CN110845814A - Nylon microsphere modified photocuring resin composite material for 3D printing and preparation method thereof - Google Patents
Nylon microsphere modified photocuring resin composite material for 3D printing and preparation method thereof Download PDFInfo
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- CN110845814A CN110845814A CN201810822593.8A CN201810822593A CN110845814A CN 110845814 A CN110845814 A CN 110845814A CN 201810822593 A CN201810822593 A CN 201810822593A CN 110845814 A CN110845814 A CN 110845814A
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- 239000004005 microsphere Substances 0.000 title claims abstract description 54
- 239000004677 Nylon Substances 0.000 title claims abstract description 39
- 229920001778 nylon Polymers 0.000 title claims abstract description 39
- 239000000463 material Substances 0.000 title claims abstract description 33
- 238000010146 3D printing Methods 0.000 title claims abstract description 21
- 239000000805 composite resin Substances 0.000 title claims abstract description 21
- 238000002360 preparation method Methods 0.000 title claims abstract description 7
- 238000000016 photochemical curing Methods 0.000 title claims description 12
- 239000011347 resin Substances 0.000 claims abstract description 33
- 229920005989 resin Polymers 0.000 claims abstract description 33
- 239000007822 coupling agent Substances 0.000 claims abstract description 12
- 239000002994 raw material Substances 0.000 claims abstract description 3
- 239000000843 powder Substances 0.000 claims description 12
- 229920002292 Nylon 6 Polymers 0.000 claims description 10
- 239000006087 Silane Coupling Agent Substances 0.000 claims description 10
- -1 hexafluorophosphate Chemical compound 0.000 claims description 10
- JHWNWJKBPDFINM-UHFFFAOYSA-N Laurolactam Chemical compound O=C1CCCCCCCCCCCN1 JHWNWJKBPDFINM-UHFFFAOYSA-N 0.000 claims description 5
- 229920000299 Nylon 12 Polymers 0.000 claims description 5
- 239000002245 particle Substances 0.000 claims description 5
- 101100459439 Caenorhabditis elegans nac-2 gene Proteins 0.000 claims description 4
- 229920000572 Nylon 6/12 Polymers 0.000 claims description 4
- ZMUCVNSKULGPQG-UHFFFAOYSA-N dodecanedioic acid;hexane-1,6-diamine Chemical compound NCCCCCCN.OC(=O)CCCCCCCCCCC(O)=O ZMUCVNSKULGPQG-UHFFFAOYSA-N 0.000 claims description 4
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 3
- 239000000178 monomer Substances 0.000 claims description 3
- WXPWZZHELZEVPO-UHFFFAOYSA-N (4-methylphenyl)-phenylmethanone Chemical compound C1=CC(C)=CC=C1C(=O)C1=CC=CC=C1 WXPWZZHELZEVPO-UHFFFAOYSA-N 0.000 claims description 2
- RWHRFHQRVDUPIK-UHFFFAOYSA-N 50867-57-7 Chemical compound CC(=C)C(O)=O.CC(=C)C(O)=O RWHRFHQRVDUPIK-UHFFFAOYSA-N 0.000 claims description 2
- 229920002126 Acrylic acid copolymer Polymers 0.000 claims description 2
- 239000004925 Acrylic resin Substances 0.000 claims description 2
- 229920000178 Acrylic resin Polymers 0.000 claims description 2
- 239000004593 Epoxy Substances 0.000 claims description 2
- 101000981987 Homo sapiens N-alpha-acetyltransferase 20 Proteins 0.000 claims description 2
- 101000640836 Homo sapiens Sodium-coupled neutral amino acid transporter 4 Proteins 0.000 claims description 2
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 claims description 2
- 102100026778 N-alpha-acetyltransferase 20 Human genes 0.000 claims description 2
- 229920000571 Nylon 11 Polymers 0.000 claims description 2
- 239000004952 Polyamide Substances 0.000 claims description 2
- 150000008062 acetophenones Chemical class 0.000 claims description 2
- 150000001336 alkenes Chemical class 0.000 claims description 2
- 150000008365 aromatic ketones Chemical class 0.000 claims description 2
- UXWSUTBOOHDZIL-UHFFFAOYSA-N bis(1-hydroxycyclohexyl)methanone Chemical compound C1CCCCC1(O)C(=O)C1(O)CCCCC1 UXWSUTBOOHDZIL-UHFFFAOYSA-N 0.000 claims description 2
- 229920001577 copolymer Polymers 0.000 claims description 2
- 125000005520 diaryliodonium group Chemical group 0.000 claims description 2
- 229920003145 methacrylic acid copolymer Polymers 0.000 claims description 2
- 229940117841 methacrylic acid copolymer Drugs 0.000 claims description 2
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 claims description 2
- HPAFOABSQZMTHE-UHFFFAOYSA-N phenyl-(2,4,6-trimethylphenyl)methanone Chemical compound CC1=CC(C)=CC(C)=C1C(=O)C1=CC=CC=C1 HPAFOABSQZMTHE-UHFFFAOYSA-N 0.000 claims description 2
- 229920002647 polyamide Polymers 0.000 claims description 2
- FZHAPNGMFPVSLP-UHFFFAOYSA-N silanamine Chemical compound [SiH3]N FZHAPNGMFPVSLP-UHFFFAOYSA-N 0.000 claims description 2
- 125000005409 triarylsulfonium group Chemical group 0.000 claims description 2
