Photocuring 3D printing resin as well as preparation method and application thereof

Abstract

The invention provides light-cured 3D printing resin as well as a preparation method and application thereof, and relates to the technical field of 3D printing. The light-cured 3D printing resin is prepared from the following raw materials in parts by weight: 10 to 60 parts of multi-cured closed polyurethane acrylate, 10 to 40 parts of low-water-absorption resin, 10 to 50 parts of low-water-absorption monomer, 5 to 30 parts of chain extender and 1 to 4 parts of initiator, the multiple curing closed type polyurethane acrylate is polyurethane acrylate terminated by ethyl 3-(2-trimethylacetamido-3-pyridyl) acrylate, and the multiple curing closed type polyurethane acrylate is polyurethane acrylate terminated by ethyl 3-(2-trimethylacetamido-3-pyridyl) acrylate; the low-water-absorption resin comprises low-water-absorption acrylate resin and / or low-water-absorption methacrylate resin, and the water absorption is less than 2%; the low-water-absorption monomer comprises a low-water-absorption acrylate monomer and / or a low-water-absorption methacrylate monomer, and the water absorption is less than 2%. The photocuring 3D printing resin has the advantages of being excellent in mechanical property, low in viscosity and high in printing speed.

Description

Technical Field

[0001] The present invention relates to the field of 3D printing technology, and particularly to a photocurable 3D printing resin, a preparation method thereof, and an application thereof. Background Art

[0002] 3D printing, also known as Additive Manufacturing, is a technology for manufacturing solid parts by a method of layer-by-layer material accumulation based on three-dimensional data.

[0003] In recent years, with the progress of software and hardware technologies and materials science, the application fields of 3D printing have been gradually expanding, such as aerospace, automotive manufacturing, construction, medical treatment, consumer electronics, education, etc. In 3D printing technology, Vat Photopolymerization is a forming technology that uses the principle of radiation curing of photosensitive resin materials to establish a 3D solid model by layer-by-layer exposure curing. Common DLP (Digital Light Processing), SLA (StereoLithography Appearance), and LCD (Liquid-crystal display) printing devices all belong to the photocuring forming method. Due to the advantages of high forming accuracy and high surface smoothness of the printed parts, it has attracted particular attention from the market and scientific researchers.

[0004] However, there are currently some problems with photocuring technology, especially in terms of materials. The material selectivity is relatively small. For materials with high performance requirements, the resin viscosity is often large, which affects the printing quality and printing accuracy, and there are a series of problems with the printed samples, such as poor aging resistance and easy stress relaxation, which seriously affect the application and development of the photocuring forming technology.

[0005] In view of this, the present invention is specifically proposed. Summary of the Invention

[0006] One of the purposes of the present invention is to provide a photocurable 3D printing resin. The photocurable 3D printing resin introduces a resin with multiple curing functions, that is, a resin containing a photocuring group and a thermal curing group, and at the same time introduces a chain extender to increase the molecular weight and crosslinking density of the resin, thereby improving the stress relaxation resistance of the material. Further, a (meth)acrylate resin and monomer with low water absorption, as well as a light absorber, an antioxidant, and a light stabilizer are introduced to improve the aging resistance of the material.

[0007] The second object of the present invention is to provide a preparation method of a photocurable 3D printing resin. The preparation method further improves the molecular weight and crosslinking density of the resin through secondary curing (simultaneous photocuring and thermal curing) and subsequent heat treatment, thereby enhancing the stress relaxation resistance of the material.

[0008] The third object of the present invention is to provide an application of the photocurable 3D printing resin in the preparation of materials for aerospace, automotive manufacturing, construction or medical use.

[0009] In order to achieve the above objects of the present invention, the following technical solutions are specifically adopted:

[0010] In the first aspect, the present invention provides a photocurable 3D printing resin. The preparation raw materials of the photocurable 3D printing resin include, by weight:

[0011]

[0012] The multi-curing blocked polyurethane acrylate is a polyurethane acrylate blocked with ethyl 3-(2-trimethylacetamido-3-pyridyl) acrylate;

[0013] The low water absorption resin includes low water absorption acrylate resins and / or low water absorption methacrylate resins, and the water absorption rate of the low water absorption resin < 2%;

[0014] The low water absorption monomer includes low water absorption acrylate monomers and / or low water absorption methacrylate monomers, and the water absorption rate of the low water absorption monomer < 2%.

