CN107652398A - A kind of high intensity 3D printing photosensitive resin material - Google Patents

A kind of high intensity 3D printing photosensitive resin material Download PDF

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Publication number
CN107652398A
CN107652398A CN201710837600.7A CN201710837600A CN107652398A CN 107652398 A CN107652398 A CN 107652398A CN 201710837600 A CN201710837600 A CN 201710837600A CN 107652398 A CN107652398 A CN 107652398A
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photosensitive resin
parts
resin material
high intensity
printing photosensitive
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刘立忠
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Jiangshan Haiwei Technology Co Ltd
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Jiangshan Haiwei Technology Co Ltd
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F267/00—Macromolecular compounds obtained by polymerising monomers on to polymers of unsaturated polycarboxylic acids or derivatives thereof as defined in group C08F22/00
    • C08F267/06—Macromolecular compounds obtained by polymerising monomers on to polymers of unsaturated polycarboxylic acids or derivatives thereof as defined in group C08F22/00 on to polymers of esters
    • 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
    • C—CHEMISTRY; METALLURGY
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    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F2/00—Processes of polymerisation
    • C08F2/46—Polymerisation initiated by wave energy or particle radiation
    • C08F2/48—Polymerisation initiated by wave energy or particle radiation by ultraviolet or visible light
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
    • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/10—Esters
    • C08F220/26—Esters containing oxygen in addition to the carboxy oxygen
    • C08F220/28—Esters containing oxygen in addition to the carboxy oxygen containing no aromatic rings in the alcohol moiety
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F222/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a carboxyl radical and containing at least one other carboxyl radical in the molecule; Salts, anhydrides, esters, amides, imides, or nitriles thereof
    • C08F222/10—Esters
    • C08F222/1006—Esters of polyhydric alcohols or polyhydric phenols
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F265/00—Macromolecular compounds obtained by polymerising monomers on to polymers of unsaturated monocarboxylic acids or derivatives thereof as defined in group C08F20/00
    • C08F265/04—Macromolecular compounds obtained by polymerising monomers on to polymers of unsaturated monocarboxylic acids or derivatives thereof as defined in group C08F20/00 on to polymers of esters
    • C08F265/06—Polymerisation of acrylate or methacrylate esters on to polymers thereof
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/20—Oxides; Hydroxides
    • C08K3/22—Oxides; Hydroxides of metals
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/24—Acids; Salts thereof
    • C08K3/26—Carbonates; Bicarbonates
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/32—Phosphorus-containing compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
    • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/10—Esters
    • C08F220/26—Esters containing oxygen in addition to the carboxy oxygen
    • C08F220/28—Esters containing oxygen in addition to the carboxy oxygen containing no aromatic rings in the alcohol moiety
    • C08F220/281—Esters containing oxygen in addition to the carboxy oxygen containing no aromatic rings in the alcohol moiety and containing only one oxygen, e.g. furfuryl (meth)acrylate or 2-methoxyethyl (meth)acrylate
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F222/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a carboxyl radical and containing at least one other carboxyl radical in the molecule; Salts, anhydrides, esters, amides, imides, or nitriles thereof
    • C08F222/10—Esters
    • C08F222/1006—Esters of polyhydric alcohols or polyhydric phenols
    • C08F222/102—Esters of polyhydric alcohols or polyhydric phenols of dialcohols, e.g. ethylene glycol di(meth)acrylate or 1,4-butanediol dimethacrylate
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/20—Oxides; Hydroxides
    • C08K3/22—Oxides; Hydroxides of metals
    • C08K2003/2227—Oxides; Hydroxides of metals of aluminium
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/20—Oxides; Hydroxides
    • C08K3/22—Oxides; Hydroxides of metals
    • C08K2003/2237—Oxides; Hydroxides of metals of titanium
    • C08K2003/2241—Titanium dioxide
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/24—Acids; Salts thereof
    • C08K3/26—Carbonates; Bicarbonates
    • C08K2003/265—Calcium, strontium or barium carbonate
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/30—Sulfur-, selenium- or tellurium-containing compounds
    • C08K2003/3045—Sulfates
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/32—Phosphorus-containing compounds
    • C08K2003/321—Phosphates
    • C08K2003/325—Calcium, strontium or barium phosphate
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K2201/00—Specific properties of additives
    • C08K2201/011—Nanostructured additives

