CN113527831B - Photosensitive resin, preparation method and forming method of photosensitive resin - Google Patents
Photosensitive resin, preparation method and forming method of photosensitive resin Download PDFInfo
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- CN113527831B CN113527831B CN202110930766.XA CN202110930766A CN113527831B CN 113527831 B CN113527831 B CN 113527831B CN 202110930766 A CN202110930766 A CN 202110930766A CN 113527831 B CN113527831 B CN 113527831B
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- photosensitive resin
- photoinitiator
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- amino resin
- curing
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- 229920005989 resin Polymers 0.000 title claims abstract description 86
- 239000011347 resin Substances 0.000 title claims abstract description 86
- 238000000034 method Methods 0.000 title claims abstract description 29
- 238000002360 preparation method Methods 0.000 title abstract description 12
- 229920003180 amino resin Polymers 0.000 claims abstract description 59
- 239000011259 mixed solution Substances 0.000 claims abstract description 18
- 238000002156 mixing Methods 0.000 claims abstract description 14
- 239000012752 auxiliary agent Substances 0.000 claims abstract description 13
- 239000003085 diluting agent Substances 0.000 claims abstract description 12
- 238000003756 stirring Methods 0.000 claims abstract description 12
- 238000000465 moulding Methods 0.000 claims abstract description 11
- -1 acrylic ester Chemical class 0.000 claims abstract description 3
- JMANVNJQNLATNU-UHFFFAOYSA-N oxalonitrile Chemical compound N#CC#N JMANVNJQNLATNU-UHFFFAOYSA-N 0.000 claims description 20
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims description 16
- LEJBBGNFPAFPKQ-UHFFFAOYSA-N 2-(2-prop-2-enoyloxyethoxy)ethyl prop-2-enoate Chemical compound C=CC(=O)OCCOCCOC(=O)C=C LEJBBGNFPAFPKQ-UHFFFAOYSA-N 0.000 claims description 12
- HCLJOFJIQIJXHS-UHFFFAOYSA-N 2-[2-[2-(2-prop-2-enoyloxyethoxy)ethoxy]ethoxy]ethyl prop-2-enoate Chemical compound C=CC(=O)OCCOCCOCCOCCOC(=O)C=C HCLJOFJIQIJXHS-UHFFFAOYSA-N 0.000 claims description 12
- 230000001678 irradiating effect Effects 0.000 claims description 9
- OMIGHNLMNHATMP-UHFFFAOYSA-N 2-hydroxyethyl prop-2-enoate Chemical compound OCCOC(=O)C=C OMIGHNLMNHATMP-UHFFFAOYSA-N 0.000 claims description 8
- HVVWZTWDBSEWIH-UHFFFAOYSA-N [2-(hydroxymethyl)-3-prop-2-enoyloxy-2-(prop-2-enoyloxymethyl)propyl] prop-2-enoate Chemical compound C=CC(=O)OCC(CO)(COC(=O)C=C)COC(=O)C=C HVVWZTWDBSEWIH-UHFFFAOYSA-N 0.000 claims description 8
- 229920002818 (Hydroxyethyl)methacrylate Polymers 0.000 claims description 6
- UDJZTGMLYITLIQ-UHFFFAOYSA-N 1-ethenylpyrrolidine Chemical compound C=CN1CCCC1 UDJZTGMLYITLIQ-UHFFFAOYSA-N 0.000 claims description 6
- QZPSOSOOLFHYRR-UHFFFAOYSA-N 3-hydroxypropyl prop-2-enoate Chemical compound OCCCOC(=O)C=C QZPSOSOOLFHYRR-UHFFFAOYSA-N 0.000 claims description 6
- DXPPIEDUBFUSEZ-UHFFFAOYSA-N 6-methylheptyl prop-2-enoate Chemical compound CC(C)CCCCCOC(=O)C=C DXPPIEDUBFUSEZ-UHFFFAOYSA-N 0.000 claims description 6
- WOBHKFSMXKNTIM-UHFFFAOYSA-N Hydroxyethyl methacrylate Chemical compound CC(=C)C(=O)OCCO WOBHKFSMXKNTIM-UHFFFAOYSA-N 0.000 claims description 6
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 claims description 6
- DAKWPKUUDNSNPN-UHFFFAOYSA-N Trimethylolpropane triacrylate Chemical compound C=CC(=O)OCC(CC)(COC(=O)C=C)COC(=O)C=C DAKWPKUUDNSNPN-UHFFFAOYSA-N 0.000 claims description 6
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 claims description 6
- YDKNBNOOCSNPNS-UHFFFAOYSA-N methyl 1,3-benzoxazole-2-carboxylate Chemical compound C1=CC=C2OC(C(=O)OC)=NC2=C1 YDKNBNOOCSNPNS-UHFFFAOYSA-N 0.000 claims description 6
- 229920003275 CYMEL® 325 Polymers 0.000 claims description 4
- 238000004519 manufacturing process Methods 0.000 claims 1
- 238000005452 bending Methods 0.000 abstract description 5
- 238000010438 heat treatment Methods 0.000 abstract description 5
- 239000007788 liquid Substances 0.000 abstract description 4
- 238000001723 curing Methods 0.000 description 49
- 238000000016 photochemical curing Methods 0.000 description 11
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 9
- 230000000052 comparative effect Effects 0.000 description 8
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 7
- 239000000463 material Substances 0.000 description 5
