CN104250436B - A kind of nylon micro-sphere modified light-sensitive resin, preparation method and its application in 3D printing - Google Patents
A kind of nylon micro-sphere modified light-sensitive resin, preparation method and its application in 3D printing Download PDFInfo
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- CN104250436B CN104250436B CN201310259644.8A CN201310259644A CN104250436B CN 104250436 B CN104250436 B CN 104250436B CN 201310259644 A CN201310259644 A CN 201310259644A CN 104250436 B CN104250436 B CN 104250436B
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- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L63/00—Compositions of epoxy resins; Compositions of derivatives of epoxy resins
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C67/00—Shaping techniques not covered by groups B29C39/00 - B29C65/00, B29C70/00 or B29C73/00
- B29C67/02—Moulding by agglomerating
- B29C67/04—Sintering
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- C08L51/00—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers
- C08L51/08—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers grafted on to macromolecular compounds obtained otherwise than by reactions only involving unsaturated carbon-to-carbon bonds
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- C08L75/00—Compositions of polyureas or polyurethanes; Compositions of derivatives of such polymers
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Abstract
The present invention provides a kind of nylon micro-sphere modified light-sensitive resin, preparation method and its application in 3D printing, and nylon micro-sphere modified light-sensitive resin is by 1~10 part of 30~50 parts of acrylate, 30~50 parts of epoxy resin, 5~50 parts of nylon micro-sphere, 0.1~5 part of the steady agent of light, 20~30 parts of diluent, 0.1~5 part of defoamer, 0.1~5 part of levelling agent, 1~10 part of cationic initiators and free radical type Photoepolymerizationinitiater initiater.Nylon micro-sphere modified light-sensitive resin prepared by the present invention has the advantages that shaping speed is fast, mechanical strength is high, good stability of the dimension, and preparation technology is simple in addition, can directly using and be extended to 3D printing field prepare with labyrinth part.
Description
Technical field
The present invention relates to technical field of macromolecules, and in particular to a kind of nylon micro-sphere modified light-sensitive resin, preparation method and
Its application in 3D printing.
Background technology
3D printer technology is the new rapid prototyping ＆ manufacturing technology based on material stacking method, first left by powder-laying roller during work
Move right, will uniformly lay on moulding cylinder for the powder in powder cylinder, then existed according to designed part model by printhead
This cross sectional shape is sprayed on first layer powder, 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.
The popularity of domestic 3D printing is relatively low, and the report about its special photosensitive resin material is even more to rarely have, early stage
Common problem has that product mechanical strength is low, curing efficiency is low and the deficiencies of poor dimensional stability in achievement in research；In addition
Nylon powder material use for 3D printing crystallizes what is separated out after nylon resin directly being crushed or being dissolved in organic solvent
Prepared by method, the stability of the raw material is poor, resulting product low intensity, poor toughness.
The present invention makes moderate progress in these areas.Nylon micro-sphere preparation method of the present invention is shown in patent CN
101077910, it is a kind of high molecular weight nylon micro-sphere of size tunable.In terms of shaping speed, provided by the present invention for 3D
The photosensitive resin curing rate of printing is fast, can significantly shorten research and development and production cycle.In terms of mechanical strength, micron level nylon
The addition of microballoon can greatly improve its every mechanical property, and improve dimensional stability.Preparation technology of the present invention is simple, can be direct
Using and be extended to 3D printing field prepare with labyrinth part.
The content of the invention
It is an object of the invention to provide Buddhist nun prepared by a kind of nylon micro-sphere modified light-sensitive resin and preparation method thereof, the present invention
The microsphere modified photosensitive resin of dragon has the advantages that shaping speed is fast, mechanical strength is high, good stability of the dimension.The 3rd of the present invention
Purpose is to provide application of the nylon micro-sphere modified light-sensitive resin in 3D printing.
To achieve the above object, the present invention uses following technical scheme：
A kind of nylon micro-sphere modified light-sensitive resin, it is characterised in that：It is prepared by weight by following components：
30~50 parts of acrylate,
30~50 parts of epoxy resin,
5~50 parts of nylon micro-sphere,
0.1~5 part of the steady agent of light,
20~30 parts of diluent,
0.1~5 part of defoamer,
0.1~5 part of levelling agent,
0.1~5 part of antioxidant
1~10 part of cationic initiators,
1~10 part of free radical type Photoepolymerizationinitiater initiater.
Described acrylate is in epoxy monoacrylate, urethane acrylate and polyalcohol acrylate acrylic acid
At least one.
