CN113683732A - Photosensitive resin and preparation method and application thereof - Google Patents
Photosensitive resin and preparation method and application thereof Download PDFInfo
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- CN113683732A CN113683732A CN202111122673.0A CN202111122673A CN113683732A CN 113683732 A CN113683732 A CN 113683732A CN 202111122673 A CN202111122673 A CN 202111122673A CN 113683732 A CN113683732 A CN 113683732A
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- acrylate
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- printing
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- 239000011347 resin Substances 0.000 title claims abstract description 120
- 229920005989 resin Polymers 0.000 title claims abstract description 120
- 238000002360 preparation method Methods 0.000 title abstract description 6
- 239000004088 foaming agent Substances 0.000 claims abstract description 39
- 238000010146 3D printing Methods 0.000 claims abstract description 37
- 238000005187 foaming Methods 0.000 claims abstract description 28
- 150000003254 radicals Chemical class 0.000 claims abstract description 24
- 239000003085 diluting agent Substances 0.000 claims abstract description 13
- 239000003999 initiator Substances 0.000 claims abstract description 10
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 claims description 29
- VFHVQBAGLAREND-UHFFFAOYSA-N diphenylphosphoryl-(2,4,6-trimethylphenyl)methanone Chemical compound CC1=CC(C)=CC(C)=C1C(=O)P(=O)(C=1C=CC=CC=1)C1=CC=CC=C1 VFHVQBAGLAREND-UHFFFAOYSA-N 0.000 claims description 22
- 239000004005 microsphere Substances 0.000 claims description 20
- 238000001723 curing Methods 0.000 claims description 19
- PBOSTUDLECTMNL-UHFFFAOYSA-N lauryl acrylate Chemical compound CCCCCCCCCCCCOC(=O)C=C PBOSTUDLECTMNL-UHFFFAOYSA-N 0.000 claims description 18
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 claims description 17
- 238000000016 photochemical curing Methods 0.000 claims description 15
- 239000002202 Polyethylene glycol Substances 0.000 claims description 14
- 229920001223 polyethylene glycol Polymers 0.000 claims description 14
- 229920000058 polyacrylate Polymers 0.000 claims description 13
- 238000003756 stirring Methods 0.000 claims description 13
- 238000000034 method Methods 0.000 claims description 10
- PSGCQDPCAWOCSH-UHFFFAOYSA-N (4,7,7-trimethyl-3-bicyclo[2.2.1]heptanyl) prop-2-enoate Chemical compound C1CC2(C)C(OC(=O)C=C)CC1C2(C)C PSGCQDPCAWOCSH-UHFFFAOYSA-N 0.000 claims description 9
- STVZJERGLQHEKB-UHFFFAOYSA-N ethylene glycol dimethacrylate Chemical compound CC(=C)C(=O)OCCOC(=O)C(C)=C STVZJERGLQHEKB-UHFFFAOYSA-N 0.000 claims description 9
- LCGLNKUTAGEVQW-UHFFFAOYSA-N Dimethyl ether Chemical compound COC LCGLNKUTAGEVQW-UHFFFAOYSA-N 0.000 claims description 6
- ISAOCJYIOMOJEB-UHFFFAOYSA-N benzoin Chemical compound C=1C=CC=CC=1C(O)C(=O)C1=CC=CC=C1 ISAOCJYIOMOJEB-UHFFFAOYSA-N 0.000 claims description 6
- 229920002635 polyurethane Polymers 0.000 claims description 6
- 239000004814 polyurethane Substances 0.000 claims description 6
- 239000000843 powder Substances 0.000 claims description 6
- 239000011342 resin composition Substances 0.000 claims description 6
- FWWXYLGCHHIKNY-UHFFFAOYSA-N 2-ethoxyethyl prop-2-enoate Chemical compound CCOCCOC(=O)C=C FWWXYLGCHHIKNY-UHFFFAOYSA-N 0.000 claims description 5
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 claims description 5
- YTLYLLTVENPWFT-UPHRSURJSA-N (Z)-3-aminoacrylic acid Chemical compound N\C=C/C(O)=O YTLYLLTVENPWFT-UPHRSURJSA-N 0.000 claims description 3
- ZDQNWDNMNKSMHI-UHFFFAOYSA-N 1-[2-(2-prop-2-enoyloxypropoxy)propoxy]propan-2-yl prop-2-enoate Chemical compound C=CC(=O)OC(C)COC(C)COCC(C)OC(=O)C=C ZDQNWDNMNKSMHI-UHFFFAOYSA-N 0.000 claims description 3
- 239000012956 1-hydroxycyclohexylphenyl-ketone Substances 0.000 claims description 3
- BTJPUDCSZVCXFQ-UHFFFAOYSA-N 2,4-diethylthioxanthen-9-one Chemical compound C1=CC=C2C(=O)C3=CC(CC)=CC(CC)=C3SC2=C1 BTJPUDCSZVCXFQ-UHFFFAOYSA-N 0.000 claims description 3
- DXPPIEDUBFUSEZ-UHFFFAOYSA-N 6-methylheptyl prop-2-enoate Chemical compound CC(C)CCCCCOC(=O)C=C DXPPIEDUBFUSEZ-UHFFFAOYSA-N 0.000 claims description 3