- 239000000126 substance Substances 0.000 description 5
- 239000012855 volatile organic compound Substances 0.000 description 5
- 230000037228 dieting effect Effects 0.000 description 4
- 238000001035 drying Methods 0.000 description 3
- 230000009977 dual effect Effects 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 229920002521 macromolecule Polymers 0.000 description 3
- 238000001029 thermal curing Methods 0.000 description 3
- 238000010146 3D printing Methods 0.000 description 2
- 239000000853 adhesive Substances 0.000 description 2
- 230000001070 adhesive effect Effects 0.000 description 2
- 230000000903 blocking effect Effects 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000013008 moisture curing Methods 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 229920000728 polyester Polymers 0.000 description 2
- 238000006116 polymerization reaction Methods 0.000 description 2
- 229920002635 polyurethane Polymers 0.000 description 2
- 239000004814 polyurethane Substances 0.000 description 2
- KCTAWXVAICEBSD-UHFFFAOYSA-N prop-2-enoyloxy prop-2-eneperoxoate Chemical compound C=CC(=O)OOOC(=O)C=C KCTAWXVAICEBSD-UHFFFAOYSA-N 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 1
- 238000004891 communication Methods 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 230000005284 excitation Effects 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 239000012767 functional filler Substances 0.000 description 1
- 238000013007 heat curing Methods 0.000 description 1
- 239000011256 inorganic filler Substances 0.000 description 1
- 229910003475 inorganic filler Inorganic materials 0.000 description 1
- 238000007639 printing Methods 0.000 description 1
- 150000003384 small molecules Chemical class 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 230000002195 synergetic effect Effects 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
- C08L51/00—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers
- C08L51/08—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers grafted on to macromolecular compounds obtained otherwise than by reactions only involving unsaturated carbon-to-carbon bonds
-
- 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
- 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
- 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
- C08F283/01—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to unsaturated polyesters
-
- 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
- C08F283/10—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to polymers containing more than one epoxy radical per molecule
- C08F283/105—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to polymers containing more than one epoxy radical per molecule on to unsaturated polymers containing more than one epoxy radical per molecule
Abstract
The invention provides a photosensitive resin, a preparation method and a molding method of the photosensitive resin, wherein the preparation method comprises the following steps: uniformly mixing and stirring an acrylic ester prepolymer, a reactive diluent, a photoinitiator and an auxiliary agent to obtain a mixed solution, wherein the auxiliary agent comprises amino resin; and obtaining the photosensitive resin based on the mixed liquid. According to the invention, the amino resin can form a stronger three-dimensional net structure in a heating environment, so that the curing degree of the inner layer of the cured model is improved, and the mechanical properties including tensile bending property, impact resistance and the like and hardness of the model can be improved.
Description
Technical Field
The invention relates to the technical field of 3D printing, in particular to a photosensitive resin, a preparation method and a forming method of the photosensitive resin.
Background
Photosensitive resins are resins that can be cured rapidly in a relatively short period of time after being irradiated with ultraviolet light.
At present, functional fillers such as anisotropic conductive adhesive, LED fluorescent adhesive and the like in photosensitive resin generally have light blocking performance, the photosensitive resin is influenced by the light blocking fillers, and in the light curing process, the inner layer of the model is not thoroughly cured, and the molding effect is poor, so that the mechanical performance and hardness of the model are poor.