Described epoxy resin be phenol aldehyde type epoxy resin, bisphenol-s epoxy resin and aminoepoxy resin at least
It is a kind of.
Described nylon micro-sphere is nylon 4, nylon 6, nylon 7, nylon 8 or the microballoon of nylon 12, and particle diameter is 0.1 μm~500 μ
m。
The steady agent of described light is 2,4- benzophenonedicarboxylic acids, chlorination BTA or 2- hydroxyl -4- n-octyloxy hexichol
At least one of ketone.
Described diluent be trimethylolpropane trimethacrylate, ethoxyquin base trimethylolpropane trimethacrylate,
At least one of ethylene glycol diglycidylether and tripropyleneglycol diglycidyl ether.
Described defoamer be dimethyl polysiloxane, ethylene oxide propylene oxide copolyether and polyether silicone in extremely
Few one kind；Described levelling agent is organosilicon-epoxide ethane copolymer, organosilicon-epoxide propane copolymer and poly dimethyl silicon
At least one of oxygen alkane；Described antioxidant be four (3,5- di-t-butyl -4- hydroxyls) benzenpropanoic acid pentaerythritol esters, three (2,
4- di-t-butyls) phenyl-phosphite or N, N'- be double-(3- (3,5- di-tert-butyl-hydroxy phenyls) propiono) hexamethylene diamine in
It is at least one..
Described cationic initiators are salt compounded of iodine or sulfonium salt.
Described free radical type Photoepolymerizationinitiater initiater be benzophenone, chlorinated diphenyl ketone and dimethoxybenzoin in extremely
Few one kind.
Second object of the present invention is to provide a kind of preparation method of above-mentioned nylon micro-sphere modified light-sensitive resin, including with
Lower step：
（1）In the special glass there-necked flask equipped with agitator and condenser pipe, 30~50 parts of acrylate, ring are sequentially added
30~50 parts of oxygen tree fat, 20~30 parts of diluent, 0.1~5 part of defoamer, 0.1~5 part of levelling agent, cationic initiators 1~
10 parts and 1~10 part of free radical type Photoepolymerizationinitiater initiater, are warming up to 50~80 DEG C, stir about 10min~30min, obtain yellowish
The homogeneous liquid of color；
（2）0.1~5 part of 5~50 parts of nylon micro-sphere, 0.1~5 part of the steady agent of light and antioxidant are added in aforesaid liquid, is surpassed
Sound disperses 10~30min to uniform state, that is, obtains nylon micro-sphere modified light-sensitive resin.
Third object of the present invention is to provide application of the nylon micro-sphere modified light-sensitive resin in 3D printing, in 3D printing
The nylon micro-sphere modified light-sensitive resin of above-mentioned preparation is prepared into product in equipment, its technological parameter is：5~15W of light source power,
1000~3000mm/s of sweep speed, sintering thickness are 0.05~0.2mm.
The invention has the advantages that：
1st, the nylon micro-sphere for having HMW in nylon micro-sphere modified light-sensitive resin components of the invention can improve modification
The mechanical strength of photosensitive resin and certain dimensional stability；Effective cooperation of light trigger and unsaturated-resin can be accelerated to be modified
The shaping speed of photosensitive resin；Unsatured epoxy resin and the co-curing chi for greatly improving modified light-sensitive resin of acrylate
Very little stability；So nylon micro-sphere modified light-sensitive resin prepared by the present invention has, shaping speed is fast, mechanical strength is high, size is steady
The advantages that qualitative good.
2nd, the preparation technology of nylon micro-sphere modified light-sensitive resin of the present invention is simple, easily realizes industrialized production.
3rd, with nylon micro-sphere modified light-sensitive resin of the present invention can directly using and be extended to 3D printing field prepare have it is multiple
The part of miscellaneous structure, the bending strength of manufactured product, shrinkage factor etc. has larger lifting, according to ASTM D790 and ASTM D
955-08 detects its bending strength and shrinkage factor, is up to 105MPa, and photosensitive resin improves 75% more before modified；The receipts of product
Shrinkage minimum 0.7%, more before modified photosensitive resin reduce 53%.
Embodiment
Present invention is further detailed with reference to specific embodiment, but the embodiment is not to this
The simple restriction of invention connotation, any simple change or equivalent substitution based on made by true spirit all should belong to
Within scope of the present invention.Unless otherwise instructed, number is parts by weight described in each embodiment.
Embodiments below is lowered with comparative examples through product sample made of 3D printing in 23 DEG C, 50% humidity environment
After section, its detection bending strength of ASTM D790 and ASTM D 955-08 is respectively adopted and shrinkage factor, specific data are shown in Table an institute
Show.