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  • Manufacturing & Machinery (AREA)
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Abstract

The invention provides a kind of high intensity 3D printing photosensitive resin material, by weight, by 20~60 parts of prepolymers and 0.5~0.8 part of light trigger, 1.5~3 parts of terminators, 5~15 parts of crosslinking agents, 0.1~3 part of functional nanoparticle, 0.5~1 part of color additives, 0.5~2 part of solubilizer, mix at room temperature, polymerization, 3D printing photosensitive resin material is made.

Description

A kind of high intensity 3D printing photosensitive resin material
Technical field
The present invention relates to 3D（Rapid shaping and manufacture class）It is especially a kind of high such as the formula and preparation method of photosensitive resin Intensity 3D printing photosensitive resin material.
Background technology
It for the material of photocureable rapid shaping is liquid photocurable resin that photosensitive resin, which is, or liquid photosensitive resin, Mainly it is made up of oligomer, light trigger, diluent.Nearly 2 years, photosensitive resin had just been used for 3D printing emerging industry, photosensitive tree Lipid 3D printing consumptive material is because its printing precision is high, and sharpness of border, surface is smooth, and interest in industry with paying attention to.
CN201510602875.3 discloses a kind of 3D printing photosensitive resin material containing modified butadiene rubber, by matter Percentage is measured by component：Modified butadiene rubber is 10-30%；Acrylic resin is 30-80%；Diluent is 10-40%； Initiator is 1-2%；Accelerator forms for 1-2%.The present invention obtains the polybutadiene with terminal hydroxy group by anionic polymerisation Telechelic polymer, then be esterified with acrylic acid, introducing the effect that double bond group obtains is：By anionic synthesis methods, obtain The narrower polymer of molecular weight distribution, beneficial to processing, rubber segment is introduced, efficiently solves the brittleness problems of generally existing, is led to Cross and carry out esterification introducing double bond with the acrylic acid of one of the original system of photosensitive resin, consistency problem is solved at all.This Invention additionally provides a kind of preparation method of the 3D printing photosensitive resin material containing modified butadiene rubber.
CN201510881469.5 disclose a kind of pure cationic 3D printing stereolithography rapid shaping photosensitive resin and Preparation method and application, it is made up of by weight percent following raw material：15~95% silicone-containing cycloaliphatic epoxy resins；1~ 30% oxetane compound；1~50% alicyclic epoxide compound；1~25% aliphatic epoxy compound；1~12% sun from Subtype initiator.The material component is mixed by described quality proportioning；Then, heat, stir, i.e., in temperature 20~80 DEG C, stir 5~120 minutes, make transparent faint yellow uniform liquid.Photosensitive resin excitant prepared by the present invention it is small and Volatile matter is few, and preparation process is easy；Light sensitivity is good, and its threshold exposure amount Ec is less than 19.0mJ/cm2.The precision of forming part is high, The warp factor CF (6) of forming part is in the range of ± 0.01, and CF (11) is in the range of ± 0.03.The light prepared using the present invention The part forming precision that the existing photosensitive resin of part forming ratio of precision that quick resin prints prints is higher.
3D printing for soft type, there is very strict requirement to the pliability of its consumptive material photosensitive resin, therefore, be made 3D printing material solve the matching of its mobility and the technical barrier that is matched with 3D printer of shaping speed, while solution is at present The problems such as commercially available 3D printing strength of materials is low, coloring is difficult, comprehensive intensity, mobility and the release property for improving 3D printing material etc. Performance, and the cost for reducing 3D printing material is that current industry breaks through difficult point.
The content of the invention
Present invention aims at solve above-mentioned technical problem present in prior art, there is provided a kind of the present invention relates to photosensitive The formula and preparation method of resin, especially a kind of high intensity 3D printing photosensitive resin material, comprise the following steps：
1st, the preparation of prepolymer：