Disclosure of Invention
The embodiment of the invention provides photosensitive resin, a preparation method and a forming method of the photosensitive resin, which are used for solving the problem that the cured photosensitive resin in the prior art is low in mechanical property and hardness.
In order to solve the technical problems, the embodiment of the invention adopts the following technical scheme:
in a first aspect, an embodiment of the present invention provides a method for preparing a photosensitive resin, the method comprising:
uniformly mixing and stirring an acrylic ester prepolymer, a reactive diluent, a photoinitiator and an auxiliary agent to obtain a mixed solution, wherein the auxiliary agent comprises amino resin;
and obtaining the photosensitive resin based on the mixed liquid.
Optionally, the content of the amino resin is 5% -45%.
Optionally, the amino resin is a methylated amino resin.
Optionally, the reactive diluent comprises at least one of hydroxypropyl acrylate, hydroxyethyl acrylate, vinyl acetate, methyl methacrylate, hydroxyethyl methacrylate, tetraethylene glycol diacrylate, pentaerythritol triacrylate, styrene, vinyl pyrrolidine, diethylene glycol diacrylate, trimethylolpropane triacrylate, isooctyl acrylate, neopentyl glycol diacrylate; and/or the number of the groups of groups,
the amino resin comprises at least one of cyanogen CYMEL308 amino resin, cyanogen CYMEL325 amino resin, FX-AM5160 general amino resin, cyanogen CYMEL303 amino resin and FB717 methylated amino resin.
Optionally, the photoinitiator comprises at least one of a BP photoinitiator, a 1173 photoinitiator, a 819 photoinitiator, a TPO photoinitiator.
Optionally, the duration of the mixing and stirring is 30 minutes to 180 minutes.
In a second aspect, embodiments of the present invention provide a photosensitive resin prepared by the method provided in the first aspect.
In a third aspect, an embodiment of the present invention provides a molding method of a photosensitive resin, where the photosensitive resin is a photosensitive resin prepared by using the method provided in the first aspect, and the molding method includes:
pouring the photosensitive resin into a mold, and irradiating for a first preset time period by using a preset light source to obtain a first curing model;
and baking the first curing model for a second preset time to obtain a second curing model.
Optionally, the preset light source is ultraviolet light, and the wavelength of the ultraviolet light is any one of 350nm, 360nm, 380nm, 405nm or 410 nm.
Optionally, the baking temperature is not less than 60 ℃.
In the embodiment of the invention, the auxiliary agent containing the amino resin is added into the photosensitive resin, and the mold obtained by photo-curing the photosensitive resin is further baked during the subsequent curing and forming, so that the amino resin can form a stronger three-dimensional network structure in a heating environment, the resin micromolecules in the photosensitive resin further form a resin macromolecule network, the curing degree of the inner layer of the mold is improved, and the mechanical properties including stretching, bending property, impact resistance and the like and the hardness of the mold can be improved. In addition, the prepared photosensitive resin has no VOC emission, so that the photosensitive resin is environment-friendly, is a single-component system, has good chemical stability and can be stored for a long time.
Drawings
In order to more clearly illustrate the technical solutions of the embodiments of the present invention, the drawings that are needed in the description of the embodiments of the present invention will be briefly described below, and it is obvious that the drawings in the following description are only some embodiments of the present invention, and other drawings may be obtained according to these drawings without inventive effort to a person of ordinary skill in the art.
FIG. 1 is a flowchart of a method for preparing a photosensitive resin according to an embodiment of the present invention;
fig. 2 is a flowchart of a molding method of a photosensitive resin according to an embodiment of the present invention.
Detailed Description
The following description of the embodiments of the present invention will be made clearly and fully with reference to the accompanying drawings, in which it is evident that the embodiments described are some, but not all embodiments of the invention. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
The embodiment of the invention provides a preparation method of photosensitive resin.
Referring to fig. 1, fig. 1 is a flowchart of a preparation method of a photosensitive resin according to an embodiment of the invention. As shown in fig. 1, the preparation method comprises the following steps:
step 101, mixing and stirring acrylate prepolymer, reactive diluent, photoinitiator and auxiliary agent uniformly to obtain mixed solution, wherein the auxiliary agent comprises amino resin.
And 102, obtaining the photosensitive resin based on the mixed liquid.