The specific embodiment of the present invention is as follows：
Embodiment 1
（1）In the special glass there-necked flask equipped with agitator and condenser pipe, sequentially add 15 parts of epoxy monoacrylate,
15 parts of urethane acrylate, 30 parts of phenol aldehyde type epoxy resin, 10 parts of trimethylolpropane trimethacrylate, the hydroxyl of ethoxyquin base three
10 parts of propane tri, 0.1 part of dimethyl polysiloxane, 0.1 part of polyether silicone, organosilicon-epoxide ethane are total to
0.1 part of polymers, 0.1 part of organosilicon-epoxide propane copolymer, 1 part of salt compounded of iodine, 1 part of sulfonium salt, 6 parts of benzophenone, chlorinated diphenyl
4 parts of ketone, 50 DEG C, stir about 30min are warming up to, obtain faint yellow homogeneous liquid；
（2）5 parts of 4 microballoon of nylon, 1 part of the steady agent 2,4- benzophenonedicarboxylic acids of light, the steady agent chlorine of light are added in aforesaid liquid
Change 4 parts of BTA, 0.1 part of antioxidant four (3,5- di-t-butyl -4- hydroxyls) benzenpropanoic acid pentaerythritol ester and antioxidant three (2,
4- di-t-butyls) 0.5 part, ultrasonic disperse 10min to uniform state of phenyl-phosphite, that is, obtain nylon micro-sphere modified light-sensitive tree
Fat；
（3）Above-mentioned nylon micro-sphere modified light-sensitive resin is prepared as product in 3D printing equipment, technological parameter is：Light source
Power 15W, sweep speed 1000mm/s, sintering thickness are 0.2mm.Molded article performance detection is shown in Table one.
Embodiment 2
（1）In the special glass there-necked flask equipped with agitator and condenser pipe, sequentially add 30 parts of epoxy monoacrylate,
50 parts of phenol aldehyde type epoxy resin, 20 parts of trimethylolpropane trimethacrylate, 0.1 part of dimethyl polysiloxane, organosilicon-ring
Oxidative ethane copolymer 1 part, 1 part of salt compounded of iodine, 8 parts of benzophenone, are warming up to 60 DEG C, stir about 20min, obtain faint yellow homogeneous
Liquid；
（2）10 parts of 4 microballoon of nylon, 2 parts of the steady agent 2,4- benzophenonedicarboxylic acids of light and antioxidant are added in aforesaid liquid
Four (3,5- di-t-butyl -4- hydroxyls) 1 part of benzenpropanoic acid pentaerythritol esters, ultrasonic disperse 10min to uniform state, that is, are used for
A kind of nylon micro-sphere modified light-sensitive resin of 3D printing；
（3）Above-mentioned material is prepared as product in 3D printing equipment, technological parameter is：Light source power 15W, sweep speed
1000mm/s, sintering thickness are 0.2mm, are prepared as required product.
Molded article performance detection is shown in Table one.
Embodiment 3
（1）In the special glass there-necked flask equipped with agitator and condenser pipe, sequentially add 30 parts of epoxy monoacrylate,
50 parts of phenol aldehyde type epoxy resin, 20 parts of trimethylolpropane trimethacrylate, 0.1 part of dimethyl polysiloxane, organosilicon-ring
2 parts of oxidative ethane copolymer, 3 parts of salt compounded of iodine, 3 parts of benzophenone, are warming up to 70 DEG C, stir about 10min, obtain faint yellow homogeneous
Liquid；
（2）20 parts of 6 microballoon of nylon, 1 part of the steady agent 2,4- benzophenonedicarboxylic acids of light and antioxidant are added in aforesaid liquid
Four (3,5- di-t-butyl -4- hydroxyls) 2 parts of benzenpropanoic acid pentaerythritol esters, ultrasonic disperse 10min to uniform state, that is, are used for
A kind of nylon micro-sphere modified light-sensitive resin of 3D printing；
（3）Above-mentioned material is prepared as product in 3D printing equipment, technological parameter is：Light source power 15W, sweep speed
1000mm/s, sintering thickness are 0.2mm, are prepared as required product.
Molded article performance detection is shown in Table one.