- FIHBHSQYSYVZQE-UHFFFAOYSA-N 6-prop-2-enoyloxyhexyl prop-2-enoate Chemical compound C=CC(=O)OCCCCCCOC(=O)C=C FIHBHSQYSYVZQE-UHFFFAOYSA-N 0.000 claims description 3
- 239000004156 Azodicarbonamide Substances 0.000 claims description 3
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 claims description 3
- 239000004721 Polyphenylene oxide Substances 0.000 claims description 3
- 244000028419 Styrax benzoin Species 0.000 claims description 3
- 235000000126 Styrax benzoin Nutrition 0.000 claims description 3
- 235000008411 Sumatra benzointree Nutrition 0.000 claims description 3
- IAXXETNIOYFMLW-COPLHBTASA-N [(1s,3s,4s)-4,7,7-trimethyl-3-bicyclo[2.2.1]heptanyl] 2-methylprop-2-enoate Chemical compound C1C[C@]2(C)[C@@H](OC(=O)C(=C)C)C[C@H]1C2(C)C IAXXETNIOYFMLW-COPLHBTASA-N 0.000 claims description 3
- 125000001931 aliphatic group Chemical group 0.000 claims description 3
- 125000003118 aryl group Chemical group 0.000 claims description 3
- XOZUGNYVDXMRKW-AATRIKPKSA-N azodicarbonamide Chemical compound NC(=O)\N=N\C(N)=O XOZUGNYVDXMRKW-AATRIKPKSA-N 0.000 claims description 3
- 235000019399 azodicarbonamide Nutrition 0.000 claims description 3
- 229960002130 benzoin Drugs 0.000 claims description 3
- RWCCWEUUXYIKHB-UHFFFAOYSA-N benzophenone Chemical compound C=1C=CC=CC=1C(=O)C1=CC=CC=C1 RWCCWEUUXYIKHB-UHFFFAOYSA-N 0.000 claims description 3
- 239000012965 benzophenone Substances 0.000 claims description 3
- 150000008366 benzophenones Chemical class 0.000 claims description 3
- MQDJYUACMFCOFT-UHFFFAOYSA-N bis[2-(1-hydroxycyclohexyl)phenyl]methanone Chemical compound C=1C=CC=C(C(=O)C=2C(=CC=CC=2)C2(O)CCCCC2)C=1C1(O)CCCCC1 MQDJYUACMFCOFT-UHFFFAOYSA-N 0.000 claims description 3
- GMSCBRSQMRDRCD-UHFFFAOYSA-N dodecyl 2-methylprop-2-enoate Chemical compound CCCCCCCCCCCCOC(=O)C(C)=C GMSCBRSQMRDRCD-UHFFFAOYSA-N 0.000 claims description 3
- 235000019382 gum benzoic Nutrition 0.000 claims description 3
- 229940119545 isobornyl methacrylate Drugs 0.000 claims description 3
- WRAQQYDMVSCOTE-UHFFFAOYSA-N phenyl prop-2-enoate Chemical compound C=CC(=O)OC1=CC=CC=C1 WRAQQYDMVSCOTE-UHFFFAOYSA-N 0.000 claims description 3
- 229920000728 polyester Polymers 0.000 claims description 3
- 229920000570 polyether Polymers 0.000 claims description 3
- 229910052708 sodium Inorganic materials 0.000 claims description 3
- 239000011734 sodium Substances 0.000 claims description 3
- 238000007639 printing Methods 0.000 claims description 2
- -1 alkenyl sulfonate Chemical compound 0.000 claims 1
- 238000000465 moulding Methods 0.000 claims 1
- 239000000463 material Substances 0.000 abstract description 5
- 230000000052 comparative effect Effects 0.000 description 14
- 238000010438 heat treatment Methods 0.000 description 10
- 238000002156 mixing Methods 0.000 description 8
- 238000005303 weighing Methods 0.000 description 8
- UHESRSKEBRADOO-UHFFFAOYSA-N ethyl carbamate;prop-2-enoic acid Chemical compound OC(=O)C=C.CCOC(N)=O UHESRSKEBRADOO-UHFFFAOYSA-N 0.000 description 6
- 239000004604 Blowing Agent Substances 0.000 description 5
- 230000004048 modification Effects 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- 238000006116 polymerization reaction Methods 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 2
- 206010001497 Agitation Diseases 0.000 description 1
- 238000013019 agitation Methods 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
- 238000000748 compression moulding Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 230000005484 gravity Effects 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 239000003504 photosensitizing agent Substances 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 238000004088 simulation Methods 0.000 description 1
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 description 1
- 239000004711 α-olefin Substances 0.000 description 1
Classifications
-
- 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
-
- 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
- B33Y70/10—Composites of different types of material, e.g. mixtures of ceramics and polymers or mixtures of metals and biomaterials