In the embodiment of the invention, the photosensitive resin is added with the auxiliary agent containing the amino resin, and the amino resin can form a stronger three-dimensional network structure under a heating environment, so that the strength and the elasticity of the photosensitive resin are improved. Specifically, during the subsequent curing and forming, the mold obtained by photo-curing the photosensitive resin is further baked, the amino resin reacts with the photo-cured resin molecules, and the amino resin also reacts, so that the resin micromolecules in the photosensitive resin further form a resin macromolecule grid, the curing degree of the inner layer of the mold is improved, and the mechanical properties including tensile bending property, impact resistance and the like and the hardness of the mold can be improved. In addition, the photosensitive resin prepared in this way has no emission of volatile organic compounds (Volatile Organic Compounds, VOC), so that the photosensitive resin is environment-friendly, is a single-component system, has good chemical stability and can be stored for a long time.
It should be noted that, the reactive diluent may reduce the viscosity of the resin system in the photosensitive resin, and when the photosensitive resin is applied to a 3D printing scene, the photosensitive resin may meet the printing requirement, and in addition, the reactive diluent may also improve the mechanical properties of the photosensitive resin to a certain extent.
In specific implementation, the content of the amino resin is optionally 5% -45%. That is, the content of the amino resin in the mixed solution is 5% to 45%.
Optionally, the amino resin is a methylated amino resin. The methylated amino resin has better curing performance, better hardness, flexibility and outdoor weather resistance during curing, and can further improve the mechanical properties of a model formed by curing the photosensitive resin.
Further optionally, the amino resin comprises at least one of a cyanocyl 308 amino resin, a cyanocyl 303 amino resin, a cyanocyl 325 amino resin, an FX-AM5160 universal amino resin, and an FB717 methylated amino resin.
Optionally, the reactive diluent comprises at least one of hydroxypropyl acrylate, hydroxyethyl acrylate, vinyl acetate, methyl methacrylate, hydroxyethyl methacrylate, tetraethylene glycol diacrylate, pentaerythritol triacrylate, styrene, vinyl pyrrolidine, diethylene glycol diacrylate, trimethylolpropane triacrylate, isooctyl acrylate, neopentyl glycol diacrylate.
Optionally, the photoinitiator comprises at least one of a BP photoinitiator, a 1173 photoinitiator, a 819 photoinitiator, a TPO photoinitiator.
Optionally, the duration of the mixing and stirring is 30 minutes to 180 minutes, preferably 60 minutes.
The temperature of the mixing may be ordinary temperature, and preferably 25 to 40 ℃.
The embodiment of the invention also provides a photosensitive resin, which is prepared by the preparation method of the photosensitive resin provided by the embodiment of the invention.
In this embodiment, the photosensitive resin includes the following components: acrylate prepolymer, reactive diluent, photoinitiator and auxiliary agent, wherein the auxiliary agent comprises amino resin.
Optionally, the content of the amino resin is 5% -45%.
Optionally, the amino resin is a methylated amino resin.
Optionally, the reactive diluent comprises at least one of hydroxypropyl acrylate, hydroxyethyl acrylate, vinyl acetate, methyl methacrylate, hydroxyethyl methacrylate, tetraethylene glycol diacrylate, pentaerythritol triacrylate, styrene, vinyl pyrrolidine, diethylene glycol diacrylate, trimethylolpropane triacrylate, isooctyl acrylate, neopentyl glycol diacrylate; and/or the number of the groups of groups,
the amino resin comprises at least one of cyanogen CYMEL308 amino resin, cyanogen CYMEL325 amino resin, FX-AM5160 general amino resin, cyanogen CYMEL303 amino resin and FB717 methylated amino resin.
Optionally, the photoinitiator comprises at least one of a BP photoinitiator, a 1173 photoinitiator, a 819 photoinitiator, a TPO photoinitiator.
It should be noted that the photosensitive resin includes all technical features related to the photosensitive resin in the preparation method of the photosensitive resin, and all technical effects related to the photosensitive resin in the preparation method of the photosensitive resin can be achieved, so that repetition is avoided, and no description is repeated here.
The embodiment of the invention also provides a molding method of the photosensitive resin, wherein the photosensitive resin is provided by the embodiment of the invention.
Referring to fig. 2, fig. 2 is a flowchart of a molding method of photosensitive resin according to an embodiment of the invention. As shown in fig. 2, the molding method includes:
step 201, pouring the photosensitive resin into a mold, and irradiating a first preset time period by using a preset light source to obtain a first curing model.
And 202, baking the first curing model for a second preset time to obtain a second curing model.