Embodiment 4
（1）In the special glass there-necked flask equipped with agitator and condenser pipe, sequentially add 30 parts of epoxy monoacrylate,
It is 50 parts of phenol aldehyde type epoxy resin, 20 parts of ethoxyquin base trimethylolpropane trimethacrylate, 1 part of dimethyl polysiloxane, organic
5 parts of silicon-ethylene oxide copolymer, 6 parts of salt compounded of iodine, 1 part of benzophenone, are warming up to 80 DEG C, stir about 30min, obtain faint yellow
Homogeneous liquid；
（2）30 parts of 6 microballoon of nylon, 0.1 part of the steady agent 2,4- benzophenonedicarboxylic acids of light and antioxygen are added in aforesaid liquid
Agent four (3,5- di-t-butyl -4- hydroxyls) 5 parts of benzenpropanoic acid pentaerythritol ester, ultrasonic disperse 10min to uniform state, that is, is used
In a kind of nylon micro-sphere modified light-sensitive resin of 3D printing；
（3）Above-mentioned material is prepared as product in 3D printing equipment, technological parameter is：Light source power 15W, sweep speed
1000mm/s, sintering thickness are 0.15mm, are prepared as required product.
Molded article performance detection is shown in Table one.
Embodiment 5
（1）In the special glass there-necked flask equipped with agitator and condenser pipe, sequentially add 40 parts of urethane acrylate,
40 parts of bisphenol-s epoxy resin, 25 parts of ethoxyquin base trimethylolpropane trimethacrylate, ethylene oxide propylene oxide copolyether
1 part, 0.1 part of organosilicon-epoxide propane copolymer, 8 parts of salt compounded of iodine, 10 parts of chlorinated diphenyl ketone, be warming up to 50 DEG C, stir about
20min, obtain faint yellow homogeneous liquid；
（2）40 parts of 6 microballoon of nylon, 5 parts of the steady agent chlorination BTA of light and the (2,4- of antioxidant three are added in aforesaid liquid
Di-t-butyl) 0.1 part, ultrasonic disperse 20min to uniform state of phenyl-phosphite, that is, obtain micro- for a kind of nylon of 3D printing
Ball modified light-sensitive resin；
（3）Above-mentioned material is prepared as product in 3D printing equipment, technological parameter is：Light source power 10W, sweep speed
2000mm/s, sintering thickness are 0.15mm, are prepared as required product.
Molded article performance detection is shown in Table one.
Embodiment 6
（1）In the special glass there-necked flask equipped with agitator and condenser pipe, sequentially add 40 parts of urethane acrylate,
40 parts of bisphenol-s epoxy resin, 25 parts of ethoxyquin base trimethylolpropane trimethacrylate, ethylene oxide propylene oxide copolyether
1 part, levelling agent organosilicon-epoxide propane copolymer 1 part, 10 parts of salt compounded of iodine, 8 parts of chlorinated diphenyl ketone, be warming up to 60 DEG C, stir
About 10min is mixed, obtains faint yellow homogeneous liquid；
（2）50 parts of 7 microballoon of nylon, 2 parts of the steady agent chlorination BTA of light and the (2,4- of antioxidant three are added in aforesaid liquid
Di-t-butyl) 1 part, ultrasonic disperse 20min to uniform state of phenyl-phosphite, that is, obtain a kind of nylon micro-sphere for 3D printing
Modified light-sensitive resin；
（3）Above-mentioned material is prepared as product in 3D printing equipment, technological parameter is：Light source power 10W, sweep speed
2000mm/s, sintering thickness are 0.15mm, are prepared as required product.
Molded article performance detection is shown in Table one.
Embodiment 7
（1）In the special glass there-necked flask equipped with agitator and condenser pipe, sequentially add 40 parts of urethane acrylate,
40 parts of bisphenol-s epoxy resin, 25 parts of ethylene glycol diglycidylether, 2 parts of ethylene oxide propylene oxide copolyether, organosilicon-
2 parts of epoxy propane copolymer, 1 part of sulfonium salt, 3 parts of chlorinated diphenyl ketone, are warming up to 70 DEG C, stir about 30min, obtain yellowish
The homogeneous liquid of color；
（2）5 parts of 7 microballoon of nylon, 1 part of the steady agent chlorination BTA of light and the (2,4- of antioxidant three are added in aforesaid liquid
Di-t-butyl) 2 parts, ultrasonic disperse 20min to uniform state of phenyl-phosphite, that is, obtain a kind of nylon micro-sphere for 3D printing
Modified light-sensitive resin；
（3）Above-mentioned material is prepared as product in 3D printing equipment, technological parameter is：Light source power 10W, sweep speed
2000mm/s, sintering thickness are 0.10mm, are prepared as required product.
Molded article performance detection is shown in Table one.