[0015] Preferably, the preparation raw materials of the multi-curing blocked polyurethane acrylate include, by molar ratio:

[0016]

[0017] Preferably, the diol includes any one or at least two combinations of dimethyl hydroxy silicone oil, hydroxy-terminated polybutadiene, hydroxy-terminated polybutylene adipate, polypropylene glycol or polyethylene glycol, and preferably dimethyl hydroxy silicone oil.

[0018] Preferably, the isocyanate includes any one or at least two combinations of hexamethylene diisocyanate, toluene diisocyanate, diphenylmethane diisocyanate, xylylene diisocyanate, isophorone diisocyanate or dicyclohexylmethane-4,4'-diisocyanate.

[0019] Preferably, the catalyst includes any one or at least two combinations of organic zinc, bismuth catalyst or mixed catalyst.

[0020] Preferably, the catalyst includes any one or a combination of at least two of BCAT-E16, BCAT-E20, BCAT-E25A, BCAT-E28A, BCAT-T100R, BCAT-E20CX, ZCAT-EY18, ZCAT-EZ22, ZCAT-T50, BX-EM14 or BX-EM23.

[0021] Preferably, the multi-curing blocked polyurethane acrylate is prepared by the following method: After mixing a diol and an isocyanate, a catalyst is added and stirred once; then ethyl 3-(2-trimethylacetamido-3-pyridyl)acrylate is added for blocking, and stirring is continued for a second time to obtain the multi-curing blocked polyurethane acrylate.

[0022] Preferably, the temperature of the first stirring is 50-80°C, the shear linear velocity of the first stirring is 10-25 m / s, and the time of the first stirring is 1-5 h.

[0023] Preferably, the temperature of the second stirring is 50-90°C, the shear linear velocity of the second stirring is 10-25 m / s, and the time of the second stirring is 1.5-3 h.

[0024] Preferably, the low water absorption resin satisfies the following parameters: water solubility at 20°C < 10 g / L, -60°C < Tg < 450°C, molecular weight < 8000 g / mol.

[0025] Preferably, the low water absorption monomer satisfies the following parameters: water solubility at 20°C < 10 g / L, -60°C < Tg < 300°C, molecular weight < 1000 g / mol.

[0026] Preferably, the low water absorption resin includes any one or a combination of at least two of CN1963NS, CN1964NS, CN1993CG, CN2920, CN2921, CN310NS, CN3211, CN8003NS, CN8010NS, CN8881NS, CN8883NS, CN8887NS, CN8889NS, CN8890NS, CN8891NS, CN8896NS, CN9001NS, CN9011, CN9014NS, CN9021NS, CN9062, CN959, CN9290, CN959, CN964NS, CN969NS, CN983NS, CN989NS, CN991NS, CN2203NS, CN2261NS, CN2282, CN2303NS, CN2302, CN2304, BR-930D, BR-941D, BR-952, BR-970BT, BR-970H, BR-990, BR-371MS, BR-372, BR-541MS, BR-571, BR-741, BR-744BT, BR-744SD, BR-742MS, BR-541S, BR-571, BR-582I10, BR-202, BR-541MB or BR-571MB.

[0027] Preferably, the low water absorption monomer includes any one or a combination of at least two of hexafluorobutyl methacrylate, dodecafluoroheptyl acrylate, tridecafluorooctyl methacrylate, perfluoroalkyl ethyl acrylate, dicyclopentenyl acrylate, 4-tert-butylcyclohexyl acrylate, o-phenylphenoxyethyl acrylate, dicyclopentenyl ethoxylated methacrylate, dicyclopentanyl methacrylate, trimethylolpropane formal acrylate, isobornyl methacrylate, isobornyl acrylate, dipropylene glycol diacrylate, (2) ethoxylated bisphenol A dimethacrylate, (4) ethoxylated bisphenol A dimethacrylate, tricyclodecane dimethanol diacrylate, dimethylaminoethyl methacrylate, trimethylolpropane triacrylate, ethoxylated trimethylolpropane triacrylate or tris(2-hydroxyethyl) isocyanurate triacrylate.

[0028] Preferably, the chain extender includes any one or a combination of at least two of polytetrahydrofuran, polycaprolactone, dimethyl hydroxy silicone oil, polybutylene adipate, N-aminoethyl aminopropyl trimethoxysilane, aminoethyl aminopropyl triethoxysilane, isophorone diamine, diethyl toluene diamine, 4,4'-methylene-bis(3-chloro-2,6-diethylaniline) or bis(sec-butylamino) diphenylmethane, and preferably any one or a combination of at least two of polytetrahydrofuran, polycaprolactone, dimethyl hydroxy silicone oil or polybutylene adipate.

