CN109867755A - A kind of photosensitive resin preparation method suitable for 3 D-printing - Google Patents
A kind of photosensitive resin preparation method suitable for 3 D-printing Download PDFInfo
- Publication number
- CN109867755A CN109867755A CN201910131971.2A CN201910131971A CN109867755A CN 109867755 A CN109867755 A CN 109867755A CN 201910131971 A CN201910131971 A CN 201910131971A CN 109867755 A CN109867755 A CN 109867755A
- Authority
- CN
- China
- Prior art keywords
- photosensitive resin
- printing
- diacrylate
- resin preparation
- viscosity
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
Abstract
The present invention discloses a kind of photosensitive resin suitable for 3 D-printing, each component including following mass percentage: the glycidyl methacrylate of 40~85wt.%, the bisphenol A modified epoxy acrylate of 2~20wt.%, the fumed silica of 0~2.5wt.%, the tripropylene glycol diacrylate of 2~20wt.%, the cycloaliphatic epoxy resin of 0.5~5wt.%, the 1 of 0.5~5wt.%, 4- cyclohexane dimethanol divinyl ether, the polypropylene glycol diglycidyl ether diacrylate of 0.5~5wt.%, the radical initiator of 0.1~12wt.%, the reactive diluent of 1~10wt.%, the dispersing agent of 0.1~6wt.%.The photosensitive resin may be directly applied to 3 D-printing and complicated product be made, and elasticity is good, and smell is small, and reactivity is high, and forming speed is fast, and obtained product is fully cured that rear cubical contraction is small, and forming precision is high.
Description
Technical field
The invention belongs to the technical fields of 3 D-printing material, and in particular to a kind of photosensitive resin system suitable for 3 D-printing
Preparation Method.
Background technique
Three-dimensional fast shaping printing abbreviation 3D printing refers to also referred to as increasing material manufacturing by the three-dimensional mould of the product of needs
Type file carries out layering discrete processes by 3D printing equipment, and consumptive material is not both 3 D-printing and the maximum area of traditional prints
Not, the main consumptive material of conventional printer is Mo Hezhi, and 3 D-printing consumptive material is then miscellaneous resin, metal etc., root
It is selected, and is needed by specially treated according to 3D printing equipment and technique, this requires selected materials with excellent
Processing performance, especially to reduce the buckling deformation of material, dimensional contraction in process, curl degree etc., to keep
High precision.Therefore, current 3 D-printing material has become the matter of utmost importance of limitation 3 D-printing development.Wherein, light
Solidify the one kind of 3 D-printing (SLA) as 3 D-printing forming technique, base of the resinous material as photocuring 3 D-printing
This material is the developing research direction of current three-dimensional printing technology.
Photosensitive resin is similar to paint, after hardening, is similar to engineering plastics, is a kind of environmentally protective curing materials,
Have many advantages, such as environmental-friendly, energy consumption less, quick solidifying, precision are high, cured product performance is excellent, be widely used in jewelry and set
The industries such as meter, building, medical instrument, automobile, aerospace.Since photosensitive resin does not need the processing technologys such as heating, high pressure, and
It is to form preset model by being layering, therefore can have the defects that matter is crisp, poor mechanical property is extensive to limit it
Using.Based on this, domestic and foreign scholars are modified by mechanical property of the methods of the activeness and quietness to photosensitive resin material.
ZL201410074336.2 discloses free radical and causes allyl ester resin composite glass fiber photosensitive resin, and obtained light is solid
Changing material has good intensity and rigidity, but content of glass fiber is excessively high to be made dispersing unevenly in its resin, and hard
And crisp also it is unfavorable for large-scale promotion；201610237237.0 disclosing prepolymer resin is the 3 D-printing that raw material is prepared
Material, the cure shrinkage of material is small, forming precision is high.
In order to improve 3 D-printing photosensitive resin material flexibility, expands the application field of photosensitive resin material, develop
Curing rate is fast, shrinking percentage is small, color inhibition, the 3 D-printing photosensitive resin material that elasticity is good become era development must
It asks.
Summary of the invention
For this purpose, technical problem to be solved by the present invention lies in overcome existing photo-curing material viscosity is high, curing rate is slow,
The technical bottlenecks such as shrinking percentage is big, develop that a kind of curing rate is fast, shrinking percentage is small, color inhibition, elasticity is good for 3 D-printing
Photosensitive resin and preparation method thereof.
