CN108690328A - A kind of photosensitive resin and preparation method thereof for 3D printing - Google Patents
A kind of photosensitive resin and preparation method thereof for 3D printing Download PDFInfo
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- CN108690328A CN108690328A CN201810531545.3A CN201810531545A CN108690328A CN 108690328 A CN108690328 A CN 108690328A CN 201810531545 A CN201810531545 A CN 201810531545A CN 108690328 A CN108690328 A CN 108690328A
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- 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
- 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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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/02—Polymeric products of isocyanates or isothiocyanates of isocyanates or isothiocyanates only
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
- C08L2205/025—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group containing two or more polymers of the same hierarchy C08L, and differing only in parameters such as density, comonomer content, molecular weight, structure
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
- C08L2205/035—Polymer mixtures characterised by other features containing three or more polymers in a blend containing four or more polymers in a blend
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- Chemical Kinetics & Catalysis (AREA)
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- Engineering & Computer Science (AREA)
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Abstract
The present invention discloses a kind of photosensitive resin and preparation method thereof for 3D printing, and the photosensitive resin includes each component of following mass percentage:The cycloaliphatc glycidyl ester of 30~50wt.%, the bisphenol A type epoxy resin of 20~40wt.%, the aliphatic epoxy acrylate of 15~30wt.%, the polyurea monomers of 0~20wt.%, the polypropylene glycol diglycidyl ether diacrylate of 5~15wt.%, the initiator of 0.05~2wt.%, the reactive diluent of 5~20wt.%, the dispersant of 0.1~4wt.%, the levelling agent of 0.1~2wt.%.The photosensitive resin may be directly applied to 3D printing and be made complicated product, and elasticity is good, and color inhibition, 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 3D printing material, and in particular to a kind of photosensitive resin and its system for 3D printing
Preparation Method.
Background technology
It refers to the three-dimensional mould for the product that will be needed that three-dimensional fast shaping, which prints abbreviation 3D printing also referred to as increasing material manufacturing,
Type file carries out layering discrete processes by 3D printing equipment, and consumptive material is not both 3D printing and the maximum difference of traditional prints,
The main consumptive material of conventional printer is Mo Hezhi, and 3D printing consumptive material is then miscellaneous resin, metal etc., to be beaten according to 3D
Printing apparatus and technique are selected, and are needed by specially treated, and this requires selected materials to have excellent processability
Can, especially to reduce the buckling deformation of material, dimensional contraction in process, curl degree etc., to keep high precision.
Therefore, current 3D printing material has become the matter of utmost importance of limitation 3D printing development.Wherein, resinous material is as 3D
The basic material of printing is the developing research direction of current 3D printing technique.
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.Due to processing technologys such as photosensitive resin need not heat, high pressures, and
It is to form preset model by being layering, therefore can have that matter is crisp, defect of poor mechanical property is extensive to limit it
Using.Based on this, domestic and foreign scholars are modified the mechanical property of photosensitive resin material by the methods of activeness and quietness.
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 a rigidity, but content of glass fiber it is excessively high can make in its resin disperse it is uneven and hard
And crisp also it is unfavorable for large-scale promotion;201610237237.0 it is the 3D printing material that raw material is prepared to disclose prepolymer resin
Material, the cure shrinkage of material is small, forming precision is high.
In order to improve 3D printing photosensitive resin material flexibility, expand the application field of photosensitive resin material, exploitation is solid
Change that speed is fast, shrinking percentage is small, color inhibition, the good 3D printing of elasticity become the inevitable requirement of era development with photosensitive resin material.
Invention content
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 are good for 3D printing
Photosensitive resin and preparation method thereof.
The purpose of the present invention is what is be achieved through the following technical solutions:
The present invention provides a kind of photosensitive resin for 3D printing, the photosensitive resin includes following weight percentage
Component:
Preferably, the light source of the photosensitive resin is the ultraviolet light of 200~500nm of wavelength.
Preferably, the degree of functionality of the cycloaliphatc glycidyl ester is 1~3, and viscosity is 800~1000cps, glass under room temperature
Glass transition temperature is 43~47 DEG C.
Preferably, the degree of functionality of the bisphenol A type epoxy resin is 2~4, and viscosity is 3300~3700cps, glass under room temperature
Glass transition temperature is 34~38 DEG C.
Preferably, the degree of functionality of the aliphatic epoxy acrylate is 1~3, and viscosity is 800~1200cps under room temperature,
Glass transition temperature is 38~42 DEG C.