-
- 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
- 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
- C08F283/00—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G
- C08F283/006—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to polymers provided for in C08G18/00
- C08F283/008—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to polymers provided for in C08G18/00 on to unsaturated polymers
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
- C08J9/32—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof from compositions containing microballoons, e.g. syntactic foams
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2351/00—Characterised by the use of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Derivatives of such polymers
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2351/00—Characterised by the use of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Derivatives of such polymers
- C08J2351/08—Characterised by the use of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Derivatives of such polymers grafted on to macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
Abstract
The invention relates to a photosensitive resin and a preparation method and application thereof. The photosensitive resin comprises the following components in parts by weight: 10 to 60 parts of free radical type prepolymer, 20 to 80 parts of active diluent, 0.1 to 10 parts of free radical initiator, 0.5 to 20 parts of foaming agent and 0 to 5 parts of nano color paste. By adjusting the types and the contents of the components in the photosensitive resin, the photosensitive cured resin cured by the photosensitive resin has good fracture extensibility and flexibility, and can bear stress change and strength change generated by foaming of a foaming agent. The photosensitive resin is suitable for the field of 3D printing and is used for preparing a low-specific-gravity material by 3D printing.
Description
Technical Field
The invention relates to the technical field of high polymer materials, in particular to photosensitive resin and a preparation method and application thereof.
Background
Photosensitive resin, commonly known as UV resin, mainly consists of a polymer monomer and a prepolymer, wherein a photosensitizer is added, and polymerization reaction is caused under the irradiation of ultraviolet light with a certain wavelength to complete solid-state conversion, so that photosensitive curing resin is obtained. Photosensitive resin is widely used in the field of 3D printing due to its properties of photocuring rapid prototyping. The conventional photosensitive resins are mostly high-hardness resins having high hardness, and accordingly, having undesirable elongation, poor flexibility, and being difficult to endure large stress variation and volume variation, subject to curing speed, and thus it is difficult to obtain a resin having low density by foam-modifying the same.
Disclosure of Invention
Therefore, it is necessary to provide a photosensitive resin which has better extensibility and flexibility and can be modified by foaming, and a preparation method and an application thereof.
In addition, a photosensitive cured resin prepared by curing the photosensitive resin and application thereof are also provided.
In addition, a 3D printing piece and a 3D printing method adopting the photosensitive resin are also provided.
In one aspect of the invention, the photosensitive resin comprises the following components in parts by mass:
wherein the free radical type prepolymer is at least one selected from polyacrylate prepolymer, aliphatic polyurethane acrylate, aromatic polyurethane acrylate, polyester acrylate, amino acrylate and polyether acrylate;
the active diluent is at least one selected from methoxy polyethylene glycol monoacrylate, polyethylene glycol dimethacrylate, trimethylolpropane formal acrylate, isobornyl acrylate, dodecyl acrylate, alkoxylated phenol acrylate, 1, 6-hexanediol diacrylate, tripropylene glycol diacrylate, lauryl acrylate, lauryl methacrylate, ethoxy ethyl acrylate, isooctyl acrylate and isobornyl methacrylate.