[0029] Preferably, the initiator includes any one or a combination of at least two of phenylbis(2,4,6-trimethylbenzoyl)phosphine oxide, 1-hydroxycyclohexyl phenyl ketone, 2-hydroxy-2-methyl-1-phenyl-1-propanone, (2,4,6-trimethylbenzoyl)-diphenylphosphine oxide, 2-isopropylthioxanthone, (2,4,6-trimethylbenzoyl)-phenylphosphonic acid ethyl ester, camphorquinone, bis-2,6-difluoro-3-pyrrolophenyl titanocene, 2-hydroxy-4'-(2-hydroxyethoxy)-2-methylphenylpropiotone, didodecylbenzene iodonium salt, long-chain alkoxydiphenyl iodonium salt, triphenylsulfonium salt or phenylthiophenyl diphenylsulfonium salt.

[0030] Preferably, the raw materials for preparing the light-curing 3D printing resin further include, by weight: 0.01 to 1 part of absorbent.

[0031] Preferably, the absorber includes a triazine ultraviolet absorber and / or a benzophenone absorber.

[0032] Preferably, the triazine ultraviolet absorber includes any one of 2-[4,6-bis(2,4-xylyl)-1,3,5-triazine-2-yl]-5-(octyloxy)phenol, 2-(4,6-diphenyl-1,3,5-triazine-2)-5-n-hexaneoxy or UV1990, or a combination of at least two thereof.

[0033] Preferably, the benzophenone absorbent includes any one of 2-hydroxy-4-n-octyloxybenzophenone, 2,4-dihydroxybenzophenone or 2-hydroxy-4-methoxybenzophenone, or a combination of at least two thereof.

[0034] Preferably, the raw materials for preparing the light-curable 3D printing resin further include, by weight: 0.01 to 1 part of an antioxidant.

[0035] Preferably, the antioxidant comprises any one or a combination of at least two of diphenylamine, p-phenylenediamine, dihydroquinoline, 2,6-di-tert-butyl-4-methylphenol, bis(3,5-di-tert-butyl-4-hydroxyphenyl) sulfide, pentaerythritol tetrakis[β-(3,5-di-tert-butyl-4-hydroxyphenyl) propionate, thiodipropionic acid diester, didodecanol ester, didetradecyl ester and didecyl ester, trioctyl ester, tridecyl ester, tridodecanol ester or trihexadecanol ester.

[0036] Preferably, the raw materials for preparing the light-curing 3D printing resin further include, by weight: 0.01 to 1 part of a light stabilizer.

[0037] Preferably, the light stabilizer includes any one or a combination of at least two of carbon black, titanium dioxide, zinc oxide, lithopone, 2,2,6,6-tetramethylpiperidine, light stabilizer 770, light stabilizer 944, light stabilizer 292, light stabilizer 791, light stabilizer 783 or light stabilizer 700.

[0038] In a second aspect, the present invention provides a method for preparing the photocurable 3D printing resin as described in the first aspect, and the preparation method includes:

[0039] Mixing the raw materials in the photocurable 3D printing resin according to the ratio, and performing stirring to obtain a mixed material;

[0040] Performing a curing treatment on the mixed material through a 3D printing device to obtain a cured product; wherein, the curing treatment includes photocuring and thermal curing performed simultaneously;

[0041] Performing a heat treatment on the cured product to obtain the photocurable 3D printing resin.

[0042] Preferably, the rotation speed of the stirring is 500 - 2000 r / min, the shear linear velocity of the stirring is 10 - 25 m / s, the temperature of the stirring is 30 - 70 °C, and the time of the stirring is 2 - 6 h.

[0043] Preferably, the light wavelength of the curing treatment is 200 - 1500 nm, the light intensity of the curing treatment is 30 - 200 mw / cm 2 , the temperature of the curing treatment is 40 - 50 °C, and the time of the curing treatment is 5 - 30 min.

[0044] Preferably, the temperature of the heat treatment is 80 - 130 °C, and the time of the heat treatment is 1 - 3 h.

[0045] In a third aspect, the present invention provides an application of the photocurable 3D printing resin as described in the first aspect in the preparation of materials for aerospace, automotive manufacturing, construction or medical use.

[0046] Compared with the prior art, the present invention has the following beneficial effects:

[0047] (1) The present invention introduces a resin with a multi-curing function capped with a specific structure, and at the same time introduces a chain extender to further increase the molecular weight and crosslinking density of the resin, thereby improving the stress relaxation resistance of the material. In addition, introducing (meth)acrylate resins and monomers with low water absorption, light absorbers, antioxidants and light stabilizers improves the aging resistance of the material.