The purpose of the present invention is what is be achieved through the following technical solutions:
In order to solve the above technical problems, the present invention provides a kind of photosensitive resin suitable for 3 D-printing, by weight percentage
Meter, the photosensitive resin include following components:
Preferably, the blue light that the light source for solidifying the photosensitive resin is 300~650nm of wavelength.
Preferably, the degree of functionality of the glycidyl methacrylate is 2~4, under room temperature viscosity be 600~
1000cps, glass transition temperature are 40~60 DEG C.
Preferably, the degree of functionality of the bisphenol A modified epoxy acrylate is 1~3, under room temperature viscosity be 2500~
3500cps, glass transition temperature are 27~37 DEG C.
Preferably, the degree of functionality of the tripropylene glycol diacrylate is 1.5~3.5, under room temperature viscosity be 700~
1700cps, glass transition temperature are 35~45 DEG C.
Preferably, the degree of functionality of the cycloaliphatic epoxy resin is 1~3, and viscosity is 600~1200cps, glass under room temperature
Changing transition temperature is 30~50 DEG C.
Preferably, the Isosorbide-5-Nitrae-cyclohexane dimethanol divinyl ether degree of functionality is 2~4, and viscosity is 1000 under room temperature
~1600cps, glass transition temperature are 30~40 DEG C.
Preferably, the degree of functionality of the polypropylene glycol diglycidyl ether diacrylate is 1~3, and viscosity is under room temperature
1400~2000cps, glass transition temperature are 25~35 DEG C.
Preferably, the room temperature is 15~35 DEG C.
Preferably, the radical initiator be camphorquinone, dimethoxybenzoin, fluorinated diphenyl titanium cyclopentadienyl, benzophenone,
At least one of dicumyl peroxide decane acid esters, 2- methyl -2- hydroxyl-alpha-naphthalene acetone.
Preferably, the reactive diluent is iso-bornyl acrylate, tripropylene glycol diacrylate, trihydroxy methyl third
At least one of alkane triacrylate.
Preferably, the dispersing agent is naphthalene sulfonic acids base, amino modified block copolymer, polybasic carboxylic acid based block copolymer
At least one of.
The invention also discloses the preparation methods for the photosensitive resin for being suitable for 3 D-printing described in any one, which is characterized in that
The method are as follows:
A, in the reaction kettle equipped with blender, thermometer, condenser and charging spout, Glycidyl methacrylate is sequentially added
Glyceride, bisphenol A modified epoxy acrylate, tripropylene glycol diacrylate, cycloaliphatic epoxy resin, Isosorbide-5-Nitrae-cyclohexyl diformazan
Alcohol divinyl ether, polypropylene glycol diglycidyl ether diacrylate and reactive diluent, 10~40min of uniform stirring, side
Mixing marginal not enters fumed silica；
B, dispersing agent, 10~50min of uniform stirring in a kettle, is added；
C, toward radical initiator is added inside reaction kettle, temperature of reaction kettle is 40~80 DEG C, low whipping speed is 40~
10~30min is stirred under the conditions of 120 revs/min, is stopped stirring after the transparent color of solution, can be as based on the cured light of blue light
Quick resin.
Photosensitive resin produced by the present invention may be directly applied to 3 D-printing and complicated product be made, and elasticity is good, gas
Taste is small, and reactivity is high, and forming speed is fast, and obtained product small, the forming precision that is fully cured rear cubical contraction
It is high.
Preferably, mixing marginal not enters fumed silica while stirring in step.
Compared with prior art, the present invention have it is following the utility model has the advantages that
(1) photosensitive resin of the invention is in use because generating ozone with blue light illumination, will not skin ambustion,
Reduction is injured caused by human eye, is avoided using violet exposure bring security risk, has been promoted 3 D-printing in daily life
Application in work；
(2) present invention uses the glycidyl methacrylate of low viscosity, bisphenol A modified epoxy acrylate, 3 third
Omega-diol diacrylate, cycloaliphatic epoxy resin, Isosorbide-5-Nitrae-cyclohexane dimethanol divinyl ether, polypropylene glycol diglycidyl ether
Diacrylate is oligomer, keeps photosensitive resin viscosity of the invention low, and molding is fast, has ensured the Quick-forming of three-dimensional objects
Property；
(3) cubical contraction of photosensitive resin of the invention realizes extremely low cubical contraction 2.0% or so,
So that larger deformation will not occur in use because of contraction for 3 D-printing product, produced for obtaining high-precision printing
Product are most important, conducive to the holding of shape of product.