In some embodiments, the free radical type prepolymer is 10 to 40 parts by weight.
In some embodiments, the reactive diluent is 35 to 70 parts by mass.
In some of the examples, the free radical initiator is 0.1 to 10 parts by mass.
In some embodiments, the foaming agent is 1 to 10 parts by mass.
In some embodiments, the nano color paste is 0 to 2.5 parts by mass.
In some of these embodiments, the free radical initiator is selected from at least one of 1-hydroxycyclohexyl phenyl ketone, (2,4, 6-trimethylbenzoyl) diphenyl phosphine oxide, diphenyl (2,4, 6-trimethylbenzoyl) phosphine oxide, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) butanone, benzophenone, chlorinated benzophenone, benzoin dimethyl ether, and 2, 4-diethylthioxanthone.
In some of these embodiments, the foaming agent is selected from at least one of a microsphere foaming agent, a carbonate complex foaming powder, an azodicarbonamide foaming powder, and a sodium alpha-olefin sulfonate foaming agent.
In some of these embodiments, the blowing agent has a foaming temperature of 140 ℃ to 160 ℃.
In another aspect of the present invention, there is also provided a method for preparing a photosensitive resin, comprising the steps of:
the components of the foamable photosensitive resin composition are stirred and mixed at 30 to 40 ℃.
In another aspect of the present invention, there is also provided a photosensitive curing resin obtained by curing the above photosensitive resin.
In another aspect of the invention, a light resin is provided, which is obtained by subjecting the photosensitive curing resin to a thermal foaming treatment.
In another aspect of the invention, the application of the foamable photosensitive resin composition in 3D printing is also provided.
In another aspect of the present invention, a 3D printing method is further provided, including the steps of: and carrying out photocuring 3D printing by adopting the photosensitive resin.
In another aspect of the invention, a 3D formed part is also provided, which is formed by 3D printing using the photosensitive resin.
The components of the photosensitive resin comprise a free radical prepolymer, an active diluent, a free radical initiator, a foaming agent and nano color paste with specific contents, wherein the free radical prepolymer and the active diluent are specific materials. By adjusting the types and the contents of the components of the photosensitive resin, the photosensitive resin has good fracture extensibility after being cured, has good flexibility after being cured, and can bear stress change and strength change generated when a foaming agent is foamed, so that foaming modification can be performed. The photosensitive resin is suitable for the field of 3D printing and is used for 3D printing to prepare low-density 3D printing parts.
Detailed Description
In order that the invention may be more fully understood, reference will now be made to the following description. The present invention may be embodied in many different forms and is not limited to the embodiments described herein. Rather, these embodiments are provided so that this disclosure will be thorough and complete.
Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. The terminology used in the description of the invention herein is for the purpose of describing particular embodiments only and is not intended to be limiting of the invention. As used herein, the term "and/or" includes any and all combinations of one or more of the associated listed items.
The invention provides a photosensitive resin which comprises the following components in parts by weight:
wherein the free radical type prepolymer is selected from at least one of polyacrylate prepolymer, aliphatic polyurethane acrylate, aromatic polyurethane acrylate, polyester acrylate, amino acrylate and polyether acrylate;
the reactive diluent is at least one selected from methoxy polyethylene glycol monoacrylate, polyethylene glycol dimethacrylate, trimethylolpropane formal acrylate, isobornyl acrylate, dodecyl acrylate, alkoxylated phenol acrylate, 1, 6-hexanediol diacrylate, tripropylene glycol diacrylate, lauryl acrylate, lauryl methacrylate, ethoxy ethyl acrylate, isooctyl acrylate and isobornyl methacrylate.
The components of the photosensitive resin comprise a free radical prepolymer, an active diluent, a free radical initiator, a foaming agent and nano color paste with specific contents, wherein the free radical prepolymer and the active diluent are specific materials. By adjusting the types and the contents of the components of the photosensitive resin, the photosensitive resin has good fracture extensibility after being cured, has good flexibility after being cured, and can bear stress change and strength change generated when a foaming agent is foamed, so that foaming modification can be performed. The photosensitive resin is suitable for the field of 3D printing and is used for 3D printing to prepare low-density 3D printing parts.