[0048] (2) The secondary photocuring in the preparation method of the present invention helps to improve the reaction rate and reaction degree of the model photocuring. In addition, the infrared long wavelength band has better transmission depth and thermal effect, which helps the model to be cured more fully and thoroughly; the subsequent heat treatment causes the multi-cured blocked polyurethane acrylate to deblock to form active isocyanate groups, which then react with the chain extender to further increase the molecular weight, thereby improving the mechanical properties. Detailed Embodiments

[0049] Unless otherwise defined herein, scientific and technical terms used in conjunction with the present invention shall have the meanings commonly understood by those of ordinary skill in the art. The meanings and scopes of the terms should be clear. However, in any case of potential ambiguity, the definitions provided herein shall prevail over any dictionary or extrinsic definition. In this application, unless otherwise specified, the use of "or" means "and / or". In addition, the use of the term "comprising" and other forms is non-limiting.

[0050] It should be noted that specific details are set forth in the following description to facilitate a thorough understanding of the present invention. However, the present invention can be implemented in many other ways different from those described herein, and those skilled in the art can make similar generalizations without departing from the connotation of the present invention. Therefore, the present invention is not limited by the specific embodiments disclosed below.

[0051] The embodiments of the present invention will be described in detail below in conjunction with the embodiments and examples. However, those skilled in the art will understand that the following embodiments and examples are only used to illustrate the present invention and should not be regarded as limiting the scope of the present invention. All other embodiments obtained by those of ordinary skill in the art based on the embodiments of the present invention without creative efforts shall fall within the scope of protection of the present invention. Those not specifying specific conditions are carried out according to conventional conditions or conditions recommended by the manufacturer. Those reagents or instruments not indicating the manufacturer can be obtained as conventional products through commercial purchase.

[0052] In a first aspect, the present invention provides a photocurable 3D printing resin, and the preparation raw materials of the photocurable 3D printing resin include, by weight parts:

[0053]

[0054]

[0055] The multi-cured blocked polyurethane acrylate is a polyurethane acrylate capped with ethyl 3-(2-trimethylacetamido-3-pyridyl)acrylate;

[0056] The low water absorption resin includes low water absorption acrylate resins and / or low water absorption methacrylate resins, and the water absorption of the low water absorption resin < 2%.

[0057] The low water absorption monomer includes a low water absorption acrylate monomer and / or a low water absorption methacrylate monomer, and the water absorption rate of the low water absorption monomer < 2%.

[0058] In the present invention, ethyl 3-(2-trimethylacetamido-3-pyridyl)acrylate-capped polyurethane acrylate and a chain extender are introduced, and the resin containing both a photocuring group and a thermocuring group can significantly increase the molecular weight and crosslinking density of the resin, thereby improving the stress relaxation resistance of the material. Further, a (meth)acrylate resin and monomer with low water absorption are introduced to improve the aging resistance of the material.

[0059] As an optional embodiment, in the raw materials for preparing the photocurable 3D printing resin, the content of the multi-curing blocked polyurethane acrylate is 10 to 60 parts, such as 10 parts, 12 parts, 14 parts, 15 parts, 16 parts, 18 parts, 20 parts, 22 parts, 24 parts, 25 parts, 26 parts, 28 parts, 30 parts, 32 parts, 34 parts, 35 parts, 36 parts, 38 parts, 40 parts, 42 parts, 44 parts, 45 parts, 46 parts, 48 parts, 50 parts, 52 parts, 54 parts, 55 parts, 56 parts, 58 parts, 60 parts, etc., preferably 35 to 45 parts, and more preferably 40 parts.

[0060] As an optional embodiment, in the raw materials for preparing the photocurable 3D printing resin, the content of the low water absorption resin is 10 to 40 parts, such as 10 parts, 12 parts, 14 parts, 15 parts, 16 parts, 18 parts, 20 parts, 22 parts, 24 parts, 25 parts, 26 parts, 28 parts, 30 parts, 32 parts, 34 parts, 35 parts, 36 parts, 38 parts, 40 parts, etc., preferably 10 to 20 parts, and more preferably 15 parts.

[0061] As an optional embodiment, in the raw materials for preparing the photocurable 3D printing resin, the content of the low water absorption monomer is 10 to 50 parts, such as 10 parts, 12 parts, 14 parts, 15 parts, 16 parts, 18 parts, 20 parts, 22 parts, 24 parts, 25 parts, 26 parts, 28 parts, 30 parts, 32 parts, 34 parts, 35 parts, 36 parts, 38 parts, 40 parts, 42 parts, 44 parts, 45 parts, 46 parts, 48 parts, 50 parts, etc., preferably 25 to 35 parts, and more preferably 30 parts.