By weight, by 10~60 parts by photosensitive resin polymer monomer, 0.01~0.1 part of rhenium carbonyl of cyclopentadiene three, 0.1-1 Double (trifluoromethyl) -1,3- octadienes of 6,6,7,7,8,8,8- seven fluoro- 5,5- of part, 0.1-1 parts α-sodium olefin sulfonate, 0.5~2 part Light trigger and 1~2 part of terminator, 5~20 parts of crosslinking agents, 100-200 part solvents, it is anti-that pre-polymerization is carried out at 90 DEG C~110 DEG C Prepolymer should be made, in 1~2.5 hour reaction time, obtain prepolymer.
, 3D printing photosensitive resin preparation
By weight, by prepolymer made from 20~60 parts of above-mentioned steps 1 and 0.5~0.8 part of light trigger, 1.5~3 parts of terminations Agent, 5~15 parts of crosslinking agents, 0.1~3 part of functional nanoparticle, 0.5~1 part of color additives, 0.5~2 part of solubilizer, room Temperature is lower to be mixed, and polymerization, 3D printing photosensitive resin material is made
Photosensitive resin polymer monomer described in step (1) is selected from：Epoxy Acrylates compound monomer, methacrylic acid Ester type compound monomer and acroleic acid polyurethane class compound monomer.
Solvent described in step (1) includes aromatic hydrocarbon solvent, fat hydrocarbon solvent, alicyclic hydrocarbon type solvent, halogenated hydrocarbon Class solvent, alcohols solvent, ether solvent, esters solvent, ketones solvent, diol, derivatives and/or nitrogen-containing solvent, preferably benzene, Toluene, dimethylbenzene, styrene, pentane, hexane, octane, hexamethylene, cyclohexanone, toluene cyclohexanone, chlorobenzene, dichloro-benzenes, dichloromethane Alkane, chloroform, perchloroethylene, trichloro ethylene, methanol, ethanol, isopropanol, ether, expoxy propane, ethylene glycol ether, tumer Ester, ethyl acetate, propyl acetate, glycol monoethyl ether, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, acetonitrile, pyridine, phenol and/ Or triethanolamine.
The particle diameter of functional nanoparticle described in step 2 is 1nm~100 μm, and it includes metal oxide particle, salt One or more in class particle, silicon-containing compound particle and nano metal powder, wherein, the metal oxide particle includes Nano scale metal simple substance, the mixture of a variety of nano scale metal simple substances and nanoscale alloy powder, preferably nano-calcium phosphate, receive Rice calcium carbonate, nano aluminium oxide.
Color additives described in step 2 include natural inorganic color additives and artificial color additive, wherein, day Right inorganic color additives are selected from jet-black, chalk, cinnabar, laterite, realgar and natural iron oxide；Artificial color additive is selected from gold Belong to oxide-based color additives and salt color additives, preferably metal oxide-type color additives, chromate face Colour additive, carbonate color additives, Sulfates color additives, sulfide-based color additives, Nitrates face Colour additive and acetic acid salt color additives.
Solubilizer described in step 2 is surfactant, including cationic surface active agent, anionic surface are lived Property at least one of agent and nonionic surface active agent, be preferably, primary amine salt surfactant, secondary amine salt surfactant, Quaternary surfactant and tertiary amine salt surfactant, heterocyclic surfactant, salt form surfactant, lecithin table Face activating agent, amino acid type surfactant, betaine type amphoteric surfactant, fatty acid glycerine ester surfactant, sapn system Surfactant and TWEEN Series surfactant.
Further, step 1 and step 2 kind：
The light trigger is selected from：Benzoin and its derivative, benzil class compound, alkylbenzene ketone compounds, acyl group phosphorus Oxide, benzophenone compound, thioxanthones compound, salt compounds, metallorganic class and organosilicon alkanes Compound；
The terminator is selected from：Quinones, nitro compound, nitroso compound, aryl polyol and sulfur-bearing Compound, preferably hydroquinones, p-tert-Butylcatechol, wood tar, SDD, sodium polysulfide And natrium nitrosum；
The crosslinking agent is melamine-formaldahyde crosslinking agent, aziridines crosslinking agent, polycarbodiimide class crosslinking agent, polyisocyanic acid Class crosslinking agent, alkylene oxides crosslinking agent, metallic-ion crosslinking agent and epoxy resin crosslinking agent.
The product of the present invention has the advantages that：
A kind of 3D of the present invention（Rapid shaping and manufacture class）Such as the formula and preparation method of photosensitive resin, can solve 3D and beat Print the requirement of material flexibility and toughness, the comprehensive intensity for improving 3D printing material.
Embodiment