In some embodiments, the photosensitive resin comprises 10 to 40 parts by weight of the free radical type prepolymer. Further, the mass portion of the free radical prepolymer is 15 to 35. Further, the mass portion of the free radical prepolymer is 20-30.
In some embodiments, the reactive diluent is 35 to 70 parts by mass of the photosensitive resin. In some of the examples, the reactive diluent is 40 to 60 parts by mass. Further, the mass portion of the active diluent is 45-55 portions.
In some of these embodiments, the free radical initiator is selected from at least one of 1-hydroxycyclohexyl phenyl ketone, (2,4, 6-trimethylbenzoyl) diphenyl phosphine oxide, diphenyl (2,4, 6-trimethylbenzoyl) phosphine oxide, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) butanone, benzophenone, chlorinated benzophenone, benzoin dimethyl ether, and 2, 4-diethylthioxanthone. In some embodiments, the amount of the radical initiator is 0.1 to 10 parts by mass in the photosensitive resin. Further, the mass part of the radical initiator is 0.1 part, 0.5 part, 0.8 part, 1 part, 2 parts, 3 parts, 4 parts, 5 parts, 6 parts, 7 parts, 8 parts, 9 parts or 10 parts.
The nanometer color paste is used for adjusting the color of the photosensitive resin composition so as to meet the preparation requirements of resin products with different colors. In some of these embodiments, the nano color paste is selected from at least one of a red UV color paste, a blue UV color paste, a violet UV color paste, a green UV color paste, a yellow UV color paste, and a black UV color paste. In some embodiments, the nano color paste is 0 to 2.5 parts by weight. It can be understood that no special requirement is required for the color of the foamable photosensitive resin composition, and no nano color paste can be added, namely the nano color paste is 0 part by mass.
In some of these embodiments, the foaming agent is selected from at least one of a microsphere foaming agent, a carbonate complex foaming powder, an azodicarbonamide foaming powder, and a sodium alpha-alkenyl sulfonate foaming agent. Preferably, the blowing agent is a microsphere blowing agent. In some embodiments, the foaming agent is 1 to 10 parts by mass of the photosensitive resin. Specifically, the foaming agent is 1 part, 2 parts, 3 parts, 4 parts, 5 parts, 6 parts, 7 parts, 8 parts, 9 parts or 10 parts by mass.
In some of these embodiments, the blowing agent has a foaming temperature of 140 ℃ to 160 ℃. In some embodiments, the foaming temperature of the blowing agent is 150 ℃.
In some embodiments, the photosensitive resin comprises the following components in parts by mass:
in some embodiments, the photosensitive resin comprises the following components in parts by mass:
another embodiment of the present invention also provides a method for preparing a photosensitive resin, comprising the steps of:
the components of the foamable photosensitive resin composition are stirred and mixed at 30 to 40 ℃.
When the stirring temperature is too low, the free radical type prepolymer is not easy to stir; when the stirring temperature is too high, polymerization occurs. The premix is controlled to be stirred at 30-40 ℃, so that the raw materials can be prevented from generating polymerization reaction, and the premix is convenient to stir uniformly. In some of these embodiments, the temperature of the agitation treatment is 30 ℃, 31 ℃, 32 ℃, 33 ℃, 34 ℃, 35 ℃, 36 ℃, 37 ℃, 38 ℃, 39 ℃ or 40 ℃.
The invention also provides a photosensitive curing resin which is prepared by curing the photosensitive resin. The photosensitive curing resin has good fracture extensibility and flexibility, and can bear large stress change. In some of these embodiments, the elongation at break of the photosensitive curable resin is 55% to 230%.
The invention also provides a light resin which is obtained by carrying out thermal foaming treatment on the photosensitive curing resin. By subjecting the photosensitive resin to a thermal foaming treatment, a porous lightweight resin can be obtained. In some of these embodiments, the thermal foaming process is heating the photocurable resin at 140 ℃ to 160 ℃. In some of these embodiments, the lightweight resin has a density of 0.2g/cm3～0.95g/cm3. Further, the method can be used for preparing a novel materialThe density of the resin after foaming is 0.4g/cm3～0.9g/cm3。
The invention also provides application of the photosensitive resin in 3D printing. Due to the photocuring property, the photosensitive resin can be applied to 3D printing technology and used as a raw material for preparing various devices or parts.
Another embodiment of the present invention further provides a 3D printing method, including the steps of: and carrying out photocuring 3D printing by adopting the photosensitive resin.