In the embodiment of the present invention, the curing and forming method may be regarded as a dual curing system, where the crosslinking or polymerization reaction in the dual curing system is mainly performed through two stages, namely, a photo-curing stage and a thermal curing stage.
The step 201 is a photo-curing stage. In this stage, the acrylate prepolymer and reactive diluent in the liquid photosensitive resin react and solidify under the irradiation of a preset light source and the excitation of a photoinitiator, so as to quickly fix the shape. However, at this stage, the mold inner layer is not completely cured due to the influence of a part of light-blocking inorganic filler in the photosensitive resin. This stage may be referred to as "skin drying" of the model.
The step 202 is a heat curing stage. In this stage, the first curing model with "surface drying" in step 1 is baked, and under the heating condition, the amino resin will react with the resin molecules after photo-curing, and the amino resin will also react, so that the resin small molecules in the photosensitive resin further form a resin macromolecular grid, and the inner layer of the model is fully cured. This stage may be referred to as "live drying" of the model.
The photosensitive resin molding method provided by the embodiment of the invention combines the advantages of polymerization reaction in various photo-curing and thermal curing, forms a better synergistic effect, can improve the curing degree of the inner layer of the model, and improves the mechanical properties including tensile bending property, impact resistance and the like and the hardness of the model. Meanwhile, the application of a curing system of the photosensitive resin can be expanded to opaque media, base materials with complex shapes, ultra-thick coatings, colored coatings and the like.
In a specific implementation, optionally, the preset light source is ultraviolet light, and the wavelength of the ultraviolet light is any one of 350nm, 360nm, 380nm, 405nm or 410 nm. The first preset duration may be 5 minutes or 8 minutes, etc., and may specifically be determined according to the actual curing amount, which is not limited herein.
Optionally, the baking temperature is not less than 60 ℃. Preferably 120℃to 160 ℃. The second preset time period may be 8 minutes or 13 minutes, and may be specifically determined according to the actual curing amount, which is not limited herein.
It should be noted that the dual curing system may also be a photo-curing+moisture curing system, or a photo-curing+oxidation curing system, or a photo-curing+anaerobic curing system, where the reaction process and effect of the amino resin in the moisture curing, the oxidation curing and the anaerobic curing are substantially the same as those of the thermal curing, and will not be described herein.
Several specific examples and comparative examples among the examples of the present invention are described below:
example 1
Step 1: 18 parts of difunctional polyester acrylate prepolymer, 15 parts of hydroxyethyl acrylate, 10 parts of styrene, 10 parts of isooctyl acrylate, 12 parts of neopentyl glycol diacrylate, 8 parts of pentaerythritol triacrylate, 10 parts of cyanotecymel 308 amino resin, 2 parts of 1173 photoinitiator and 2 parts of BP photoinitiator are weighed into a beaker.
Step 2: and (3) uniformly mixing and stirring the weighed substances in the step (1) to obtain a mixed solution, then placing a proper amount of the mixed solution into a test mold, and irradiating for 5 minutes by using a 350nm ultraviolet lamp to obtain a first curing model.
Step 3: and placing the first curing model in an oven at 120 ℃ for baking for 10 minutes to obtain a second curing model. And then taking out the second curing model to perform mechanical property test.
Example 2
Step 1: 22 parts of difunctional epoxy acrylate prepolymer, 18 parts of hydroxypropyl acrylate, 10 parts of vinyl acetate, 10 parts of methyl methacrylate, 15 parts of tetraethylene glycol diacrylate, 7 parts of pentaerythritol triacrylate, 9 parts of cyanogen CYMEL325 amino resin, 7 parts of FX-AM5160 general amino resin, 2 parts of 1173 photoinitiator and 3 parts of 819 photoinitiator are weighed into a beaker.
Step 2: and (3) uniformly mixing and stirring the weighed substances in the step (1) to obtain a mixed solution, then placing a proper amount of the mixed solution into a test mold, and irradiating for 5 minutes by using a 380nm ultraviolet lamp to obtain a first curing model.
Step 3: and placing the first curing model in an oven at 120 ℃ for baking for 13 minutes to obtain a second curing model. And then taking out the second curing model to perform mechanical property test.