Preferably, the degree of functionality of the cycloaliphatc glycidyl ester is 1~3, and viscosity is 800~1000cps, glass under room temperature
Glass transition temperature is 43~47 DEG C.
Preferably, the viscosity of the polyurea monomers at normal temperatures is 3000~3400cps, and elongation at break is more than 400%;
The polyurea monomers are toluene di-isocyanate(TDI) modified polyurea monomer, and preparation method is as follows:Take toluene diisocyanate
Polyurea monomers are made with the acetone solvent of rear addition 30~60% in sodium hydroxide in acid esters after washing, dehydration, separation.
Preferably, the degree of functionality of the polypropylene glycol diglycidyl ether diacrylate is 1~3, and viscosity is under room temperature
1500~1900cps, glass transition temperature are 30~34 DEG C.
Preferably, the initiator is camphorquinone, dimethoxybenzoin, fluorinated diphenyl titanium cyclopentadienyl, benzophenone, peroxidating
At least one of isopropylbenzene decane acid esters, 2- methyl -2- hydroxyl-alphas-naphthalene acetone.
Preferably, the reactive diluent is iso-bornyl acrylate, tripropylene glycol class diacrylate, trihydroxy methyl
At least one of propane triacrylate.More preferable reactive diluent is the tripropylene glycol class diacrylate of 2 degrees of functionality.
Preferably, the dispersant is naphthalene sulfonic acids base, amino modified block copolymer, polybasic carboxylic acid based block copolymer
At least one of.
Preferably, the levelling agent is one kind in polyacrylate, polyether-modified dimethyl siloxane.
The present invention provides a kind of preparation methods of the photosensitive resin for 3D printing, the described method comprises the following steps:
A, in a kettle, be added cycloaliphatc glycidyl ester, bisphenol A type epoxy resin, aliphatic epoxy acrylate,
Polypropylene glycol diglycidyl ether diacrylate, polyurea monomers and reactive diluent, 5~30min of uniform stirring;
B, again in a kettle, dispersant, levelling agent, 5~40min of uniform stirring is added;
C, initiator is added in a kettle again, temperature of reaction kettle is 30~70 DEG C, is stopped after the transparent color of solution
Stirring is to get the photosensitive resin.
Photosensitive resin produced by the present invention may be directly applied to 3D printing and complicated product, elastic good, resistance to Huang be made
Become, smell is small, and reactivity is high, and forming speed is fast, and obtained product small, the molding essence that is fully cured rear cubical contraction
Density is high.
Compared with prior art, the present invention has following advantageous effect:
(1) present invention is shunk using the cycloaliphatc glycidyl ester, bisphenol A type epoxy resin and polypropylene glycol two of low viscosity
Glycerin ether diacrylate is oligomer, keeps the photosensitive resin viscosity of the present invention low, and molding is fast, has ensured the fast short-term training of 3D products
Shape;
(2) using DPGDA bifunctional as diluent, photosensitive resin of the present invention has higher reactivity and solidification
Speed;
(3) cubical contraction of photosensitive resin of the invention realizes extremely low cubical contraction 2.0% or so,
So that 3D printing product will not occur in use because of contraction compared with large deformation, for obtaining high-precision printed product
It is most important, it is conducive to the holding of shape of product.
Specific implementation mode
With reference to specific embodiment, the present invention is described in detail.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 domain.
Following embodiment provides a kind of photosensitive resin for 3D printing, and the photosensitive resin includes following weight percent
The component of content:
The light source of the photosensitive resin is the ultraviolet light of 200~500nm of wavelength.
The degree of functionality of the cycloaliphatc glycidyl ester is 1~3, and viscosity is 800~1000cps under room temperature, and vitrifying turns
Temperature is 43~47 DEG C.
The degree of functionality of the bisphenol A type epoxy resin is 2~4, and viscosity is 3300~3700cps under room temperature, and vitrifying turns
Temperature is 34~38 DEG C.
The degree of functionality of the aliphatic epoxy acrylate is 1~3, and viscosity is 800~1200cps, vitrifying under room temperature
Transition temperature is 38~42 DEG C.
The degree of functionality of the cycloaliphatc glycidyl ester is 1~3, and viscosity is 800~1000cps under room temperature, and vitrifying turns
Temperature is 43~47 DEG C.
The viscosity of the polyurea monomers at normal temperatures is 3000~3400cps, and elongation at break is more than 400%.