Embodiment 8
（1）In the special glass there-necked flask equipped with agitator and condenser pipe, sequentially add 40 parts of urethane acrylate,
40 parts of bisphenol-s epoxy resin, 25 parts of ethylene glycol diglycidylether, 2 parts of ethylene oxide propylene oxide copolyether, organosilicon-
5 parts of epoxy propane copolymer, 3 parts of sulfonium salt, 1 part of chlorinated diphenyl ketone, are warming up to 80 DEG C, stir about 20min, obtain yellowish
The homogeneous liquid of color；
（2）Added in aforesaid liquid 10 parts of nylon 8 microballoon, 0.1 part of the steady agent chlorination BTA of light and antioxidant three (2,
4- di-t-butyls) 5 parts, ultrasonic disperse 20min to uniform state of phenyl-phosphite, that is, obtain micro- for a kind of nylon of 3D printing
Ball modified light-sensitive resin；
（3）Above-mentioned material is prepared as product in 3D printing equipment, technological parameter is：Light source power 10W, sweep speed
2000mm/s, sintering thickness are 0.10mm, are prepared as required product.
Molded article performance detection is shown in Table one.
Embodiment 9
（1）In the special glass there-necked flask equipped with agitator and condenser pipe, polyalcohol acrylate propylene is sequentially added
50 parts of acid, 30 parts of aminoepoxy resin, 30 parts of ethylene glycol diglycidylether, 2 parts of polyether silicone, dimethyl silicone polymer
0.1 part, 6 parts of sulfonium salt, 10 parts of dimethoxybenzoin, be warming up to 50 DEG C, stir about 10min, obtain faint yellow homogeneous liquid；
（2）Added in aforesaid liquid 20 parts of nylon 8 microballoon, 5 parts of the steady agent 2-hydroxy-4-n-octoxybenzophenone of light and
N, N'- pairs-(3- (3,5- di-tert-butyl-hydroxy phenyl) propiono) 0.1 part of hexamethylene diamine of antioxidant, ultrasonic disperse 30min is extremely
Uniform state, that is, obtain a kind of nylon micro-sphere modified light-sensitive resin for 3D printing；
（3）Above-mentioned material is prepared as product in 3D printing equipment, technological parameter is：Light source power 5W, sweep speed
3000mm/s, sintering thickness are 0.10mm, are prepared as required product.
Molded article performance detection is shown in Table one.
Embodiment 10
（1）In the special glass there-necked flask equipped with agitator and condenser pipe, polyalcohol acrylate propylene is sequentially added
50 parts of acid, 30 parts of aminoepoxy resin, 30 parts of tripropyleneglycol diglycidyl ether, 5 parts of polyether silicone, polydimethylsiloxanes
1 part of alkane, 8 parts of sulfonium salt, 8 parts of dimethoxybenzoin, are warming up to 60 DEG C, stir about 30min, obtain faint yellow homogeneous liquid；
（2）Added in aforesaid liquid 30 parts of nylon 8 microballoon, 5 parts of the steady agent 2-hydroxy-4-n-octoxybenzophenone of light and
Antioxidant N, N'- be double-(3- (3,5- di-tert-butyl-hydroxy phenyl) propiono) 1 part of hexamethylene diamine, ultrasonic disperse 30min is to equal
One state, that is, obtain a kind of nylon micro-sphere modified light-sensitive resin for 3D printing；
（3）Above-mentioned material is prepared as product in 3D printing equipment, technological parameter is：Light source power 5W, sweep speed
3000mm/s, sintering thickness are 0.05mm, are prepared as required product.
Molded article performance detection is shown in Table one.
Embodiment 11
（1）In the special glass there-necked flask equipped with agitator and condenser pipe, polyalcohol acrylate propylene is sequentially added
50 parts of acid, 30 parts of aminoepoxy resin, 30 parts of tripropyleneglycol diglycidyl ether, 5 parts of polyether silicone, polydimethylsiloxanes
2 parts of alkane, 10 parts of sulfonium salt, 3 parts of dimethoxybenzoin, are warming up to 70 DEG C, stir about 20min, obtain faint yellow homogeneous liquid；
（2）40 parts of 12 microballoon of nylon, 1 part of the steady agent 2-hydroxy-4-n-octoxybenzophenone of light are added in aforesaid liquid
With antioxidant N, N'- pairs-(3- (3,5- di-tert-butyl-hydroxy phenyl) propiono) 2 parts of hexamethylene diamine, ultrasonic disperse 30min is extremely
Uniform state, that is, obtain a kind of nylon micro-sphere modified light-sensitive resin for 3D printing；
（3）Above-mentioned material is prepared as product in 3D printing equipment, technological parameter is：Light source power 5W, sweep speed
3000mm/s, sintering thickness are 0.05mm, are prepared as required product.