- UKRDPEFKFJNXQM-UHFFFAOYSA-N vinylsilane Chemical compound [SiH3]C=C UKRDPEFKFJNXQM-UHFFFAOYSA-N 0.000 claims description 2
- 239000000203 mixture Substances 0.000 claims 2
- CERQOIWHTDAKMF-UHFFFAOYSA-M Methacrylate Chemical compound CC(=C)C([O-])=O CERQOIWHTDAKMF-UHFFFAOYSA-M 0.000 claims 1
- 239000003999 initiator Substances 0.000 claims 1
- 238000005336 cracking Methods 0.000 abstract description 2
- WVDDGKGOMKODPV-UHFFFAOYSA-N Benzyl alcohol Chemical compound OCC1=CC=CC=C1 WVDDGKGOMKODPV-UHFFFAOYSA-N 0.000 description 6
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 6
- 238000002156 mixing Methods 0.000 description 6
- 238000000465 moulding Methods 0.000 description 6
- 239000000523 sample Substances 0.000 description 6
- 238000000034 method Methods 0.000 description 5
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 4
- 239000007788 liquid Substances 0.000 description 4
- 229920000642 polymer Polymers 0.000 description 4
- 239000012496 blank sample Substances 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 238000001723 curing Methods 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- HRPUANCEDYZMFT-UHFFFAOYSA-N 2-(1-hydroxycyclohexyl)-1-phenylethanone Chemical compound C=1C=CC=CC=1C(=O)CC1(O)CCCCC1 HRPUANCEDYZMFT-UHFFFAOYSA-N 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 235000019445 benzyl alcohol Nutrition 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 238000004132 cross linking Methods 0.000 description 2
- 239000003085 diluting agent Substances 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 230000001788 irregular Effects 0.000 description 2
- 239000011259 mixed solution Substances 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 2
- 238000009210 therapy by ultrasound Methods 0.000 description 2
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 description 1
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 1
- 238000005299 abrasion Methods 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 239000013065 commercial product Substances 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 229910010272 inorganic material Inorganic materials 0.000 description 1
- 239000011147 inorganic material Substances 0.000 description 1
- 239000011344 liquid material Substances 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 150000002734 metacrylic acid derivatives Chemical class 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 239000012798 spherical particle Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L33/00—Compositions of homopolymers or 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 of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
- C08L33/04—Homopolymers or copolymers of esters
- C08L33/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, which oxygen atoms are present only as part of the carboxyl radical
- C08L33/062—Copolymers with monomers not covered by C08L33/06
- C08L33/064—Copolymers with monomers not covered by C08L33/06 containing anhydride, COOH or COOM groups, with M being metal or onium-cation
-
- 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
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L33/00—Compositions of homopolymers or 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 of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
- C08L33/24—Homopolymers or copolymers of amides or imides
- C08L33/26—Homopolymers or copolymers of acrylamide or methacrylamide
-
- 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
- C08L2205/14—Polymer mixtures characterised by other features containing polymeric additives characterised by shape
- C08L2205/18—Spheres
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Materials Engineering (AREA)
Abstract
The invention discloses a nylon microsphere modified light-cured resin composite material for 3D printing, which is prepared from the following raw materials: 70-100 parts of light-cured resin, 0-30 parts of nylon microspheres, 0-2 parts of coupling agent and 0-1 part of photoinitiator. The invention also discloses a preparation method of the nylon microsphere modified light-cured resin composite material. The light-cured resin is modified by the nylon microspheres, so that the problems of part deformation, warping, cracking and the like during curing shrinkage and the problems of non-ideal wear resistance and scratch resistance are solved, and the product has the advantages of high size precision, wear resistance, scratch resistance and the like.
Description
Technical Field
The invention belongs to the technical field of polymer 3D printing materials, and relates to a nylon microsphere modified photocuring resin composite material for 3D printing and a preparation method thereof.