Following instance is only to further illustrate the present invention, is not limitation the scope of protection of the invention.
Embodiment 1
1st, the preparation of prepolymer：
By weight, by 48.8 parts of dimethacrylates, 0.03 part of rhenium carbonyl of cyclopentadiene three, 0.2 part 6,6, Double (trifluoromethyl) -1,3- octadienes of 7,7,8,8,8- seven fluoro- 5,5-, 0.2 part of α-sodium olefin sulfonate, 1 part of acure369 (BDMB) it is dissolved in 100 parts of dichloromethane, is carried out at 90 DEG C pre- with 1.0 parts of hydroquinones and 10.0 parts of methyl-etherified melamines The prepolymer that the degree of polymerization is 50~200 is made in poly- reaction, and the viscosity of prepolymer is about 7000cps；
2nd, the preparation of 3D printing photosensitive resin
By weight, by prepolymer obtained above and 28.5 parts of dimethacrylates, 0.65 part of acure369 (BDMB), 2 parts of hydroquinones, 10.0 parts of methyl-etherified melamines, 1.0 parts of nano-calcium carbonates, 0.75 part of TiO2 and 1 part of octyl Phenol APEO -10, are mixed at room temperature, polymerize and the 3D printing photosensitive resin material M-1 is made.
Embodiment 2
1st, the preparation of prepolymer：
By weight, will be by 60.0 parts of photosensitive resin polymer monomer double pentaerythritol methacrylates, 0.1 part of cyclopentadiene three Rhenium carbonyl, 0.1 part 6, double (trifluoromethyl) -1,3- octadienes of 6,7,7,8,8,8- seven fluoro- 5,5-, 1 part of α-sodium olefin sulfonate, 2.0 parts of 4- methyl benzophenones, 2.0 parts of SDDs and 5.0 parts of methyl-etherified melamines are dissolved in 200 parts In chloroform, prepolymerization reaction is carried out at 110 DEG C the prepolymer that the degree of polymerization is 50~200 is made, the viscosity of prepolymer is about 10000cps；
2nd, the preparation of 3D printing photosensitive resin
By weight, by prepolymer obtained above and 60.0 parts of esters of bipentaerythrite acrylic acid six, 0.8 part of 4- methyldiphenyl first Ketone, 3.0 parts of SDDs, 15 parts of methyl-etherified melamines, 3 parts of nano-calcium phosphates, 1 part of cobalt blue and 2.0 Part AEO -7, are mixed at room temperature, polymerize and the 3D printing photosensitive resin material M-2 is made.
Embodiment 3
1st, the preparation of prepolymer：
By weight, by 10.0 parts of ethylene glycol methyl ether acrylates, 0.01 part of rhenium carbonyl of cyclopentadiene three, 1 part 6,6,7, Double (trifluoromethyl) -1,3- octadienes of 7,8,8,8- seven fluoro- 5,5-, 0.1 part of α-sodium olefin sulfonate, 0.5 part of benzoin (Benzoin) it is dissolved in 1.0 parts of SDDs and 20.0 parts of ethylenediamines in 150 parts of acetone, at 80 DEG C Carry out prepolymerization reaction and the prepolymer that the degree of polymerization is 50~200 is made, the viscosity of prepolymer is about 3000cps；
2nd, the preparation of 3D printing photosensitive resin
By weight, by prepolymer obtained above and 20.0 parts of esters of bipentaerythrite acrylic acid six, 0.5 part of benzoin (Benzoin), 1.5 parts of SDDs, 5 parts of crosslinking agent ethylenediamines, 0.1 part of nano aluminium oxide, 0.5 part CuSO4 and 0.5 part of Tween 80 mixing, is mixed at room temperature, polymerize and the 3D printing photosensitive resin material M-3 is made.
Comparative example 1
Step 2 is added without photosensitive resin polymerized monomer, and other conditions are the same as embodiment 1.Production code member M-4.
Comparative example 2
Step 2 is added without the rhenium carbonyl of cyclopentadiene three, and other conditions are the same as embodiment 1.Production code member M-5.
Comparative example 3
Step 2 is added without double (trifluoromethyl) -1,3- octadienes of 6,6,7,7,8,8,8- seven fluoro- 5,5-, and other conditions are the same as implementation Example 1.Production code member M-6.
Comparative example 4
Step 2 is added without functional nanoparticle, and other conditions are the same as embodiment 1.Production code member M-7.
Comparative example 5
Step 1 is cancelled, the other the same as in Example 1.Production code member M-8.
Embodiment 4
The 3D printing photosensitive resin material that embodiment 1-3 and comparative example 1-5 are produced, carry out liquid viscosity（cps/30 ℃）, solid carries out bending strength MPA, bending modulus MPA, elongation at break % detection after photocuring, and concrete outcome is shown in Table 1.
Table 1：The 3D printing photosensitive resin material viscosity that different process is produced（cps/30℃）, solid state bending after photocuring Intensity（MPA）, bending modulus（MPA）, elongation at break %/elastic recovery section % testing results.