Molded article performance detection is shown in Table one.
Embodiment 12
（1）In the special glass there-necked flask equipped with agitator and condenser pipe, polyalcohol acrylate propylene is sequentially added
50 parts of acid, 30 parts of aminoepoxy resin, 30 parts of tripropyleneglycol diglycidyl ether, 5 parts of polyether silicone, polydimethylsiloxanes
5 parts of alkane, 10 parts of sulfonium salt, 1 part of dimethoxybenzoin, are warming up to 80 DEG C, stir about 10min, obtain faint yellow homogeneous liquid；
（2）50 parts of 12 microballoon of nylon, the steady agent 2-hydroxy-4-n-octoxybenzophenone 0.1 of light are added in aforesaid liquid
N, N'- pairs-(3- (3,5- di-tert-butyl-hydroxy phenyl) propiono) 5 parts of hexamethylene diamine of part and antioxidant, ultrasonic disperse 30min
To uniform state, that is, obtain a kind of nylon micro-sphere modified light-sensitive resin for 3D printing；
（3）Above-mentioned material is prepared as product in 3D printing equipment, technological parameter is：Light source power 5W, sweep speed
3000mm/s, sintering thickness are 0.05mm, are prepared as required product.
Molded article performance detection is shown in Table one.
Comparative examples 1
（1）Raw material is equipped with the following proportions：
30 parts of epoxy monoacrylate,
50 parts of phenol aldehyde type epoxy resin,
20 parts of diluent trimethylolpropane trimethacrylate,
0.1 part of defoamer dimethyl polysiloxane,
2 parts of levelling agent organosilicon-epoxide ethane copolymer,
3 parts of cationic initiators salt compounded of iodine,
3 parts of free radical type Photoepolymerizationinitiater initiater benzophenone.
（2）In the special glass there-necked flask equipped with agitator and condenser pipe, above-mentioned raw materials are sequentially added, are warming up to 70
DEG C, stir about 10min, obtain faint yellow homogeneous liquid；
（3）Above-mentioned material is prepared as product in 3D printing equipment, technological parameter is：Light source power 15W, sweep speed
1000mm/s, sintering thickness are 0.2mm, are prepared as required product.
Molded article performance detection is shown in Table one.
Comparative examples 2
（1）Raw material is equipped with the following proportions：
50 parts of polyalcohol acrylate acrylic acid,
30 parts of aminoepoxy resin,
30 parts of diluent tripropyleneglycol diglycidyl ether,
5 parts of defoamer polyether silicone,
2 parts of levelling agent dimethyl silicone polymer,
10 parts of cationic initiators sulfonium salt,
3 parts of free radical type Photoepolymerizationinitiater initiater dimethoxybenzoin.
（2）In the special glass there-necked flask equipped with agitator and condenser pipe, above-mentioned raw materials are sequentially added, are warming up to 70
DEG C, stir about 20min, obtain faint yellow homogeneous liquid；
（3）Above-mentioned material is prepared as product in 3D printing equipment, technological parameter is：Light source power 5W, sweep speed
3000mm/s, sintering thickness are 0.05mm, are prepared as required product.
Molded article performance detection is shown in Table one.
Bending strength and shrinkage factor the test table of the 3D printing product of table one, embodiment 1-12 and comparative examples 1-2：
| Performance | Bending strength（MPa） | Shrinkage factor（%） |
| Embodiment 1 | 94 | 0.8 |
| Embodiment 2 | 98 | 0.7 |
| Embodiment 3 | 102 | 0.7 |
| Embodiment 4 | 84 | 0.8 |
| Embodiment 5 | 88 | 0.8 |
| Embodiment 6 | 91 | 0.9 |
| Embodiment 7 | 95 | 0.9 |
| Embodiment 8 | 98 | 0.8 |
| Embodiment 9 | 100 | 0.9 |
| Embodiment 10 | 101 | 1.0 |
| Embodiment 11 | 105 | 0.8 |
| Embodiment 12 | 103 | 0.9 |
| Comparative examples 1 | 60 | 1.3 |
| Comparative examples 2 | 62 | 1.5 |
Nylon micro-sphere modified light-sensitive resin of the present invention has that shaping speed is fast, mechanical strength is high, good stability of the dimension etc. is excellent
Point.By the data of table one, the bending strength of product prepared by the 3D printing of nylon micro-sphere modified light-sensitive resin is up to
105MPa, more before modified photosensitive resin improve 75%；The shrinkage factor minimum 0.7% of product, more before modified photosensitive resin reduction
53%.In addition preparation technology is simple, can directly using and be extended to 3D printing field prepare with labyrinth part.