The preparation method of the polyurea monomers is as follows:Take toluene di-isocyanate(TDI), in sodium hydroxide and it is rear be added 30~
Polyurea monomers are made in 60% acetone solvent after washing, dehydration, separation.
The degree of functionality of the polypropylene glycol diglycidyl ether diacrylate is 1~3, under room temperature viscosity be 1500~
1900cps, glass transition temperature are 30~34 DEG C.
The initiator is camphorquinone, dimethoxybenzoin, fluorinated diphenyl titanium cyclopentadienyl, benzophenone, dicumyl peroxide
At least one of decane acid esters, 2- methyl -2- hydroxyl-alphas-naphthalene acetone.
The reactive diluent is iso-bornyl acrylate, tripropylene glycol class diacrylate, trimethylolpropane tris
At least one of acrylate.
The dispersant is naphthalene sulfonic acids base, amino modified block copolymer, in polybasic carboxylic acid based block copolymer extremely
Few one kind.
The levelling agent is one kind in polyacrylate, polyether-modified dimethyl siloxane.
Embodiment 1
The photosensitive resin for 3D printing is present embodiments provided, component and mass percent are:The alicyclic ring of 50wt.%
Race's ethylene oxidic ester, the bisphenol A type epoxy resin of 20wt.%, the aliphatic epoxy acrylate of 15wt.%, 2.8wt.%'s
The activity of polyurea monomers, the polypropylene glycol diglycidyl ether diacrylate of 5wt.%, the initiator of 2wt.%, 5wt.% is dilute
Release agent, the dispersant of 0.1wt.%, the levelling agent of 0.1wt.%.
Preparation method:
A, prepared by polyurea monomers:Toluene di-isocyanate(TDI) is taken, with the acetone solvent of rear addition 60% in sodium hydroxide, is passed through
Polyurea monomers are made after washing, dehydration, separation;
B, in the reaction kettle equipped with blender, thermometer, condenser and charging spout, addition cycloaliphatc glycidyl ester,
Bisphenol A type epoxy resin, aliphatic epoxy acrylate, polypropylene glycol diglycidyl ether diacrylate, polyurea monomers and
Reactive diluent, uniform stirring 5min;
C, in a kettle, dispersant, levelling agent, uniform stirring 5min is added;
D, it is 30 DEG C toward addition initiator, temperature of reaction kettle inside reaction kettle, stops stirring after the transparent color of solution.
The ultraviolet light that light source for curing the photosensitive resin is wavelength 200nm.
Embodiment 2
The photosensitive resin for 3D printing is present embodiments provided, component and mass percent are:The alicyclic ring of 30wt.%
Race's ethylene oxidic ester, the bisphenol A type epoxy resin of 20wt.%, the aliphatic epoxy acrylate of 15wt.%, 20wt.%'s is poly-
The activity of urea monomer, the polypropylene glycol diglycidyl ether diacrylate of 7.8wt.%, the initiator of 2wt.%, 5wt.% is dilute
Release agent, the dispersant of 0.1wt.%, the levelling agent of 0.1wt.%.
Preparation method:
A, prepared by polyurea monomers:Toluene di-isocyanate(TDI) is taken, with the acetone solvent of rear addition 30% in sodium hydroxide, is passed through
Polyurea monomers are made after washing, dehydration, separation;
B, in the reaction kettle equipped with blender, thermometer, condenser and charging spout, addition cycloaliphatc glycidyl ester,
Bisphenol A type epoxy resin, aliphatic epoxy acrylate, polypropylene glycol diglycidyl ether diacrylate, polyurea monomers and
Reactive diluent, uniform stirring 30min;
C, in a kettle, dispersant, levelling agent, uniform stirring 40min is added;
D, it is 70 DEG C toward addition initiator, temperature of reaction kettle inside reaction kettle, stops stirring after the transparent color of solution.
The ultraviolet light that light source for curing the photosensitive resin is wavelength 500nm.
Embodiment 3
The photosensitive resin for 3D printing is present embodiments provided, component and mass percent are:The alicyclic ring of 30wt.%
Race's ethylene oxidic ester, the bisphenol A type epoxy resin of 25wt.%, the aliphatic epoxy acrylate of 15wt.%, 2wt.%'s is poly-
The activity of urea monomer, the polypropylene glycol diglycidyl ether diacrylate of 15wt.%, the initiator of 2wt.%, 5wt.% is dilute
Release agent, the dispersant of 4wt.%, the levelling agent of 2wt.%.