[0062] As an alternative embodiment, the content of the chain extender in the raw materials for preparing the photocurable 3D printing resin is 5 to 30 parts, for example, it can be 5 parts, 6 parts, 7 parts, 8 parts, 9 parts, 10 parts, 12 parts, 14 parts, 15 parts, 16 parts, 18 parts, 20 parts, 22 parts, 24 parts, 25 parts, 26 parts, 28 parts, 30 parts, etc., preferably 5 to 15 parts, and more preferably 10 parts.

[0063] As an alternative embodiment, the content of the initiator in the raw materials for preparing the photocurable 3D printing resin is 1 part, 1.2 parts, 1.4 parts, 1.5 parts, 1.6 parts, 1.8 parts, 2 parts, 2.2 parts, 2.4 parts, 2.5 parts, 2.6 parts, 2.8 parts, 3 parts, 3.2 parts, 3.4 parts, 3.5 parts, 3.6 parts, 3.8 parts, 4 parts, etc., preferably 1.5 to 2.5 parts, and more preferably 2 parts.

[0064] As an alternative embodiment, the water absorption rate of the low water absorption resin is < 2%, for example, it can be 1.9%, 1.8%, 1.7%, 1.6%, 1.5%, 1.4%, 1.3%, 1.2%, 1.1%, 1.0%, 0.9%, 0.8%, 0.7%, 0.6%, 0.5%, 0.4%, 0.3%, 0.2%, 0.1%, etc.

[0065] As an alternative embodiment, the water absorption rate of the low water absorption monomer is < 2%, for example, it can be 1.9%, 1.8%, 1.7%, 1.6%, 1.5%, 1.4%, 1.3%, 1.2%, 1.1%, 1.0%, 0.9%, 0.8%, 0.7%, 0.6%, 0.5%, 0.4%, 0.3%, 0.2%, 0.1%, etc.

[0066] As an alternative embodiment, the raw materials for preparing the multi-curing blocked polyurethane acrylate include, by molar ratio:

[0067]

[0068] As an alternative embodiment, the content of the diol in the raw materials for preparing the multi-curing blocked polyurethane acrylate is 24 to 40 mol, for example, it can be 24 mol, 25 mol, 26 mol, 27 mol, 28 mol, 29 mol, 30 mol, 31 mol, 32 mol, 33 mol, 34 mol, 35 mol, 36 mol, 37 mol, 38 mol, 39 mol, 40 mol, etc.

[0069] As an alternative embodiment, the content of the isocyanate in the raw materials for preparing the multi-curing blocked polyurethane acrylate is 60 mol.

[0070] As an alternative embodiment, the content of the catalyst in the raw materials for preparing the multi-curing blocked polyurethane acrylate is 0.01 to 5 mol. For example, it can be 0.01 mol, 0.02 mol, 0.04 mol, 0.05 mol, 0.06 mol, 0.08 mol, 0.1 mol, 0.15 mol, 0.2 mol, 0.25 mol, 0.3 mol, 0.35 mol, 0.4 mol, 0.5 mol, 0.6 mol, 0.8 mol, 1 mol, 1.5 mol, 2 mol, 2.5 mol, 3 mol, 4 mol, 5 mol, etc.

[0071] As an alternative embodiment, the content of ethyl 3-(2-trimethylacetylamino-3-pyridyl)acrylate in the raw materials for preparing the multi-curing blocked polyurethane acrylate is 40 to 72 mol. For example, it can be 40 mol, 42 mol, 44 mol, 46 mol, 48 mol, 50 mol, 52 mol, 54 mol, 56 mol, 58 mol, 60 mol, 62 mol, 64 mol, 66 mol, 68 mol, 70 mol, 72 mol, etc.

[0072] As an alternative embodiment, the diol includes any one or a combination of at least two of dimethyl hydroxy silicone oil, hydroxyl-terminated polybutadiene, hydroxyl-terminated polybutylene adipate, polypropylene glycol (PPG), or polyethylene glycol (PEG).

[0073] As a preferred embodiment, the diol is dimethyl hydroxy silicone oil.

[0074] In the present invention, the diol is preferably dimethyl hydroxy silicone oil because the bond energy of the Si-O bond is greater than that of the C-C bond and the C-O bond, having better anti-aging performance and high-temperature resistance. In addition, the Si-O bond has a larger bond length and bond angle, having better flexibility.