In some of these embodiments, the photocuring 3D printing is performed using commercially available DLP, LCD, or extruded photocuring modeling 3D printing equipment.
The invention further provides a 3D formed part which is formed by 3D printing through the photosensitive resin.
The photosensitive resin of the present invention is further illustrated by the following specific examples. The selection and content of the raw materials of examples 1-6 and comparative examples 1-2 are shown in Table 1.
Example 1:
the photosensitive resin of this example was composed of the following components: 25g of polyacrylate, 30g of isobornyl acrylate, 20g of trimethylolpropane formal acrylate, 20g of dodecyl acrylate, 2g of (2,4, 6-trimethylbenzoyl) diphenyl phosphine oxide, 3g of microsphere foaming agent and 0.5g of nano color paste.
Weighing 25g of polyacrylate, 30g of isobornyl acrylate, 20g of trimethylolpropane formal acrylate, 20g of dodecyl acrylate, 2g of (2,4, 6-trimethylbenzoyl) diphenylphosphine oxide, 3g of microsphere foaming agent and 0.5g of nano color paste, adding into a mixing device, heating to 40 ℃, stirring for 90min at the rotating speed of 400rpm, and carrying out photocuring 3D printing to obtain the photosensitive curing resin.
Example 2:
the photosensitive resin of this example was composed of the following components: 35g of urethane acrylate, 25g of polyethylene glycol dimethacrylate, 20g of trimethylolpropane formal acrylate, 15g of lauryl acrylate, 2g of (2,4, 6-trimethylbenzoyl) diphenyl phosphine oxide, 2g of microsphere foaming agent and 1g of nano color paste.
Weighing 35g of urethane acrylate, 25g of polyethylene glycol dimethacrylate, 20g of trimethylolpropane formal acrylate, 15g of lauryl acrylate, 2g of (2,4, 6-trimethylbenzoyl) diphenyl phosphine oxide, 2g of microsphere foaming agent and 1g of nano color paste, adding into a mixing device, heating to 40 ℃, stirring for 90min at the rotating speed of 400rpm, and carrying out photocuring 3D printing to obtain the photosensitive curing resin.
Example 3:
the photosensitive resin of this example was composed of the following components: 25g of polyacrylate, 10g of methoxy polyethylene glycol monoacrylate, 40g of trimethylolpropane formal acrylate, 15g of ethoxy ethyl acrylate, 2g of (2,4, 6-trimethylbenzoyl) diphenyl phosphine oxide, 5g of microsphere foaming agent and 1g of nano color paste.
Weighing 25g of polyacrylate, 10g of methoxy polyethylene glycol monoacrylate, 40g of trimethylolpropane formal acrylate, 15g of ethoxy ethyl acrylate, 2g of (2,4, 6-trimethylbenzoyl) diphenyl phosphine oxide, 5g of microsphere foaming agent and 1g of nano color paste, adding into a mixing device, heating to 40 ℃, stirring for 90min at the rotating speed of 400rpm, and carrying out photocuring 3D printing to obtain the photosensitive curing resin.
Example 4:
the photosensitive resin of this example was composed of the following components: 30g of urethane acrylate, 40g of polyethylene glycol dimethacrylate, 20g of trimethylolpropane formal acrylate, 5g of lauryl acrylate, 2g of (2,4, 6-trimethylbenzoyl) diphenyl phosphine oxide, 4g of microsphere foaming agent and 1g of nano color paste.
Weighing 30g of urethane acrylate, 40g of polyethylene glycol dimethacrylate, 20g of trimethylolpropane formal acrylate, 5g of lauryl acrylate, 2g of (2,4, 6-trimethylbenzoyl) diphenyl phosphine oxide, 4g of microsphere foaming agent and 1g of nano color paste, adding into a mixing device, heating to 40 ℃, stirring for 90min at the rotating speed of 400rpm, and carrying out photocuring 3D printing to obtain the photosensitive curing resin.
Example 5:
the photosensitive resin of this example was composed of the following components: 10g of polyacrylate, 40g of polyethylene glycol dimethacrylate, 30g of trimethylolpropane formal acrylate, 10g of lauryl acrylate, 2g of (2,4, 6-trimethylbenzoyl) diphenyl phosphine oxide, 20g of microsphere foaming agent and 1g of nano color paste.