Preparation method:
A, prepared by polyurea monomers:Toluene di-isocyanate(TDI) is taken, with the acetone solvent of rear addition 45% in sodium hydroxide, is passed through
Polyurea monomers are made after washing, dehydration, separation;
B, in the reaction kettle equipped with blender, thermometer, condenser and charging spout, addition cycloaliphatc glycidyl ester,
Bisphenol A type epoxy resin, aliphatic epoxy acrylate, polypropylene glycol diglycidyl ether diacrylate, polyurea monomers and
Reactive diluent, uniform stirring 15min;
C, in a kettle, dispersant, levelling agent, uniform stirring 20min is added;
D, it is 50 DEG C toward addition initiator, temperature of reaction kettle inside reaction kettle, stops stirring after the transparent color of solution.
The ultraviolet light that light source for curing the photosensitive resin is wavelength 350nm.
Embodiment 4
The photosensitive resin for 3D printing is present embodiments provided, component and mass percent are:The alicyclic ring of 30wt.%
Race's ethylene oxidic ester, the bisphenol A type epoxy resin of 20wt.%, the aliphatic epoxy acrylate of 30wt.%, 5wt.%'s is poly-
Propylene glycol diglycidylether diacrylate, the initiator of 2wt.%, the reactive diluent of 7wt.%, the dispersion of 4wt.%
Agent, the levelling agent of 2wt.%.
Preparation method:
A, in the reaction kettle equipped with blender, thermometer, condenser and charging spout, addition cycloaliphatc glycidyl ester,
Bisphenol A type epoxy resin, aliphatic epoxy acrylate, polypropylene glycol diglycidyl ether diacrylate, polyurea monomers and
Reactive diluent, uniform stirring 20min;
B, in a kettle, dispersant, levelling agent, uniform stirring 5min is added;
C, it is 70 DEG C toward addition initiator, temperature of reaction kettle inside reaction kettle, stops stirring after the transparent color of solution.
The ultraviolet light that light source for curing the photosensitive resin is wavelength 400nm.
Embodiment 5
The photosensitive resin for 3D printing is present embodiments provided, component and mass percent are:The alicyclic ring of 30wt.%
Race's ethylene oxidic ester, the bisphenol A type epoxy resin of 40wt.%, the aliphatic epoxy acrylate of 15wt.%, 5wt.%'s is poly-
Propylene glycol diglycidylether diacrylate, the initiator of 0.05wt.%, the reactive diluent of 5wt.%, point of 4wt.%
Powder, the levelling agent of 0.95wt.%.
Preparation method:
A, in the reaction kettle equipped with blender, thermometer, condenser and charging spout, addition cycloaliphatc glycidyl ester,
Bisphenol A type epoxy resin, aliphatic epoxy acrylate, polypropylene glycol diglycidyl ether diacrylate, polyurea monomers and
Reactive diluent, uniform stirring 30min;
B, in a kettle, dispersant, levelling agent, uniform stirring 15min is added;
C, it is 30 DEG C toward addition initiator, temperature of reaction kettle inside reaction kettle, stops stirring after the transparent color of solution.
The ultraviolet light that light source for curing the photosensitive resin is wavelength 300nm.
Embodiment 6
The photosensitive resin for 3D printing is present embodiments provided, component and mass percent are:The alicyclic ring of 30wt.%
Race's ethylene oxidic ester, the bisphenol A type epoxy resin of 20wt.%, the aliphatic epoxy acrylate of 15wt.%, 20wt.%'s is poly-
Urea monomer, the polypropylene glycol diglycidyl ether diacrylate of 5wt.%, the initiator of 2wt.%, the activity dilution of 5wt.%
Agent, the dispersant of 1wt.%, the levelling agent of 2wt.%.
Preparation method:
A, prepared by polyurea monomers:Toluene di-isocyanate(TDI) is taken, with the acetone solvent of rear addition 50% in sodium hydroxide, is passed through
Polyurea monomers are made after washing, dehydration, separation;
B, in the reaction kettle equipped with blender, thermometer, condenser and charging spout, addition cycloaliphatc glycidyl ester,
Bisphenol A type epoxy resin, aliphatic epoxy acrylate, polypropylene glycol diglycidyl ether diacrylate, polyurea monomers and
Reactive diluent, uniform stirring 10min;
C, in a kettle, dispersant, levelling agent, uniform stirring 10min is added;
D, it is 60 DEG C toward addition initiator, temperature of reaction kettle inside reaction kettle, stops stirring after the transparent color of solution.