Specific embodiment
The present invention is described in detail combined with specific embodiments below.Following embodiment will be helpful to the technology of this field
Personnel further understand the present invention, but the invention is not limited in any way.It should be pointed out that the ordinary skill of this field
For personnel, without departing from the inventive concept of the premise, various modifications and improvements can be made.These belong to the present invention
Protection scope.
Following embodiment provides a kind of photosensitive resin for 3 D-printing, and the photosensitive resin includes following weight hundred
Divide the component of content:
The blue light that light source for solidifying the photosensitive resin is 300~650nm of wavelength.
The degree of functionality of the glycidyl methacrylate is 2~4, and viscosity is 600~1000cps, glass under room temperature
Changing transition temperature is 40~60 DEG C.
The degree of functionality of the bisphenol A modified epoxy acrylate is 1~3, and viscosity is 2500~3500cps, glass under room temperature
Glass transition temperature is 27~37 DEG C.
The degree of functionality of the tripropylene glycol diacrylate is 1.5~3.5, and viscosity is 700~1700cps, glass under room temperature
Glass transition temperature is 35~45 DEG C.
The degree of functionality of the cycloaliphatic epoxy resin is 1~3, and viscosity is 600~1200cps, glass transition under room temperature
Temperature is 30~50 DEG C.
The Isosorbide-5-Nitrae-cyclohexane dimethanol divinyl ether degree of functionality is 2~4, under room temperature viscosity be 1000~
1600cps, glass transition temperature are 30~40 DEG C.
The degree of functionality of the polypropylene glycol diglycidyl ether diacrylate is 1~3, under room temperature viscosity be 1400~
2000cps, glass transition temperature are 25~35 DEG C.
The radical initiator is camphorquinone, dimethoxybenzoin, fluorinated diphenyl titanium cyclopentadienyl, benzophenone, peroxidating
At least one of isopropylbenzene decane acid esters, 2- methyl -2- hydroxyl-alpha-naphthalene acetone.
The reactive diluent is iso-bornyl acrylate, tripropylene glycol diacrylate, trimethylolpropane tris third
At least one of olefin(e) acid ester.
The dispersing agent be naphthalene sulfonic acids base, amino modified block copolymer, in polybasic carboxylic acid based block copolymer extremely
Few one kind.
Embodiment 1
Present embodiments provide the photosensitive resin for 3 D-printing, component and mass percent are as follows: the first of 40wt.%
Base glycidyl acrylate, the bisphenol A modified epoxy acrylate of 20wt.%, the fumed silica of 2.5wt.%,
The tripropylene glycol diacrylate of 10wt.%, the cycloaliphatic epoxy resin of 5wt.%, Isosorbide-5-Nitrae-cyclohexane dimethanol of 5wt.%
Divinyl ether, the polypropylene glycol diglycidyl ether diacrylate of 5wt.%, the radical initiator of 6wt.%, 5wt.%
Reactive diluent, the dispersing agent of 1.5wt.%.
Preparation method:
A, in the reaction kettle equipped with blender, thermometer, condenser and charging spout, Glycidyl methacrylate is sequentially added
Glyceride, bisphenol A modified epoxy acrylate, tripropylene glycol diacrylate, cycloaliphatic epoxy resin, Isosorbide-5-Nitrae-cyclohexyl diformazan
Alcohol divinyl ether, polypropylene glycol diglycidyl ether diacrylate and reactive diluent, uniform stirring 10min, side mixing
Marginal not enters fumed silica；
B, dispersing agent, uniform stirring 10min in a kettle, is added；
C, toward addition radical initiator inside reaction kettle, temperature of reaction kettle is 40 DEG C, and low whipping speed is 40 revs/min
Under the conditions of stir 30min, after the transparent color of solution stop stirring, can as be based on the cured photosensitive resin of blue light.
The blue light that light source for solidifying the photosensitive resin is wavelength 300nm.
Embodiment 2
Present embodiments provide the photosensitive resin for 3 D-printing, component and mass percent are as follows: the first of 85wt.%
Base glycidyl acrylate, the bisphenol A modified epoxy acrylate of 2wt.%, the tripropylene glycol diacrylate of 2wt.%,
The cycloaliphatic epoxy resin of 0.5wt.%, Isosorbide-5-Nitrae-cyclohexane dimethanol divinyl ether of 0.5wt.%, poly- the third of 0.5wt.%
Hexanediol diglycidyl ether diacrylate, the radical initiator of 3wt.%, the reactive diluent of 5wt.%, 1.5wt.%
Dispersing agent.