Background
The Stereolithography (SLA) process is based on the principle of photopolymerization of liquid photocurable resins. The liquid material can rapidly generate photopolymerization reaction under the irradiation of ultraviolet light with certain wavelength and power, the molecular weight is increased rapidly, and the material is converted from a liquid state to a solid state. The material for photocuring rapid molding is liquid photosensitive resin which mainly comprises oligomer, photoinitiator and diluent. The oligomer is the main body of photosensitive resin, is a base material containing unsaturated functional group, and its terminal has polymerizable active group, once it has active species, it can be continuously polymerized and grown, and once polymerized, its molecular weight can be quickly raised, and can be quickly made into solid. The photoinitiator is a special group for exciting the crosslinking reaction of the photosensitive resin, can become a free group with high activity when acted by photons with specific wavelength, acts on the high molecular polymer of the base material to generate the crosslinking reaction, and changes the original linear polymer into a reticular polymer so as to be presented as a solid state. The properties of the photoinitiator determine the degree and speed of curing of the photosensitive resin. The diluent is a functional monomer, has unsaturated double bonds in the structure, such as vinyl, allyl and the like, can adjust the viscosity of the oligomer, is not easy to volatilize, and can participate in polymerization.
The linear shrinkage rate of the light-cured resin is about 3% in the 3D printing and curing process, the curing shrinkage causes the problems of part deformation, warping, cracking and the like, the precision of the molded part is influenced, and the low-shrinkage resin is beneficial to molding the high-precision part. In addition, the surface hardness of the light-cured resin molding products of partial varieties is low, and the problems of abrasion resistance and non-ideal scratch resistance exist. Therefore, attempts have been made to add nano ceramic powder, short fibers, etc. to SLA photocurable resins to solve the above problems and to improve the material strength and heat resistance. However, the compatibility of inorganic powder materials and organic light-cured resins is poor, the inorganic powder materials are easy to precipitate in low-viscosity grade light-cured resins, the shapes of part of inorganic powder are irregular, the surface area is large, and the viscosity of the resin is greatly increased due to the addition of a small amount of the inorganic powder materials.
Disclosure of Invention
In order to solve the above problems, a first object of the present invention is to provide a photocurable resin composite material modified with nylon microspheres for 3D printing.
The second purpose of the invention is to provide a preparation method of the photo-curing resin composite material modified by the nylon microspheres for 3D printing.
The technical scheme of the invention is as follows:
the invention relates to a nylon microsphere modified light-cured resin composite material for 3D printing, which is prepared from the following raw materials:
in an embodiment of the present invention, the photo-curable resin is prepared by copolymerizing a photo-curable acrylic resin with methacrylates and other olefin monomers, and has a molecular weight of 2000-.
In a specific embodiment of the present invention, the photocurable resin is one or more of a methyl methacrylate/acrylic acid copolymer, a methacrylate-methacrylic acid copolymer, or an acrylic acid-acrylamide-cetyl methacrylate copolymer.
In a specific embodiment of the present invention, the spherical polyamide powder with the particle size of the nylon microsphere of 0.1-100um comprises one or more of nylon 6 microsphere, nylon 12 microsphere, nylon 6/12 microsphere or nylon 11 microsphere.
In an embodiment of the invention, the nylon microsphere is arkema nylon powder Orgasol@One or more of PA 122002 ES6 NAT3, PA 61002 ES4 NAT 1 or PA 6/123502D NAT 1.
In a specific embodiment of the present invention, the coupling agent is one or more of a silane coupling agent and a titanate coupling agent.
In a specific embodiment of the invention, the coupling agent is one or more of an epoxy silane coupling agent KH560, an amino silane coupling agent KH550 or a vinyl silane coupling agent KH 171.
In a specific embodiment of the present invention, the photoinitiator is one or more of acetophenone derivatives, aromatic ketones, diaryl iodonium salts, or triaryl sulfonium salts.
In a specific embodiment of the present invention, the photoinitiator is one or more selected from 2-hydroxy-2-methyl-1-phenyl acetone, 1-hydroxycyclohexyl ketone, 2, 4, 6-trimethyl benzophenone, 4-methyl benzophenone, 4 '-dimethyl diphenyl iodonium hexafluorophosphate, 4-methyl-4' -isobutyl diphenyl iodonium hexafluorophosphate, 4-chlorophenyl diphenyl sulfide hexafluorophosphate or 3-nitrophenyldiphenyl sulfide hexafluorophosphate.