The ultraviolet light that light source for curing the photosensitive resin is wavelength 450nm.
Embodiment 7
The photosensitive resin for 3D printing is present embodiments provided, component and mass percent are:The alicyclic ring of 30wt.%
Race's ethylene oxidic ester, the bisphenol A type epoxy resin of 20wt.%, the aliphatic epoxy acrylate of 15wt.%, 6wt.%'s is poly-
The activity of urea monomer, the polypropylene glycol diglycidyl ether diacrylate of 5wt.%, the initiator of 2wt.%, 20wt.% is dilute
Release agent, the dispersant of 1wt.%, the levelling agent of 1wt.%.
Preparation method:
A, prepared by polyurea monomers:Toluene di-isocyanate(TDI) is taken, with the acetone solvent of rear addition 40% in sodium hydroxide, is passed through
Polyurea monomers are made after washing, dehydration, separation;
B, in the reaction kettle equipped with blender, thermometer, condenser and charging spout, addition cycloaliphatc glycidyl ester,
Bisphenol A type epoxy resin, aliphatic epoxy acrylate, polypropylene glycol diglycidyl ether diacrylate, polyurea monomers and
Reactive diluent, uniform stirring 20min;
C, in a kettle, dispersant, levelling agent, uniform stirring 25min is added;
D, it is 50 DEG C toward addition initiator, temperature of reaction kettle inside reaction kettle, stops stirring after the transparent color of solution.
The ultraviolet light that light source for curing the photosensitive resin is wavelength 250nm.
Embodiment 8
The photosensitive resin for 3D printing is present embodiments provided, component and mass percent are:The alicyclic ring of 30wt.%
Race's ethylene oxidic ester, the bisphenol A type epoxy resin of 20wt.%, the aliphatic epoxy acrylate of 15wt.%, 5wt.%'s is poly-
The activity of urea monomer, the polypropylene glycol diglycidyl ether diacrylate of 5wt.%, the initiator of 1wt.%, 18wt.% is dilute
Release agent, the dispersant of 4wt.%, the levelling agent of 2wt.%.
Preparation method:
A, prepared by polyurea monomers:Toluene di-isocyanate(TDI) is taken, with the acetone solvent of rear addition 40% in sodium hydroxide, is passed through
Polyurea monomers are made after washing, dehydration, separation;
B, in the reaction kettle equipped with blender, thermometer, condenser and charging spout, addition cycloaliphatc glycidyl ester,
Bisphenol A type epoxy resin, aliphatic epoxy acrylate, polypropylene glycol diglycidyl ether diacrylate, polyurea monomers and
Reactive diluent, uniform stirring 25min;
C, in a kettle, dispersant, levelling agent, uniform stirring 35min is added;
D, it is 45 DEG C toward addition initiator, temperature of reaction kettle inside reaction kettle, stops stirring after the transparent color of solution.
The ultraviolet light that light source for curing the photosensitive resin is wavelength 500nm.
The each component mass percentage of the photosensitive resin for 3D printing described in embodiment 1-8 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 3D printing UV curing photosensitive resin, and component and content are as shown in table 2,
Preparation method is same as Example 1.
Comparative example 2
This comparative example provides a kind of 3D printing UV curing photosensitive resin, and component and content are as shown in table 2,
Preparation method is same as Example 1.
Comparative example 3
Comparative example 3 provides a kind of 3D printing UV curing photosensitive resin, and component and content are as shown in table 2,
Preparation method is same as Example 4.
Comparative example 4
This comparative example provides a kind of 3D printing UV curing photosensitive resin, and component and content are as shown in table 2,
Preparation method is same as Example 5.
Comparative example 5
This comparative example provides a kind of 3D printing UV curing photosensitive resin, and component and content are as shown in table 2,
Preparation method is same as Example 6.
Comparative example 6
This comparative example provides a kind of 3D printing UV curing photosensitive resin, and component and content are as shown in table 2,
Preparation method is same as Example 6.
The mass percentage of each component in 1 embodiment of table
Comparative example 7
This comparative example provides a kind of 3D printing UV curing photosensitive resin, component and content and 2 base of embodiment
This is identical, the difference is that only:Using unmodified polyurea monomers in this comparative example.
Preparation method is same as Example 6.
Compliance test result:
Photo-curing material prepared by embodiment and comparative example is placed in 3D printer and carries out printing test, to 3D printing light
The performance of solidification 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 domain 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 domain.