The above-mentioned description to embodiment is understood that for ease of those skilled in the art and using this hair
It is bright.Person skilled in the art obviously easily can make various modifications to these embodiments, and described herein
General Principle is applied in other embodiment without by performing creative labour.Therefore, the invention is not restricted to implementation here
Example, for those skilled in the art according to the announcement of the present invention, not departing from improvement that scope made and modification all should be
Within protection scope of the present invention.
Claims (10)
- A kind of 1. nylon micro-sphere modified light-sensitive resin, it is characterised in that：It is prepared by weight by following components：30~50 parts of acrylate,30~50 parts of epoxy resin,5~50 parts of nylon micro-sphere,0.1~5 part of the steady agent of light,20~30 parts of diluent,0.1~5 part of defoamer,0.1~5 part of levelling agent,0.1~5 part of antioxidant1~10 part of cationic initiators,1~10 part of free radical type Photoepolymerizationinitiater initiater,Described nylon micro-sphere is the microballoon of nylon 4 that particle diameter is 0.1~500 μm, the microballoon of nylon 6, the microballoon of nylon 7, nylon 8 microballoon Or the microballoon of nylon 12.
- A kind of 2. nylon micro-sphere modified light-sensitive resin according to claim 1, it is characterised in that：Described acrylate is At least one of epoxy monoacrylate, urethane acrylate and polyalcohol acrylate.
- A kind of 3. nylon micro-sphere modified light-sensitive resin according to claim 1, it is characterised in that：Described epoxy resin is At least one of phenol aldehyde type epoxy resin, bisphenol-s epoxy resin and aminoepoxy resin.
- A kind of 4. nylon micro-sphere modified light-sensitive resin according to claim 1, it is characterised in that：The steady agent of described light is 2, At least one of 4- benzophenonedicarboxylic acids, chlorination BTA or 2-hydroxy-4-n-octoxybenzophenone.
- A kind of 5. nylon micro-sphere modified light-sensitive resin according to claim 1, it is characterised in that：Described diluent is three Hydroxymethyl-propane triacrylate, ethoxyquin trimethylolpropane trimethacrylate, ethylene glycol diglycidylether and 3 the third two At least one of alcohol diglycidyl ether.
- A kind of 6. nylon micro-sphere modified light-sensitive resin according to claim 1, it is characterised in that：Described defoamer is two At least one of methyl polysiloxane, ethylene oxide propylene oxide copolyether and polyether silicone；Described levelling agent is organosilicon-epoxide ethane copolymer, organosilicon-epoxide propane copolymer and dimethyl silicone polymer At least one of.
- A kind of 7. nylon micro-sphere modified light-sensitive resin according to claim 1, it is characterised in that：Described antioxidant is four (3,5- di-t-butyl -4- hydroxyls) benzenpropanoic acid pentaerythritol ester, three (2,4- di-t-butyls) phenyl-phosphites or N, N'- couples-(3- At least one of (3,5- di-tert-butyl-hydroxy phenyls) propiono) hexamethylene diamine.
- 8. a kind of nylon micro-sphere modified light-sensitive resin according to claim 1, it is characterised in that described cationic is drawn It is salt compounded of iodine or sulfonium salt to send out agent；Described free radical type Photoepolymerizationinitiater initiater is at least one in benzophenone, chlorinated diphenyl ketone and dimethoxybenzoin Kind.
- A kind of 9. preparation method of nylon micro-sphere modified light-sensitive resin as claimed in claim 1, it is characterised in that：Including following Step：（1）In the special glass there-necked flask equipped with agitator and condenser pipe, 30~50 parts of acrylate, asphalt mixtures modified by epoxy resin are sequentially added 30~50 parts of fat, 20~30 parts of diluent, 0.1~5 part of defoamer, 0.1~5 part of levelling agent, 1~10 part of cationic initiators With 1~10 part of free radical type Photoepolymerizationinitiater initiater, 50~80 DEG C are warming up to, 10~30min is stirred, obtains faint yellow homogeneous liquid Body；（2）0.1~5 part of 5~50 parts of nylon micro-sphere, 0.1~5 part of the steady agent of light and antioxidant, ultrasound point are added in aforesaid liquid 10min~30min is dissipated to uniform state, that is, obtains nylon micro-sphere modified light-sensitive resin.