Weighing 10g of polyacrylate, 40g of polyethylene glycol dimethacrylate, 30g of trimethylolpropane formal acrylate, 10g of lauryl acrylate, 2g of (2,4, 6-trimethylbenzoyl) diphenyl phosphine oxide, 20g of microsphere foaming agent and 1g of nano color paste, adding into a mixing device, heating to 40 ℃, stirring for 90min at the rotating speed of 400rpm, and carrying out photocuring 3D printing to obtain the photosensitive curing resin.
Example 6:
the photosensitive resin of this example was composed of the following components: 60g of urethane acrylate, 10g of trimethylolpropane formal acrylate, 10g of lauryl acrylate, 2g of (2,4, 6-trimethylbenzoyl) diphenyl phosphine oxide, 0.5g of microsphere foaming agent and 1g of nano color paste.
Weighing 60g of urethane acrylate, 10g of trimethylolpropane formal acrylate, 10g of lauryl acrylate, 2g of (2,4, 6-trimethylbenzoyl) diphenylphosphine oxide, 0.5g of microsphere foaming agent and 1g of nano color paste, adding into a mixing device, heating to 40 ℃, stirring for 90min at the rotating speed of 400rpm, and carrying out photocuring 3D printing to obtain the photosensitive curing resin.
Comparative example 1:
the photosensitive resin of this comparative example was composed of the following components: 70g of polyacrylate, 10g of isobornyl acrylate, 2g of (2,4, 6-trimethylbenzoyl) diphenylphosphine oxide, 3g of microsphere foaming agent and 0.5g of nano color paste.
Weighing 70g of polyacrylate, 10g of isobornyl acrylate, 2g of (2,4, 6-trimethylbenzoyl) diphenylphosphine oxide, 3g of microsphere foaming agent and 0.5g of nano color paste, adding into a mixing device, heating to 40 ℃, stirring at the rotating speed of 400rpm for 90min, and carrying out photocuring 3D printing to obtain the photosensitive curing resin.
Comparative example 2:
the photosensitive resin of this comparative example was composed of the following components: 5g of polyacrylate, 30g of isobornyl acrylate, 30g of trimethylolpropane formal acrylate, 30g of dodecyl acrylate, 2g of (2,4, 6-trimethylbenzoyl) diphenyl phosphine oxide, 3g of microsphere foaming agent and 0.5g of nano color paste.
Weighing 5g of polyacrylate, 30g of isobornyl acrylate, 30g of trimethylolpropane formal acrylate, 30g of dodecyl acrylate, 2g of (2,4, 6-trimethylbenzoyl) diphenyl phosphine oxide, 3g of microsphere foaming agent and 0.5g of nano color paste, adding into a mixing device, heating to 40 ℃, stirring for 90min at the rotating speed of 400rpm, and carrying out photocuring 3D printing to obtain the photosensitive curing resin.
Comparative example 3:
comparative example 3 is a 3D printing resin produced from a commercially available photosensitive resin (manufacturer's brand of creative three-dimensional high temperature compression molding resin high temperature resin).
TABLE 1
The elongation at break of the photosensitive cured resins prepared in examples 1 to 6 and comparative examples 1 to 3 was measured according to ASTM D638-98, and the results are shown in Table 2.
The photosensitive cured resins prepared in examples 1 to 6 and comparative examples 1 to 2 were subjected to a heat treatment at 150 ℃ to carry out a foaming treatment, thereby obtaining a lightweight resin. The density of the light weight resin, the test results are shown in table 2.
TABLE 2
As can be seen from the relevant data described in Table 2, the elongation at break of the commercially available 3D printing resin of comparative example 3 was extremely low, the flexibility of the obtained photosensitive cured resin was poor, and the photosensitive cured resin of comparative example 3 could not be subjected to foaming treatment due to the absence of the addition of the foaming agent, and had a density of 1.21g/cm3. The elongation at break of the photosensitive cured resin prepared in the comparative examples 1-2 is slightly higher than that of the commercially available 3D printing resin prepared in the comparative example 3, but the elongation at break is still low, the flexibility of the photosensitive cured resin is poor, the stress generated by foaming treatment is hard to bear, the photosensitive cured resin in the comparative examples 1-2 is subjected to expansion fracture in the foaming process, and the foaming modified light resin cannot be obtained. The photosensitive cured resins prepared in examples 1 to 6 have high elongation at break, and the density of the resin material can be reduced through foaming treatment to obtain light resin. To a certain extent, the greater the elongation at break of the photosensitive cured resin, the greater the amount of the foaming agent added to the photosensitive resin, and the lower the density of the light resin obtained after foaming the prepared photosensitive cured resin. The light resin prepared by the photosensitive resin of the embodiment 5 can achieve the lightest effect, but the appearance of 3D printing is slightly distorted, and the accuracy of a printed product is inferior to that of the photosensitive resin of the embodiments 1-4. The photosensitive cured resin prepared in example 6 is inferior to the photosensitive cured resins prepared in examples 1 to 5 in the degree of density reduction after foaming because the amount of the foaming agent added in the photosensitive resin is small. The light resin of embodiments 1 to 4 has both appropriate density and printing simulation degree, and is particularly suitable for low specific gravity materials in the field of aerospace.