The invention also discloses a preparation method of the nylon microsphere modified photocuring resin composite material for 3D printing, which comprises the steps of putting 0-30 parts of nylon microspheres into a high-speed mixer preheated to 20-200 ℃, adding 0-2 parts of coupling agent, mixing at high speed for 5-60min, cooling to below 80 ℃, adding 70-100 parts of photocuring resin and 0-1 part of photoinitiator into a homogenizer, and uniformly stirring to obtain the nylon microsphere modified photocuring resin composite material.
Compared with the prior art, the invention has the following beneficial effects:
since the density and polarity of the nylon resin are close to those of the SLA photocurable resin, and the surface area of the high sphericity powder of the nylon resin is lower than that of the irregular morphology powder of the inorganic material. Therefore, the viscosity increase of the system is lower at the same loading. In addition, the 'ball effect' of the spherical particles can bring special hand feeling of the material, and obviously improve the wear resistance and scratch resistance of the matrix material, so the nylon microspheres are added into the liquid light-cured resin, and the size precision, wear resistance and scratch resistance of the product are obviously improved.
Detailed Description
The invention will be further illustrated with reference to the following specific examples. It should be understood that these examples are only for illustrating the present invention and are not intended to limit the scope of the present invention. In practice, the invention will be understood to cover all modifications and variations of this invention provided they come within the scope of the appended claims.
Example 1
Adding 1kg of nylon 12 microspheres with the average particle size of 10um into a 2L high-speed mixer preheated to 150 ℃, adding 10g of organic titanate coupling agent NXT-105, mixing at high speed for 20min, and cooling the treated nylon 12 microspheres to 50 ℃. The processed nylon microsphere powder is added into 9kg of SP-RD204 photocuring resin (a commercial product of a new Changzhou Longtu material) to obtain the photocuring resin material modified by the nylon microspheres for 3D printing, and compared with the photocuring resin modified by not adding the nylon microspheres, the molding shrinkage is reduced by 15%. The scratch resistance of the photo-cured sample is tested according to the method specified in the ISO 7724 standard, and compared with a blank sample without the added nylon 12 microspheres, the scratch resistance grade of the sample in the embodiment is improved from grade 2 to grade 5.
Example 2
1kg of nylon 6 microspheres with the average particle size of 20um is added into a 2L high-speed mixer preheated to 150 ℃, 10g of silane coupling agent KH560 is added for high-speed mixing for 20min, and the treated nylon 6 microspheres are cooled to 50 ℃. Mixing the nylon 6 microspheres treated by the coupling agent and 4kg of 3, 4-epoxy cyclohexyl methyl-3, 4-epoxy cyclohexyl formic ether/tetrahydrofuran solution (50 wt%) in a beaker, and carrying out ultrasonic treatment for 36h by using an ultrasonic instrument with the power of 32W and the frequency of 40 KHz; and adding 0.1Kg of triaryl hexafluoro phosphonium phosphate sulfonium salt, 0.08Kg of 1-hydroxycyclohexyl acetophenone and 0.03g of dimethyl carbinol benzyl alcohol into the mixed solution, and distilling under reduced pressure to remove a tetrahydrofuran solvent to obtain the modified light-cured resin, wherein the modified light-cured resin is stored in a dark place, and the molding shrinkage is reduced by 20% compared with the light-cured resin without the nylon microsphere. The scratch resistance of the photo-cured sample is tested according to the method specified in the ISO 7724 standard, and compared with a blank sample without the nylon 6 microspheres, the scratch resistance grade of the sample in the embodiment is improved from grade 2 to grade 5.
Example 3
1.5kg of nylon 6/12 microspheres with the average particle size of 10um are added into a 2L high-speed mixer preheated to 150 ℃, 10g of silane coupling agent KH560 is added for high-speed mixing for 20min, and the treated nylon 6 microspheres are cooled to 50 ℃. Mixing the nylon 6 microspheres treated by the coupling agent and 3.5kg of 3, 4-epoxy cyclohexyl methyl-3, 4-epoxy cyclohexyl formic ether/tetrahydrofuran solution (50 wt%) in a beaker, and carrying out ultrasonic treatment for 36h by using an ultrasonic instrument with the power of 32W and the frequency of 40 KHz; and adding 0.1Kg of triaryl hexafluoro phosphonium phosphate sulfonium salt, 0.08Kg of 1-hydroxycyclohexyl acetophenone and 0.03g of dimethyl carbinol benzyl alcohol into the mixed solution, and distilling under reduced pressure to remove a tetrahydrofuran solvent to obtain the modified light-cured resin, wherein the molding shrinkage rate of the modified light-cured resin is reduced by 20% compared with that of the light-cured resin without the added nylon microspheres. The light-cured sample is tested for scratch resistance according to the method specified in the ISO 7724 standard, and compared with a blank sample without the added nylon 6/12 microspheres, the scratch resistance grade of the sample in the embodiment is improved from grade 2 to grade 5.