Example 3
Step 1: 25 parts of difunctional polyurethane acrylate prepolymer, 15 parts of hydroxyethyl acrylate, 8 parts of hydroxyethyl methacrylate, 10 parts of styrene, 10 parts of vinyl pyrrolidine, 12 parts of diethylene glycol diacrylate, 8 parts of trimethylolpropane triacrylate, 10 parts of cyanote CYMEL303 amino resin, 5 parts of FB717 methylated amino resin, 2 parts of TPO photoinitiator and 2 parts of 819 photoinitiator are weighed into a beaker.
Step 2: and (3) uniformly mixing and stirring the materials weighed in the step (1) to obtain a mixed solution, then placing a proper amount of the mixed solution into a test die, and irradiating for 5 minutes by using an ultraviolet lamp with the wavelength of 405 nm.
Step 3: and placing the first curing model in an oven at 160 ℃ for baking for 8 minutes to obtain a second curing model. And then taking out the second curing model to perform mechanical property test.
Comparative example 1
Step 1: 18 parts of difunctional polyester acrylate prepolymer, 15 parts of hydroxyethyl acrylate, 10 parts of styrene, 10 parts of isooctyl acrylate, 12 parts of neopentyl glycol diacrylate, 8 parts of pentaerythritol triacrylate, 2 parts of 1173 photoinitiator and 2 parts of BP photoinitiator are weighed into a beaker.
Step 2: and (3) uniformly mixing and stirring the materials weighed in the step (1) to obtain a mixed solution, then placing a proper amount of the mixed solution into a test die, and irradiating for 5 minutes by using a 350nm ultraviolet lamp.
Step 3: and placing the first curing model in an oven at 120 ℃ for baking for 10 minutes to obtain a second curing model. And then taking out the second curing model to perform mechanical property test.
Comparative example 2
Step 1: 22 parts of difunctional epoxy acrylate prepolymer, 18 parts of hydroxypropyl acrylate, 10 parts of vinyl acetate, 10 parts of methyl methacrylate, 15 parts of tetraethylene glycol diacrylate, 7 parts of pentaerythritol triacrylate, 7 parts of FX-AM5160 general amino resin, 2 parts of 1173 photoinitiator and 3 parts of 819 photoinitiator are weighed into a beaker.
Step 2: and (3) uniformly mixing and stirring the materials weighed in the step (1) to obtain a mixed solution, then placing a proper amount of the mixed solution into a test die, and irradiating for 5 minutes by using a 380nm ultraviolet lamp.
Step 3: and placing the first curing model in an oven at 120 ℃ for baking for 13 minutes to obtain a second curing model. And then taking out the second curing model to perform mechanical property test.
Comparative example 3
Step 1: 25 parts of difunctional polyurethane acrylate prepolymer, 15 parts of hydroxyethyl acrylate, 8 parts of hydroxyethyl methacrylate, 10 parts of styrene, 10 parts of vinyl pyrrolidine, 12 parts of diethylene glycol diacrylate, 8 parts of trimethylolpropane triacrylate, 5 parts of FB717 methylated amino resin, 2 parts of TPO photoinitiator and 2 parts of 819 photoinitiator are weighed into a beaker.
Step 2: and (3) uniformly mixing and stirring the materials weighed in the step (1) to obtain a mixed solution, then placing a proper amount of the mixed solution into a test die, and irradiating for 5 minutes by using an ultraviolet lamp with the wavelength of 405 nm.
Step 3: and placing the first curing model in an oven at 160 ℃ for baking for 8 minutes to obtain a second curing model. And then taking out the second curing model to perform mechanical property test.
As can be seen from table 1, example 1 was improved in flexural modulus, tensile modulus, notched impact strength and hardness as compared with comparative example 1, example 2 was improved in comparison with comparative example 2, and example 3 was improved in comparison with comparative example 3. And the mechanical property level of the photosensitive resin can be adjusted by controlling the content ratio of each component in the photosensitive resin and the type of the amino resin compared with the three of the embodiment 1, the embodiment 2 and the embodiment 3.
Table 1 summary of test results for examples and comparative samples
In summary, in the embodiment of the present invention, an auxiliary agent containing an amino resin is added to the photosensitive resin, and during the subsequent curing and forming, the mold can be made to reach "surface dry" by photo-curing the photosensitive resin, and then the mold obtained by photo-curing is further baked, wherein the amino resin can form a stronger three-dimensional network structure in a heating environment, so that the resin micromolecules in the photosensitive resin further form a resin macromolecule network, and the curing degree of the inner layer of the mold is improved, so that the mold can reach "solid" and the mechanical properties including tensile bending property, impact resistance and the like and hardness of the cured mold can be improved. In addition, the prepared photosensitive resin has no VOC emission, so that the photosensitive resin is environment-friendly, is a single-component system, has good chemical stability and can be stored for a long time.