[0075] As an alternative embodiment, the isocyanate is any one or a combination of at least two of hexamethylene diisocyanate (HDI), toluene diisocyanate (TDI), diphenylmethane diisocyanate (MDI), xylylene diisocyanate (XDI), isophorone diisocyanate (IPDI), or dicyclohexylmethane-4,4'-diisocyanate (HMDI).

[0076] As an alternative embodiment, the catalyst includes any one or a combination of at least two of organic zinc, bismuth catalyst, or mixed catalyst.

[0077] As an alternative embodiment, the catalyst includes any one or a combination of at least two of BCAT-E16, BCAT-E20, BCAT-E25A, BCAT-E28A, BCAT-T100R, BCAT-E20CX, ZCAT-EY18, ZCAT-EZ22, ZCAT-T50, BX-EM14 or BX-EM23 of Guangzhou Yourun Synthetic Materials Co., Ltd.

[0078] As an alternative embodiment, the multi-curing blocked polyurethane acrylate is prepared by the following preparation method:

[0079] After mixing the diol and the isocyanate, a catalyst is added and stirred once; then ethyl 3-(2-trimethylacetamido-3-pyridyl)acrylate is added for capping, and stirring is continued for a second time to obtain the multi-curing blocked polyurethane acrylate.

[0080] As an alternative embodiment, the temperature of the first stirring is 50 to 80 °C, for example, it can be 50 °C, 55 °C, 60 °C, 65 °C, 70 °C, 75 °C, 80 °C, etc.

[0081] As an alternative embodiment, the shear line speed of the first stirring is 10 to 25 m / s, for example, it can be 10 m / s, 12 m / s, 14 m / s, 15 m / s, 16 m / s, 18 m / s, 20 m / s, 22 m / s, 24 m / s, 25 m / s, etc.

[0082] As an alternative embodiment, the time of the first stirring is 1 to 5 h, for example, it can be 1 h, 1.5 h, 2 h, 2.5 h, 3 h, 3.5 h, 4 h, 4.5 h, 5 h, etc.

[0083] As an alternative embodiment, the temperature of the second stirring is 50 to 90 °C, for example, it can be 50 °C, 55 °C, 60 °C, 65 °C, 70 °C, 75 °C, 80 °C, 85 °C, 90 °C, etc.

[0084] As an alternative embodiment, the shear line speed of the second stirring is 10 to 25 m / s, for example, it can be 10 m / s, 12 m / s, 14 m / s, 15 m / s, 16 m / s, 18 m / s, 20 m / s, 22 m / s, 24 m / s, 25 m / s, etc.

[0085] As an alternative embodiment, the time of the second stirring is 1.5 to 3 h, for example, it can be 1.5 h, 2 h, 2.5 h, 3 h, etc.

[0086] As an alternative embodiment, the low water absorption resin satisfies the following parameters (according to ASTM D570-98 standard): water solubility at 20 °C < 10 g / L, -60 °C < Tg < 450 °C, molecular weight < 8000 g / mol.

[0087] As an alternative embodiment, at 20 °C, the water solubility of the low water absorption resin < 10 g / L, for example, it can be 9.9 g / L, 9.8 g / L, 9.6 g / L, 9.5 g / L, 9.4 g / L, 9.2 g / L, 9 g / L, 8.8 g / L, 8.5 g / L, 8.2 g / L, 8 g / L, 7.5 g / L, 7 g / L, 6.5 g / L, 6 g / L, 5.5 g / L, 5 g / L, 4 g / L, 3 g / L, 2 g / L, 1 g / L, etc.

[0088] As an alternative embodiment, the Tg of the low water absorption resin is -60 to 450 °C (excluding the endpoint values), for example, it can be -50 °C, -40 °C, -30 °C, -20 °C, -10 °C, -5 °C, 0 °C, 5 °C, 10 °C, 20 °C, 40 °C, 50 °C, 60 °C, 80 °C, 90 °C, 100 °C, 120 °C, 140 °C, 150 °C, 160 °C, 180 °C, 200 °C, 250 °C, 300 °C, 350 °C, 400 °C, 450 °C, etc.

[0089] As an alternative embodiment, the molecular weight of the low water absorption resin < 8000 g / mol, for example, it can be 7900 g / mol, 7800 g / mol, 7600 g / mol, 7500 g / mol, 7400 g / mol, 7200 g / mol, 7000 g / mol, 6900 g / mol, 6800 g / mol, 6600 g / mol, 6500 g / mol, 6400 g / mol, 6200 g / mol, 6000 g / mol, 5500 g / mol, 5000 g / mol, 4500 g / mol, 4000 g / mol, 3500 g / mol, 3000 g / mol, 2500 g / mol, 2000 g / mol, 1500 g / mol, 1000 g / mol, 500 g / mol, etc.