The preferred embodiments of the invention disclosed above are intended to be illustrative only. The preferred embodiments are not intended to be exhaustive or to limit the invention to the precise embodiments disclosed. Obviously, many modifications and variations are possible in light of the above teaching. The embodiments were chosen and described in order to best explain the principles of the invention and the practical application, to thereby enable others skilled in the art to best utilize the invention. The invention is limited only by the claims and their full scope and equivalents.
Claims (10)
1. The nylon microsphere modified light-cured resin composite material for 3D printing is characterized by being prepared from the following raw materials:
2. the photo-curable resin composite material modified by nylon microspheres for 3D printing as claimed in claim 1, wherein the photo-curable resin is prepared by copolymerizing photo-curable acrylic resin with methacrylate and other olefin monomers, and has a molecular weight of 2000-.
3. The nylon microsphere modified light-cured resin composite material for 3D printing according to claim 1 or 2, wherein the light-cured resin is one or more of methyl methacrylate/acrylic acid copolymer, methacrylate-methacrylic acid copolymer or acrylic acid-acrylamide-cetyl methacrylate copolymer.
4. The nylon microsphere modified photocurable resin composite material for 3D printing according to claim 1, wherein the nylon microsphere is spherical polyamide powder with a particle size of 0.1-100um, and comprises one or more of nylon 6 microsphere, nylon 12 microsphere, nylon 6/12 microsphere or nylon 11 microsphere.
5. The photo-curable resin composite material modified by nylon microspheres for 3D printing according to claim 1 or 4, wherein the nylon microspheres are Achima nylon powder Orgasol@One or more of PA 122002 ES6 NAT3, PA 61002 ES4 NAT 1 or PA 6/123502D NAT 1.
6. The nylon microsphere modified photocurable resin composite material for 3D printing according to claim 1, wherein the coupling agent is one or more of silane coupling agents and titanate coupling agents.
7. The nylon microsphere modified photocurable resin composite material for 3D printing according to claim 1 or 6, wherein the coupling agent is one or more of epoxy silane coupling agent KH560, amino silane coupling agent KH550 or vinyl silane coupling agent KH 171.
8. The photo-curing resin composite material modified by nylon microspheres for 3D printing as claimed in claim 1, wherein the photo-initiator is one or more of acetophenone derivatives, aromatic ketones, diaryl iodonium salts or triaryl sulfonium salts.
9. The photocurable resin composite material modified with nylon microspheres for 3D printing according to claim 1 or 8, wherein the photoinitiator is one or more of 2-hydroxy-2-methyl-1-phenyl acetone, 1-hydroxycyclohexyl ketone, 2, 4, 6-trimethylbenzophenone, 4-methylbenzophenone, 4 '-dimethyldiphenyliodonium hexafluorophosphate, 4-methyl-4' -isobutyldiphenyliodonium hexafluorophosphate, 4-chlorophenyldiphenylsulfonium hexafluorophosphate or 3-nitrophenyldiphenylsulfonium hexafluorophosphate.
10. The preparation method of the nylon microsphere modified photocurable resin composite material for 3D printing as claimed in any one of claims 1 to 9, characterized in that 0-30 parts of nylon microspheres are placed into a high-speed mixer preheated to 20-200 ℃, 0-2 parts of coupling agent is added to be mixed at high speed for 5-60min, then the mixture is cooled to below 80 ℃, and the mixture is added into a homogenizer together with 70-100 parts of photocurable resin and 0-1 part of photoinitiator to be uniformly stirred, so as to prepare the nylon microsphere modified photocurable resin composite material.
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| Application Number | Priority Date | Filing Date | Title |
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| CN201810822593.8A CN110845814A (en) | 2018-07-24 | 2018-07-24 | Nylon microsphere modified photocuring resin composite material for 3D printing and preparation method thereof |
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| Application Number | Priority Date | Filing Date | Title |
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| CN201810822593.8A CN110845814A (en) | 2018-07-24 | 2018-07-24 | Nylon microsphere modified photocuring resin composite material for 3D printing and preparation method thereof |
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| CN110845814A true CN110845814A (en) | 2020-02-28 |
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| CN108148355A (en) * | 2016-12-05 | 2018-06-12 | 合肥杰事杰新材料股份有限公司 | It is a kind of for nylon micro-sphere composite material of Stereolithography and preparation method thereof |
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2018
- 2018-07-24 CN CN201810822593.8A patent/CN110845814A/en active Pending
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