Claims (13)
1. a kind of photosensitive resin for 3D printing, which is characterized in that the photosensitive resin includes following weight percentage
Each component:
2. being used for the photosensitive resin of 3D printing as described in claim 1, which is characterized in that the light source of the photosensitive resin is wave
The ultraviolet light of long 200~500nm.
3. being used for the photosensitive resin of 3D printing as described in claim 1, which is characterized in that the cycloaliphatc glycidyl ester
Degree of functionality is 1~3, and viscosity is 800~1000cps under room temperature, and glass transition temperature is 43~47 DEG C.
4. being used for the photosensitive resin of 3D printing as described in claim 1, which is characterized in that the bisphenol A type epoxy resin
Degree of functionality is 2~4, and viscosity is 3300~3700cps under room temperature, and glass transition temperature is 34~38 DEG C.
5. being used for the photosensitive resin of 3D printing as described in claim 1, which is characterized in that the aliphatic epoxy acrylate
Degree of functionality be 1~3, viscosity is 800~1200cps under room temperature, and glass transition temperature is 38~42 DEG C.
6. being used for the photosensitive resin of 3D printing as described in claim 1, which is characterized in that the cycloaliphatc glycidyl ester
Degree of functionality is 1~3, and viscosity is 800~1000cps under room temperature, and glass transition temperature is 43~47 DEG C.
7. being used for the photosensitive resin of 3D printing as described in claim 1, which is characterized in that the polyurea monomers are at normal temperatures
Viscosity is 3000~3400cps, and elongation at break is more than 400%;
The preparation method of the polyurea monomers is as follows:Toluene di-isocyanate(TDI) is taken, 30~60% are added with rear in sodium hydroxide
Acetone solvent, after washing, dehydration, separation be made polyurea monomers.
8. being used for the photosensitive resin of 3D printing as described in claim 1, which is characterized in that the polypropylene glycol diglycidyl
The degree of functionality of ether diacrylate is 1~3, and viscosity is 1500~1900cps under room temperature, and glass transition temperature is 30~34
℃。
9. being used for the photosensitive resin of 3D printing as described in claim 1, which is characterized in that the initiator is camphorquinone, peace
The fragrant dimethyl ether of breath, fluorinated diphenyl titanium cyclopentadienyl, benzophenone, dicumyl peroxide decane acid esters, 2- methyl -2- hydroxyl-alphas-naphthalene third
At least one of ketone.
10. being used for the photosensitive resin of 3D printing as described in claim 1, which is characterized in that the reactive diluent is different ice
At least one of chip base acrylate, tripropylene glycol class diacrylate, trimethylolpropane trimethacrylate.
11. as described in claim 1 be used for 3D printing photosensitive resin, which is characterized in that the dispersant be naphthalene sulfonic acids base,
At least one of amino modified block copolymer, polybasic carboxylic acid based block copolymer.
12. being used for the photosensitive resin of 3D printing as described in claim 1, which is characterized in that the levelling agent is polyacrylic acid
One kind in ester, polyether-modified dimethyl siloxane.
13. a kind of preparation method of photosensitive resin such as claim 1-12 any one of them for 3D printing, feature exist
In the described method comprises the following steps:
A, in a kettle, cycloaliphatc glycidyl ester, bisphenol A type epoxy resin, aliphatic epoxy acrylate, poly- third is added
Hexanediol diglycidyl ether diacrylate, polyurea monomers and reactive diluent, 5~30min of uniform stirring;
B, again in a kettle, dispersant, levelling agent, 5~40min of uniform stirring is added;
C, initiator is added in a kettle again, temperature of reaction kettle is 30~70 DEG C, stops stirring after the transparent color of solution,
Up to the photosensitive resin.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810531545.3A CN108690328A (en) | 2018-05-29 | 2018-05-29 | A kind of photosensitive resin and preparation method thereof for 3D printing |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810531545.3A CN108690328A (en) | 2018-05-29 | 2018-05-29 | A kind of photosensitive resin and preparation method thereof for 3D printing |
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| CN109867756A (en) * | 2019-02-22 | 2019-06-11 | 苏州轻金三维科技有限公司 | A kind of 3 D-printing blue light curing photosensitive resin and preparation method thereof |
| CN109867755A (en) * | 2019-02-22 | 2019-06-11 | 苏州轻金三维科技有限公司 | A kind of photosensitive resin preparation method suitable for 3 D-printing |
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Application publication date: 20181023 |