Preparation method:
A, in the reaction kettle equipped with blender, thermometer, condenser and charging spout, Glycidyl methacrylate is sequentially added
Glyceride, bisphenol A modified epoxy acrylate, tripropylene glycol diacrylate, cycloaliphatic epoxy resin, Isosorbide-5-Nitrae-cyclohexyl diformazan
Alcohol divinyl ether, polypropylene glycol diglycidyl ether diacrylate and reactive diluent, uniform stirring 40min；
B, dispersing agent, uniform stirring 50min in a kettle, is added；
C, toward addition radical initiator inside reaction kettle, temperature of reaction kettle is 80 DEG C, and low whipping speed is 120 revs/min
Under the conditions of stir 10min, after the transparent color of solution stop stirring, can as be based on the cured photosensitive resin of blue light.
The blue light that light source for solidifying the photosensitive resin is wavelength 650nm.
Embodiment 3
Present embodiments provide the photosensitive resin for 3 D-printing, component and mass percent are as follows: the first of 40wt.%
Base glycidyl acrylate, the bisphenol A modified epoxy acrylate of 10wt.%, the fumed silica of 1.5wt.%,
The tripropylene glycol diacrylate of 20wt.%, the cycloaliphatic epoxy resin of 5wt.%, Isosorbide-5-Nitrae-cyclohexane dimethanol of 5wt.%
Divinyl ether, the polypropylene glycol diglycidyl ether diacrylate of 2.4wt.%, the radical initiator of 6wt.%,
The reactive diluent of 10wt.%, the dispersing agent of 0.1wt.%.
Preparation method:
A, in the reaction kettle equipped with blender, thermometer, condenser and charging spout, Glycidyl methacrylate is sequentially added
Glyceride, bisphenol A modified epoxy acrylate, tripropylene glycol diacrylate, cycloaliphatic epoxy resin, Isosorbide-5-Nitrae-cyclohexyl diformazan
Alcohol divinyl ether, polypropylene glycol diglycidyl ether diacrylate and reactive diluent, uniform stirring 20min, side mixing
Marginal not enters fumed silica；
B, dispersing agent, uniform stirring 25min in a kettle, is added；
C, toward addition radical initiator inside reaction kettle, temperature of reaction kettle is 50 DEG C, and low whipping speed is 80 revs/min
Under the conditions of stir 20min, after the transparent color of solution stop stirring, can as be based on the cured photosensitive resin of blue light.
The blue light that light source for solidifying the photosensitive resin is wavelength 400nm.
Embodiment 4
Present embodiments provide the photosensitive resin for 3 D-printing, component and mass percent are as follows: the first of 40wt.%
Base glycidyl acrylate, the bisphenol A modified epoxy acrylate of 10wt.%, the fumed silica of 2.5wt.%,
The tripropylene glycol diacrylate of 20wt.%, the cycloaliphatic epoxy resin of 2.5wt.%, Isosorbide-5-Nitrae-cyclohexyl diformazan of 3.5wt.%
Alcohol divinyl ether, the polypropylene glycol diglycidyl ether diacrylate of 2.5wt.%, the radical initiator of 12wt.%,
The reactive diluent of 1wt.%, the dispersing agent of 6wt.%.
Preparation method:
A, in the reaction kettle equipped with blender, thermometer, condenser and charging spout, Glycidyl methacrylate is sequentially added
Glyceride, bisphenol A modified epoxy acrylate, tripropylene glycol diacrylate, cycloaliphatic epoxy resin, Isosorbide-5-Nitrae-cyclohexyl diformazan
Alcohol divinyl ether, polypropylene glycol diglycidyl ether diacrylate and reactive diluent, uniform stirring 30min, side mixing
Marginal not enters fumed silica；
B, dispersing agent, uniform stirring 30min in a kettle, is added；
C, toward addition radical initiator inside reaction kettle, temperature of reaction kettle is 60 DEG C, and low whipping speed is 60 revs/min
Under the conditions of stir 20min, after the transparent color of solution stop stirring, can as be based on the cured photosensitive resin of blue light.
The blue light that light source for solidifying the photosensitive resin is wavelength 450nm.
