that it is made up of the raw material of following portions by weight
's：Urethane acrylate 5 ~ 45, epoxy resin 5 ~ 45, reactive diluent 10 ~ 25, cation-type photopolymerization initiators 1 ~ 8, from
By fundamental mode Photoepolymerizationinitiater initiater 1 ~ 8, micron silica 1 ~ 10, polyethylene wax powder 1 ~ 10, nonionic surfactant 1 ~ 3.
2. photocureable rapid shaping according to claim 1 is with sub- light photosensitive resin, it is characterised in that：The micron dioxy
SiClx is 1 with the ratio of the parts by weight of polyethylene wax powder:3~6:1, the particle diameter of the micron silica and polyethylene wax powder is equal
For 1 ~ 15 micron, index of refraction is 1.45 ~ 1.54.
3. photocureable rapid shaping according to claim 1 is with sub- light photosensitive resin, it is characterised in that：The photocuring is fast
The viscosity of rapid-result type Asia light photosensitive resin is 100 ~ 300 mPas.
4. photocureable rapid shaping according to claim 1 is with sub- light photosensitive resin, it is characterised in that：The epoxy resin
For the one kind in aliphatic glycidyl ether epoxy resin, cycloaliphatic epoxy resin or its mixture.
5. photocureable rapid shaping according to claim 4 is with sub- light photosensitive resin, it is characterised in that：The aliphatic ring
Oxygen tree fat be 3,4- epoxy radicals -6- methylcyclohexyls formic acid -3 ', 4 '-epoxy radicals -6 '-methylcyclohexyl methyl esters.
6. photocureable rapid shaping according to claim 1 is with sub- light photosensitive resin, it is characterised in that：Reactive diluent is
One or two in ethylene glycol diglycidylether diacrylate or tripropyleneglycol diglycidyl ether diacrylate are mixed
Compound.
7. photocureable rapid shaping according to claim 1 is with sub- light photosensitive resin, it is characterised in that：The cationic
Photoepolymerizationinitiater initiater is Diaryl iodonium hexafluorophosphate, Diaryl iodonium hexafluoro arsenate or triaryl sulphur hexafluorophosphate
In one or more mixture.
8. photocureable rapid shaping according to claim 1 is with sub- light photosensitive resin, it is characterised in that：The free radical type
Photoepolymerizationinitiater initiater is one or more in dimethoxybenzoin, chlorinated diphenyl ketone, 1- hydroxy cyclohexyl phenylketones
Mixture.
9. photocureable rapid shaping according to claim 1 is with sub- light photosensitive resin, it is characterised in that：The nonionic table
Face activating agent is in AEO, fatty acid methyl ester ethoxylate, polyoxyethylene sorbitan monostearate
The mixture of one or more.
10. according to the preparation method of the arbitrary described washable ultraviolet laser solidification rapid shaping photosensitive resin of claim 1 ~ 9,
It is characterized in that step is as follows：According to weight proportion, first by micron silica, polyethylene wax powder and nonionic surfactant
Stir, be subsequently adding remaining urethane acrylate, epoxy resin, reactive diluent, cation-type photopolymerization and cause
Agent and free radical type Photoepolymerizationinitiater initiater, are then heated to 60 ~ 80 °C of stirrings and make faint yellow uniform liquid in 60 ~ 120 minutes
Body.
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