[0090] As an alternative embodiment, the low water absorption monomer satisfies the following parameters (according to ASTM D570-98 standard): water solubility at 20 °C < 10 g / L, -60 °C < Tg < 300 °C, molecular weight < 1000 g / mol.

[0091] As an alternative embodiment, at 20 °C, the water solubility of the low water absorption monomer is < 10 g / L, and may be, for example, 9.9 g / L, 9.8 g / L, 9.6 g / L, 9.5 g / L, 9.4 g / L, 9.2 g / L, 9 g / L, 8.8 g / L, 8.5 g / L, 8.2 g / L, 8 g / L, 7.5 g / L, 7 g / L, 6.5 g / L, 6 g / L, 5.5 g / L, 5 g / L, 4 g / L, 3 g / L, 2 g / L, 1 g / L, etc.

[0092] As an alternative embodiment, the Tg of the low water absorption monomer is -60 to 300 °C (excluding the endpoint values), and may be, for example, -50 °C, -40 °C, -30 °C, -20 °C, -10 °C, -5 °C, 0 °C, 5 °C, 10 °C, 20 °C, 40 °C, 50 °C, 60 °C, 80 °C, 90 °C, 100 °C, 120 °C, 140 °C, 150 °C, 160 °C, 180 °C, 200 °C, 250 °C, 300 °C, etc.

[0093] As an alternative embodiment, the molecular weight of the low water absorption monomer is < 1000 g / mol, and may be, for example, 990 g / mol, 980 g / mol, 960 g / mol, 950 g / mol, 940 g / mol, 920 g / mol, 900 g / mol, 890 g / mol, 880 g / mol, 860 g / mol, 850 g / mol, 840 g / mol, 820 g / mol, 800 g / mol, 750 g / mol, 700 g / mol, 650 g / mol, 600 g / mol, 550 g / mol, 500 g / mol, 450 g / mol, 400 g / mol, 350 g / mol, 300 g / mol, 250 g / mol, 200 g / mol, 150 g / mol, 100 g / mol, 50 g / mol, etc.

[0094] As an alternative embodiment, the low water absorption resin includes any one or a combination of at least two of Sartomer's CN1963NS, CN1964NS, CN1993CG, CN2920, CN2921, CN310NS, CN3211, CN8003NS, CN8010NS, CN8881NS, CN8883NS, CN8887NS, CN8889NS, CN8890NS, CN8891NS, CN8896NS, CN9001NS, CN9011, CN9014NS, CN9021NS, CN9062, CN959, CN9290, CN959, CN964NS, CN969NS, CN983NS, CN989NS, CN991NS, CN2203NS, CN2261NS, CN2282, CN2303NS, CN2302, CN2304; and any one or a combination of at least two of Dymax's BR-930D, BR-941D, BR-952, BR-970BT, BR-970H, BR-990, BR-371MS, BR-372, BR-541MS, BR-571, BR-741, BR-744BT, BR-744SD, BR-742MS, BR-541S, BR-571, BR-582I10, BR-202, BR-541MB or BR-571MB.

[0095] As an alternative embodiment, the low water absorption monomer includes any one or a combination of at least two of hexafluorobutyl methacrylate, dodecafluoroheptyl acrylate, tridecafluorooctyl methacrylate, perfluoroalkyl ethyl acrylate, dicyclopentenyl acrylate, 4-tert-butylcyclohexyl acrylate, o-phenylphenoxyethyl acrylate, dicyclopentenyl ethoxylated methacrylate, dicyclopentanyl methacrylate, trimethylolpropane formal acrylate, isobornyl methacrylate, isobornyl acrylate, dipropylene glycol diacrylate, (2) ethoxylated bisphenol A dimethacrylate, (4) ethoxylated bisphenol A dimethacrylate, tricyclodecane dimethanol diacrylate, dimethylaminoethyl carbamate dimethacrylate, trimethylolpropane triacrylate, ethoxylated trimethylolpropane triacrylate, or tris(2-hydroxyethyl) isocyanurate triacrylate.

[0096] As an alternative embodiment, the chain extender includes any one or a combination of at least two of polytetrahydrofuran, polycaprolactone, dimethyl hydroxy silicone oil, polybutylene adipate, N-aminoethyl-3-aminopropyltrimethoxysilane, aminoethyl aminopropyl triethoxysilane, isophorone diamine, diethyl toluene diamine, 4,4'-methylene-bis(3-chloro-2,6-diethylaniline), or bis(sec-butylamino) diphenyl methane.