- 10. nylon micro-sphere modified light-sensitive resin as claimed in claim 1 is in the application of 3D printing, it is characterised in that：Beaten in 3D Nylon micro-sphere modified light-sensitive resin is prepared into product on printing apparatus, its technological parameter is：5~15W of light source power, sweep speed 1000~3000mm/s, sintering thickness are 0.05~0.2mm.
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| CN106146752A (en) * | 2015-04-01 | 2016-11-23 | 合肥杰事杰新材料股份有限公司 | A kind of potassium titanate crystal whisker modified light-sensitive resin and preparation method thereof |
| CN106280284A (en) * | 2015-06-11 | 2017-01-04 | 合肥杰事杰新材料股份有限公司 | A kind of modified light-sensitive resin for rapid shaping and preparation method thereof |
| CN105176070A (en) * | 2015-09-16 | 2015-12-23 | 东莞深圳清华大学研究院创新中心 | Modified 3D printing material and preparation method thereof |
| CN107434891B (en) * | 2016-05-27 | 2019-10-22 | 中国科学院理化技术研究所 | A kind of nylon/polystyrene alloy microballoon and the preparation method and application thereof |
| CN106046648A (en) * | 2016-05-30 | 2016-10-26 | 南京禾宇化工有限公司 | Corrosion-resistant and high-temperature-resistant resin and preparing method thereof |
| CN108148355A (en) * | 2016-12-05 | 2018-06-12 | 合肥杰事杰新材料股份有限公司 | It is a kind of for nylon micro-sphere composite material of Stereolithography and preparation method thereof |
| CN107603201B (en) * | 2017-09-07 | 2021-02-26 | 金华造物新材料有限公司 | 3D printing photosensitive resin for precision casting of ornaments and dentistry |
| CN110845814A (en) * | 2018-07-24 | 2020-02-28 | 上海杰事杰新材料(集团)股份有限公司 | Nylon microsphere modified photocuring resin composite material for 3D printing and preparation method thereof |
| EP3768494B1 (en) * | 2018-08-01 | 2023-04-19 | Carbon, Inc. | Production of low density products by additive manufacturing |
| CN109777024B (en) * | 2019-01-08 | 2021-06-01 | 宁波浙创科技有限公司 | SLA elastic photosensitive resin for 3D printing and preparation method thereof |
| CN111978479B (en) * | 2020-08-11 | 2021-11-12 | 珠海赛纳三维科技有限公司 | Material for three-dimensional molding, three-dimensional object, and sliced layer thereof |
| CN113185653A (en) * | 2021-06-17 | 2021-07-30 | 江西金石三维智能制造科技有限公司 | High-strength high-toughness three-dimensional photo-molding resin and preparation method thereof |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101481492A (en) * | 2009-02-12 | 2009-07-15 | 浙江工业大学 | UV curing photosensitive resin for rapid moulding injection mold |
| CN102311637A (en) * | 2010-07-01 | 2012-01-11 | 湖南华曙高科技有限责任公司 | Nylon composite material used for selective laser sintering and preparation method thereof |
| CN102337021A (en) * | 2010-07-29 | 2012-02-01 | 湖南华曙高科技有限责任公司 | Nylon composite powder material for selective laser sintering |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE102005002930A1 (en) * | 2005-01-21 | 2006-07-27 | Degussa Ag | Polymer powder with polyamide, use in a molding process and molding, made from this polymer powder |
-
2013
- 2013-06-26 CN CN201310259644.8A patent/CN104250436B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101481492A (en) * | 2009-02-12 | 2009-07-15 | 浙江工业大学 | UV curing photosensitive resin for rapid moulding injection mold |
| CN102311637A (en) * | 2010-07-01 | 2012-01-11 | 湖南华曙高科技有限责任公司 | Nylon composite material used for selective laser sintering and preparation method thereof |
| CN102337021A (en) * | 2010-07-29 | 2012-02-01 | 湖南华曙高科技有限责任公司 | Nylon composite powder material for selective laser sintering |
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Effective date of registration: 20220811 Address after: 241200 Chungu 3D Printing Industrial Park, Fanchang Economic Development Zone, Wuhu City, Anhui Province Patentee after: Wuhu Weiqiu New Material Technology Co., Ltd. Address before: 230601 No. 2388 Lianhua Road, Hefei economic and Technological Development Zone, Anhui, China Patentee before: HEFEI GENIUS NEW MATERIALS Co.,Ltd. |