Claims (5)

1. a kind of high intensity 3D printing photosensitive resin material, it is characterised in that its preparation method comprises the following steps：
By weight, by 20~60 parts of prepolymers and 0.5~0.8 part of light trigger, 1.5~3 parts of terminators, 5~15 parts of crosslinkings Agent, 0.1~3 part of functional nanoparticle, 0.5~1 part of color additives, 0.5~2 part of solubilizer, are mixed at room temperature, polymerization, 3D printing photosensitive resin material is made.
A kind of 2. high intensity 3D printing photosensitive resin material described in claim 1, it is characterised in that the preparation of the prepolymer Method comprises the following steps：
By weight, by 10~60 parts by photosensitive resin polymer monomer, 0.01~0.1 part of rhenium carbonyl of cyclopentadiene three, 0.1-1 Double (trifluoromethyl) -1,3- octadienes of 6,6,7,7,8,8,8- seven fluoro- 5,5- of part, 0.1-1 parts α-sodium olefin sulfonate, 0.5~2 part Light trigger and 1~2 part of terminator, 5~20 parts of crosslinking agents, 100-200 part solvents, it is anti-that pre-polymerization is carried out at 90 DEG C~110 DEG C Prepolymer should be made, in 1~2.5 hour reaction time, obtain prepolymer.
3. a kind of high intensity 3D printing photosensitive resin material described in claim 1, it is characterised in that described photosensitive resin gathers Monomer adduct includes Epoxy Acrylates compound monomer, methyl acrylic ester compound monomer and acroleic acid polyurethane class Compound monomer.
A kind of 4. high intensity 3D printing photosensitive resin material described in claim 1, it is characterised in that described functionalized nano Particle includes nano-calcium phosphate, nano-calcium carbonate, nano aluminium oxide.
A kind of 5. high intensity 3D printing photosensitive resin material described in claim 1, it is characterised in that the terminator include pair Benzenediol.
CN201710837600.7A 2017-09-18 2017-09-18 A kind of high intensity 3D printing photosensitive resin material Pending CN107652398A (en)

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Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104151526A (en) * 2014-08-07 2014-11-19 浙江闪铸三维科技有限公司 Novel photosensitive resin material applied to DLP3D printer
CN104710573A (en) * 2014-01-03 2015-06-17 刘毓海 Preparation method of 3D printing material
CN106957378A (en) * 2017-04-07 2017-07-18 南京先临三维科技有限公司 A kind of 3D printing preparation method of polymeric gradient material

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104710573A (en) * 2014-01-03 2015-06-17 刘毓海 Preparation method of 3D printing material
CN104710548A (en) * 2014-01-03 2015-06-17 刘毓海 3D printing core material
CN104151526A (en) * 2014-08-07 2014-11-19 浙江闪铸三维科技有限公司 Novel photosensitive resin material applied to DLP3D printer
CN106957378A (en) * 2017-04-07 2017-07-18 南京先临三维科技有限公司 A kind of 3D printing preparation method of polymeric gradient material

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Application publication date: 20180202