Embodiment 5
Present embodiments provide the photosensitive resin for 3 D-printing, component and mass percent are as follows: the first of 60wt.%
Base glycidyl acrylate, the bisphenol A modified epoxy acrylate of 13.5wt.%, the fumed silica of 2wt.%,
The tripropylene glycol diacrylate of 10wt.%, the cycloaliphatic epoxy resin of 2wt.%, Isosorbide-5-Nitrae-cyclohexane dimethanol of 2wt.%
Divinyl ether, the polypropylene glycol diglycidyl ether diacrylate of 2.4wt.%, the radical initiator of 0.1wt.%,
The reactive diluent of 5wt.%, the dispersing agent of 3wt.%.
Preparation method:
A, in the reaction kettle equipped with blender, thermometer, condenser and charging spout, Glycidyl methacrylate is sequentially added
Glyceride, bisphenol A modified epoxy acrylate, tripropylene glycol diacrylate, cycloaliphatic epoxy resin, Isosorbide-5-Nitrae-cyclohexyl diformazan
Alcohol divinyl ether, polypropylene glycol diglycidyl ether diacrylate and reactive diluent, uniform stirring 30min, side mixing
Marginal not enters fumed silica；
B, dispersing agent, uniform stirring 40min in a kettle, is added；
C, toward addition radical initiator inside reaction kettle, temperature of reaction kettle is 70 DEG C, and low whipping speed is 80 revs/min
Under the conditions of stir 10min, after the transparent color of solution stop stirring, can as be based on the cured photosensitive resin of blue light.
The blue light that light source for solidifying the photosensitive resin is wavelength 500nm.
Embodiment 6
Present embodiments provide the photosensitive resin for 3 D-printing, component and mass percent are as follows: the first of 50wt.%
Base glycidyl acrylate, the bisphenol A modified epoxy acrylate of 16wt.%, the fumed silica of 1wt.%,
The tripropylene glycol diacrylate of 16wt.%, the cycloaliphatic epoxy resin of 3wt.%, Isosorbide-5-Nitrae-cyclohexyl diformazan of 0.5wt.%
Alcohol divinyl ether, the polypropylene glycol diglycidyl ether diacrylate of 5wt.%, the radical initiator of 2wt.%,
The reactive diluent of 4.5wt.%, the dispersing agent of 2wt.%.
Preparation method:
A, in the reaction kettle equipped with blender, thermometer, condenser and charging spout, Glycidyl methacrylate is sequentially added
Glyceride, bisphenol A modified epoxy acrylate, tripropylene glycol diacrylate, cycloaliphatic epoxy resin, Isosorbide-5-Nitrae-cyclohexyl diformazan
Alcohol divinyl ether, polypropylene glycol diglycidyl ether diacrylate and reactive diluent, uniform stirring 30min, side mixing
Marginal not enters fumed silica；
B, dispersing agent, uniform stirring 40min in a kettle, is added；
C, toward addition radical initiator inside reaction kettle, temperature of reaction kettle is 40 DEG C, and low whipping speed is 40 revs/min
Under the conditions of stir 30min, after the transparent color of solution stop stirring, can as be based on the cured photosensitive resin of blue light.
The blue light that light source for solidifying the photosensitive resin is wavelength 550nm.
Embodiment 7
Present embodiments provide the photosensitive resin for 3 D-printing, component and mass percent are as follows: the first of 70wt.%
Base glycidyl acrylate, the bisphenol A modified epoxy acrylate of 8wt.%, the fumed silica of 0.5wt.%,
The tripropylene glycol diacrylate of 10wt.%, the cycloaliphatic epoxy resin of 4wt.%, Isosorbide-5-Nitrae-cyclohexyl diformazan of 0.5wt.%
Alcohol divinyl ether, the polypropylene glycol diglycidyl ether diacrylate of 1wt.%, the radical initiator of 2wt.%,
The reactive diluent of 3wt.%, the dispersing agent of 1wt.%.
Preparation method:
A, in the reaction kettle equipped with blender, thermometer, condenser and charging spout, Glycidyl methacrylate is sequentially added
Glyceride, bisphenol A modified epoxy acrylate, tripropylene glycol diacrylate, cycloaliphatic epoxy resin, Isosorbide-5-Nitrae-cyclohexyl diformazan
Alcohol divinyl ether, polypropylene glycol diglycidyl ether diacrylate and reactive diluent, uniform stirring 40min, side mixing
Marginal not enters fumed silica；
B, dispersing agent, uniform stirring 50min in a kettle, is added；
C, toward addition radical initiator inside reaction kettle, temperature of reaction kettle is 80 DEG C, and low whipping speed is 120 revs/min
Under the conditions of stir 10min, after the transparent color of solution stop stirring, can as be based on the cured photosensitive resin of blue light.