The technical features of the embodiments described above may be arbitrarily combined, and for the sake of brevity, all possible combinations of the technical features in the embodiments described above are not described, but should be considered as being within the scope of the present specification as long as there is no contradiction between the combinations of the technical features.
The above-mentioned embodiments only express several embodiments of the present invention, so as to understand the technical solutions of the present invention specifically and in detail, but not to be understood as the limitation of the protection scope of the invention. It should be noted that, for a person skilled in the art, several variations and modifications can be made without departing from the inventive concept, which falls within the scope of the present invention. It should be understood that the technical solutions provided by the present invention, which are obtained by logical analysis, reasoning or limited experiments, are within the scope of the present invention as set forth in the appended claims. Therefore, the protection scope of the patent of the invention is subject to the content of the appended claims, and the description can be used for explaining the content of the claims.
Claims (11)
1. The photosensitive resin is characterized by comprising the following components in parts by mass:
wherein the free radical type prepolymer is at least one selected from polyacrylate prepolymer, aliphatic polyurethane acrylate, aromatic polyurethane acrylate, polyester acrylate, amino acrylate and polyether acrylate;
the active diluent is at least one selected from methoxy polyethylene glycol monoacrylate, polyethylene glycol dimethacrylate, trimethylolpropane formal acrylate, isobornyl acrylate, dodecyl acrylate, alkoxylated phenol acrylate, 1, 6-hexanediol diacrylate, tripropylene glycol diacrylate, lauryl acrylate, lauryl methacrylate, ethoxy ethyl acrylate, isooctyl acrylate and isobornyl methacrylate.
2. The photosensitive resin according to claim 1, wherein the radical type prepolymer is 10 to 40 parts by mass;
and/or 35-70 parts of active diluent;
and/or 0.1 to 10 parts of free radical initiator;
and/or 1-10 parts of foaming agent;
and/or 0-2.5 parts of nano color paste.
3. The photosensitive resin according to claim 1 or 2, wherein the radical initiator is at least one selected from the group consisting of 1-hydroxycyclohexyl phenyl ketone, (2,4, 6-trimethylbenzoyl) diphenyl phosphine oxide, diphenyl (2,4, 6-trimethylbenzoyl) phosphine oxide, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) butanone, benzophenone, chlorinated benzophenone, benzoin dimethyl ether, and 2, 4-diethylthioxanthone.
4. The photosensitive resin according to claim 1 or 2, wherein the foaming agent is at least one selected from a microsphere foaming agent, a carbonate complex foaming powder, an azodicarbonamide foaming powder and an alpha-sodium alkenyl sulfonate foaming agent.
5. The photosensitive resin according to claim 1 or 2, wherein the foaming temperature of the foaming agent is 140 ℃ to 160 ℃.
6. A method for preparing a photosensitive resin, comprising the steps of:
the foamable photosensitive resin composition according to any one of claims 1 to 5, wherein the respective components are mixed with stirring at 30 to 40 ℃.
7. A photosensitive curable resin obtained by curing the photosensitive resin according to any one of claims 1 to 5.
8. A lightweight resin obtained by subjecting the photosensitive curable resin according to claim 7 to a thermal foaming treatment.
9. Use of the photosensitive resin of any one of claims 1 to 5 in 3D printing.
10. A3D printing method is characterized by comprising the following steps:
photocuring 3D printing is performed using the photosensitive resin according to any one of claims 1 to 5.
11. A 3D molded article characterized by being subjected to 3D printing molding using the photosensitive resin according to any one of claims 1 to 5.
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