It should be noted that, the various alternative embodiments described in the embodiments of the present invention may be implemented in combination with each other, or may be implemented separately, which is not limited to the embodiments of the present invention.
In the description of the present invention, it should be understood that the terms "upper," "lower," "left," "right," and the like indicate an orientation or a positional relationship based on that shown in the drawings, and are merely for convenience of description and for simplifying the description, and do not indicate or imply that the apparatus or element in question must have a specific orientation, as well as a specific orientation configuration and operation, and thus should not be construed as limiting the present invention. Furthermore, the terms "first," "second," and the like, are used for descriptive purposes only and are not to be construed as indicating or implying a relative importance or implicitly indicating the number of technical features indicated. Thus, a feature defining "a first" or "a second" may explicitly or implicitly include one or more such feature. In the description of the present invention, unless otherwise indicated, the meaning of "a plurality" is two or more.
In the description of the present invention, it should be noted that, unless explicitly specified and limited otherwise, the terms "mounted," "connected," and the like are to be construed broadly and may be, for example, fixedly connected, detachably connected, or integrally connected; can be mechanically or electrically connected; can be directly connected or indirectly connected through an intermediate medium, and can be communication between two elements. The specific meaning of the above terms in the present invention will be understood in specific cases by those of ordinary skill in the art.
The embodiments described above are described with reference to the drawings, and other different forms and embodiments are possible without departing from the principle of the invention, and therefore, the invention should not be construed as limited to the embodiments set forth herein. Rather, these embodiments are provided so that this disclosure will be thorough and complete, and will convey the scope of the invention to those skilled in the art. In the drawings, component dimensions and relative dimensions may be exaggerated for clarity. The terminology used herein is for the purpose of describing particular embodiments only and is not intended to be limiting. The terms "comprises," "comprising," and/or "includes," when used in this specification, specify the presence of stated features, integers, components, and/or groups thereof, but do not preclude the presence or addition of one or more other features, integers, components, and/or groups thereof. Unless otherwise indicated, a range of values includes the upper and lower limits of the range and any subranges therebetween.
While the foregoing is directed to the preferred embodiments of the present invention, it will be appreciated by those skilled in the art that various modifications and changes can be made without departing from the principles of the present invention, and such modifications and changes are intended to be within the scope of the present invention.
Claims (9)
1. A method for producing a photosensitive resin, comprising:
uniformly mixing and stirring an acrylic ester prepolymer, a reactive diluent, a photoinitiator and an auxiliary agent to obtain a mixed solution, wherein the auxiliary agent comprises amino resin;
obtaining the photosensitive resin based on the mixed solution;
wherein the amino resin comprises at least one of cyanogen CYMEL308 amino resin, cyanogen CYMEL325 amino resin and cyanogen CYMEL303 amino resin.
2. The method according to claim 1, wherein the content of the amino resin is 5% -45%.
3. The method of claim 1, wherein the reactive diluent comprises at least one of hydroxypropyl acrylate, hydroxyethyl acrylate, vinyl acetate, methyl methacrylate, hydroxyethyl methacrylate, tetraethylene glycol diacrylate, pentaerythritol triacrylate, styrene, vinyl pyrrolidine, diethylene glycol diacrylate, trimethylolpropane triacrylate, isooctyl acrylate, neopentyl glycol diacrylate.
4. The method of claim 1, wherein the photoinitiator comprises at least one of a BP photoinitiator, 1173 photoinitiator, 819 photoinitiator, TPO photoinitiator.
5. The method of claim 1, wherein the duration of the mixing is 30 minutes to 180 minutes.
6. A photosensitive resin prepared by the method of any one of claims 1 to 5.
7. A molding method of a photosensitive resin, wherein the photosensitive resin is the photosensitive resin prepared by the method of any one of claims 1 to 5, the molding method comprising:
pouring the photosensitive resin into a mold, and irradiating for a first preset time period by using a preset light source to obtain a first curing model;
and baking the first curing model for a second preset time to obtain a second curing model.
8. The method of claim 7, wherein the predetermined light source is ultraviolet light having a wavelength of any one of 350nm, 360nm, 380nm, 405nm, or 410 nm.
9. The method of claim 7, wherein the baking temperature is not less than 60 ℃.
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