The blue light that light source for solidifying the photosensitive resin is wavelength 600nm.
Embodiment 8
Present embodiments provide the photosensitive resin for 3 D-printing, component and mass percent are as follows: the first of 40wt.%
Base glycidyl acrylate, the bisphenol A modified epoxy acrylate of 20wt.%, the fumed silica of 2.5wt.%,
The tripropylene glycol diacrylate of 20wt.%, the cycloaliphatic epoxy resin of 1.5wt.%, Isosorbide-5-Nitrae-cyclohexyl diformazan of 2.5wt.%
Alcohol divinyl ether, the polypropylene glycol diglycidyl ether diacrylate of 5wt.%, the radical initiator of 2wt.%,
The reactive diluent of 4.5wt.%, the dispersing agent of 2wt.%.
Preparation method:
A, in the reaction kettle equipped with blender, thermometer, condenser and charging spout, Glycidyl methacrylate is sequentially added
Glyceride, bisphenol A modified epoxy acrylate, tripropylene glycol diacrylate, cycloaliphatic epoxy resin, Isosorbide-5-Nitrae-cyclohexyl diformazan
Alcohol divinyl ether, polypropylene glycol diglycidyl ether diacrylate and reactive diluent, uniform stirring 10min, side mixing
Marginal not enters fumed silica；
B, dispersing agent, uniform stirring 10min in a kettle, is added；
C, toward addition radical initiator inside reaction kettle, temperature of reaction kettle is 40 DEG C, and low whipping speed is 40 revs/min
Under the conditions of stir 30min, after the transparent color of solution stop stirring, can as be based on the cured photosensitive resin of blue light.
The blue light that light source for solidifying the photosensitive resin is wavelength 650nm.
The each component mass percentage of photosensitive resin described in embodiment 1-8 for 3 D-printing is as shown in table 1.
The mass percentage of each component in 1 embodiment of table
Comparative example 1
This comparative example provides a kind of 3 D-printing blue light curing photosensitive resin, component and content as shown in table 2,
Preparation method is same as Example 1.
Comparative example 2
This comparative example provides a kind of 3 D-printing blue light curing photosensitive resin, component and content as shown in table 2,
Preparation method is same as Example 1.
Comparative example 3
Comparative example 3 provides a kind of 3 D-printing blue light curing photosensitive resin, component and content as shown in table 2,
Preparation method is same as Example 4.
Comparative example 4
This comparative example provides a kind of 3 D-printing blue light curing photosensitive resin, component and content as shown in table 2,
Preparation method is same as Example 5.
Comparative example 5
This comparative example provides a kind of 3 D-printing blue light curing photosensitive resin, component and content as shown in table 2,
Preparation method is same as Example 6.
Comparative example 6
This comparative example provides a kind of 3 D-printing blue light curing photosensitive resin, component and content as shown in table 2,
Preparation method is same as Example 6.
The mass percentage of each component in 2 embodiment of table
Compliance test result:
Photo-curing material prepared by embodiment and comparative example is placed in three-dimensional printer and carries out printing test, three-dimensional is beaten
The performance of print photocuring solid material and shaped article is tested, and test result is as shown in table 3:
Table 3
There are many concrete application approach of the present invention, the above is only a preferred embodiment of the present invention.More than it should be pointed out that
Embodiment is merely to illustrate the present invention, and the protection scope being not intended to restrict the invention.For the common skill of the art
For art personnel, without departing from the principle of the present invention, several improvement can also be made, these improvement also should be regarded as this hair
Bright protection scope.
Claims (10)
1. a kind of photosensitive resin preparation method suitable for 3 D-printing, which is characterized in that the photosensitive resin includes following weight
The each component of percentage composition:
Glycidyl methacrylate 40~85%；
Bisphenol A modified epoxy acrylate 2~20%；
Fumed silica 0~2.5%；
Tripropylene glycol diacrylate 2~20%；
Cycloaliphatic epoxy resin 0.5~5%；
Isosorbide-5-Nitrae-cyclohexane dimethanol divinyl ether 0.5~5%；
Polypropylene glycol diglycidyl ether diacrylate 0.5~5%；
Radical initiator 0.1~12%；
Reactive diluent 1~10%；
Dispersing agent 0.1~6%.
2. being suitable for the photosensitive resin preparation method of 3 D-printing as described in claim 1, which is characterized in that the photosensitive resin
Light source be 300~650nm of wavelength blue light.
3. being suitable for the photosensitive resin preparation method of 3 D-printing as described in claim 1, which is characterized in that the metering system
The degree of functionality of acid glycidyl ester is 2~4, and viscosity is 600~1000cps under room temperature, and glass transition temperature is 40~60 DEG C；
The degree of functionality of the bisphenol A modified epoxy acrylate is 1~3, and viscosity is 2500~3500cps, glass transition under room temperature
Temperature is 27~37 DEG C.
4. being suitable for the photosensitive resin preparation method of 3 D-printing as described in claim 1, which is characterized in that the tripropylene glycol
The degree of functionality of diacrylate is 1.5~3.5, and viscosity is 700~1700cps under room temperature, and glass transition temperature is 35~45
℃；The degree of functionality of the cycloaliphatic epoxy resin is 1~3, and viscosity is 600~1200cps under room temperature, and glass transition temperature is
30~50 DEG C.
5. being suitable for the photosensitive resin preparation method of 3 D-printing as described in claim 1, which is characterized in that the Isosorbide-5-Nitrae-hexamethylene
The degree of functionality of base dimethanol divinyl ether is 2~4, and viscosity is 1000~1600cps, glass transition temperature 30 under room temperature
~40 DEG C；The degree of functionality of the polypropylene glycol diglycidyl ether diacrylate is 1~3, under room temperature viscosity be 1400~
2000cps, glass transition temperature are 25~35 DEG C.
6. being suitable for the photosensitive resin preparation method of 3 D-printing as described in claim 1, which is characterized in that the free radical draws
Hair agent is camphorquinone, dimethoxybenzoin, fluorinated diphenyl titanium cyclopentadienyl, benzophenone, dicumyl peroxide decane acid esters, 2- first
At least one of base -2- hydroxyl-alpha-naphthalene acetone.
7. being suitable for the photosensitive resin preparation method of 3 D-printing as described in claim 1, which is characterized in that the activity dilution
Agent is at least one of iso-bornyl acrylate, tripropylene glycol diacrylate, trimethylolpropane trimethacrylate.
8. being suitable for the photosensitive resin preparation method of 3 D-printing as described in claim 1, which is characterized in that the dispersing agent is
At least one of naphthalene sulfonic acids base, amino modified block copolymer, polybasic carboxylic acid based block copolymer.
9. a kind of such as the described in any item photosensitive resin preparation methods suitable for 3 D-printing of claim 1-8, which is characterized in that
The following steps are included:
A, in the reaction kettle equipped with blender, thermometer, condenser and charging spout, methyl propenoic acid glycidyl is sequentially added
Ester, bisphenol A modified epoxy acrylate, tripropylene glycol diacrylate, cycloaliphatic epoxy resin, Isosorbide-5-Nitrae-cyclohexane dimethanol two
Vinyl ethers, polypropylene glycol diglycidyl ether diacrylate and reactive diluent, 10~40min of uniform stirring；
B, dispersing agent, 10~50min of uniform stirring in a kettle, is added；
C, toward addition radical initiator inside reaction kettle, temperature of reaction kettle is 40~80 DEG C, and low whipping speed is 40~120
10~30min is stirred under the conditions of rev/min, can as be based on the cured photosensitive resin of blue light.
10. a kind of photosensitive resin preparation method for being suitable for 3 D-printing as claimed in claim 9, which is characterized in that in step A
In mix marginal not while stirring and enter fumed silica.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910131971.2A CN109867755A (en) | 2019-02-22 | 2019-02-22 | A kind of photosensitive resin preparation method suitable for 3 D-printing |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910131971.2A CN109867755A (en) | 2019-02-22 | 2019-02-22 | A kind of photosensitive resin preparation method suitable for 3 D-printing |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN109867755A true CN109867755A (en) | 2019-06-11 |
Family
ID=66919032
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201910131971.2A Pending CN109867755A (en) | 2019-02-22 | 2019-02-22 | A kind of photosensitive resin preparation method suitable for 3 D-printing |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN109867755A (en) |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103755889A (en) * | 2014-01-10 | 2014-04-30 | 上海那恒新材料有限公司 | Light-emitting high precision three-dimensionally moulded photosensitive resin composition |
| WO2016108519A1 (en) * | 2014-12-29 | 2016-07-07 | Samsung Electronics Co., Ltd. | Ink compositions for 3d printing, 3d printer and method for controlling of the same |
| CN108690328A (en) * | 2018-05-29 | 2018-10-23 | 上海云铸三维科技有限公司 | A kind of photosensitive resin and preparation method thereof for 3D printing |
| CN108690327A (en) * | 2018-05-29 | 2018-10-23 | 上海云铸三维科技有限公司 | A kind of 3D printing UV curing photosensitive resin and preparation method thereof |
-
2019
- 2019-02-22 CN CN201910131971.2A patent/CN109867755A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103755889A (en) * | 2014-01-10 | 2014-04-30 | 上海那恒新材料有限公司 | Light-emitting high precision three-dimensionally moulded photosensitive resin composition |
| WO2016108519A1 (en) * | 2014-12-29 | 2016-07-07 | Samsung Electronics Co., Ltd. | Ink compositions for 3d printing, 3d printer and method for controlling of the same |
| CN108690328A (en) * | 2018-05-29 | 2018-10-23 | 上海云铸三维科技有限公司 | A kind of photosensitive resin and preparation method thereof for 3D printing |
| CN108690327A (en) * | 2018-05-29 | 2018-10-23 | 上海云铸三维科技有限公司 | A kind of 3D printing UV curing photosensitive resin and preparation method thereof |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN106243290B (en) | A kind of rubber-type photocuring 3D printing material and preparation method thereof | |
| CN105131581B (en) | For the moulder obtained by the photocurable liquid resin combination and its photocuring of 3 D stereo shaping | |
| CN108690327A (en) | A kind of 3D printing UV curing photosensitive resin and preparation method thereof | |
| CN104788625A (en) | Free radical photo-curing material for manufacturing flexographic plate as well as preparation method and application of photo-curing material | |
| CN104371488A (en) | Quick bonding repair method of ultraviolet-curing composite material | |
| CN104403268A (en) | Ultraviolet-curable resin composition and fiber reinforced resin-based composite material thereof | |
| CN109517340A (en) | A kind of transparent 3D printing photosensitive resin of heatproof | |
| CN109867756A (en) | A kind of 3 D-printing blue light curing photosensitive resin and preparation method thereof | |
| CN105404095A (en) | Washable ultraviolet laser curing and rapid prototyping photosensitive resin and preparation method thereof | |
| CN113583188A (en) | High-weather-resistance high-toughness photocuring material for laser 3D printing and preparation method thereof | |
| CN109867755A (en) | A kind of photosensitive resin preparation method suitable for 3 D-printing | |
| CN108690328A (en) | A kind of photosensitive resin and preparation method thereof for 3D printing | |
| CN109438631B (en) | High-precision and high-thermal-deformation-temperature stereolithography 3D printing photosensitive resin and preparation method thereof | |
| CN113881279A (en) | 3D printing shape memory epoxy resin ink, preparation method and application thereof, and 3D printing epoxy resin | |
| CN104762815A (en) | Method for grafting modification preparation of ultraviolet-resistant fiber or fabric | |
| CN112480293B (en) | Self-repairable or recyclable photocuring 3D printing part and preparation method and application thereof | |
| CN110628046B (en) | Method for preparing high-strength hydrogel based on tanning principle | |
| CN105400144B (en) | Pultrusion prepares light curing compound material, its preparation method and application | |
| CN108078789B (en) | Preparation method of multicolor integrated dental repair material | |
| CN104845441A (en) | Acid resistance type protective ink and preparation method thereof | |
| CN112480329A (en) | Light-cured resin model material based on DLP (digital light processing) type 3D printing and preparation method thereof | |
| CN106344969A (en) | Dental composite-resin high-strength fiber periodontal bundle band and preparation method thereof | |
| CN108047621A (en) | A kind of efficiency light triggering cures 3D printing material and preparation method thereof | |
| CN114213810A (en) | High-strength 3D printing photosensitive resin material | |
| CN101954769A (en) | Imitation marble and method for manufacturing bathroom equipment by using same |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| RJ01 | Rejection of invention patent application after publication | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20190611 |