[0097] As a preferred embodiment, it is preferably any one or a combination of at least two of polytetrahydrofuran, polycaprolactone, dimethyl hydroxy silicone oil or polybutylene adipate, and has a low water absorption rate.

[0098] As a preferred embodiment, the initiator includes any one or a combination of at least two of phenylbis(2,4,6-trimethylbenzoyl)phosphine oxide, 1-hydroxycyclohexyl phenyl ketone, 2-hydroxy-2-methyl-1-phenyl-1-propanone, (2,4,6-trimethylbenzoyl)-diphenylphosphine oxide, 2-isopropylthioxanthone, ethyl (2,4,6-trimethylbenzoyl)phenylphosphonate, camphorquinone, bis(2,6-difluoro-3-pyrrolophenyl)titanocene dichloride, 2-hydroxy-4'-(2-hydroxyethoxy)-2-methylpropiophenone, didodecylbenzeneiodonium salt, long-chain alkoxydiphenyl iodonium salt, triphenylsulfonium salt or phenylthiophenyldiphenylsulfonium salt.

[0099] As a preferred embodiment, the raw materials for preparing the photocurable 3D printing resin further include, by weight: 0.01 to 1 part of an absorbent.

[0100] As an alternative embodiment, the content of the absorbent in the raw materials for preparing the photocurable 3D printing resin is 0.01 to 1 part, for example, it can be 0.01 part, 0.02 part, 0.04 part, 0.05 part, 0.06 part, 0.08 part, 0.1 part, 0.15 part, 0.2 part, 0.25 part, 0.3 part, 0.35 part, 0.4 part, 0.5 part, 0.6 part, 0.8 part, 1 part, etc., preferably 0.1 to 0.3 part, and more preferably 0.2 part.

[0101] As an alternative embodiment, the absorbent includes triazine ultraviolet absorbers and / or benzophenone absorbers.

[0102] As an alternative embodiment, the triazine ultraviolet absorbers include any one or a combination of at least two of 2-[4,6-bis(2,4-dimethylphenyl)-1,3,5-triazin-2-yl]-5-(octyloxy)phenol (UV-1164), 2-(4,6-diphenyl-1,3,5-triazin-2)-5-n-hexyloxy (UV-1577) or UV1990 (Eutec Chemical).

[0103] As an alternative embodiment, the benzophenone absorbers include any one or a combination of at least two of 2-hydroxy-4-n-octyloxybenzophenone (UV-531), 2,4-dihydroxybenzophenone (UV-O) or 2-hydroxy-4-methoxybenzophenone (UV-9).

[0104] As an alternative embodiment, the raw materials for preparing the photocurable 3D printing resin further include, by weight: 0.01 to 1 part of an antioxidant.

[0105] As an alternative embodiment, the content of the antioxidant in the raw materials for preparing the photocurable 3D printing resin is 0.01 to 1 part, for example, it can be 0.01 part, 0.02 part, 0.04 part, 0.05 part, 0.06 part, 0.08 part, 0.1 part, 0.15 part, 0.2 part, 0.25 part, 0.3 part, 0.35 part, 0.4 part, 0.5 part, 0.6 part, 0.8 part, 1 part, etc., preferably 0.1 to 0.3 part, and more preferably 0.2 part.

[0106] As an alternative embodiment, the antioxidant includes any one or a combination of at least two of diphenylamine, p-phenylenediamine, dihydroquinoline, 2,6-di-tert-butyl-4-methylphenol, bis(3,5-di-tert-butyl-4-hydroxyphenyl) sulfide, pentaerythritol tetra[β-(3,5-di-tert-butyl-4-hydroxyphenyl) propionate], thiodipropionate diester, didodecyl ester, ditetradecyl ester, dioctadecyl ester, trioctyl ester, tridecyl ester, tris(dodecyl alcohol) ester, or tris(hexadecyl alcohol) ester.

[0107] As an alternative embodiment, the raw materials for preparing the photocurable 3D printing resin further include, by weight: 0.01 to 1 part of a light stabilizer.

[0108] As an alternative embodiment, the content of the light stabilizer in the raw materials for preparing the photocurable 3D printing resin is 0.01 to 1 part, for example, it can be 0.01 part, 0.02 part, 0.04 part, 0.05 part, 0.06 part, 0.08 part, 0.1 part, 0.15 part, 0.2 part, 0.25 part, 0.3 part, 0.35 part, 0.4 part, 0.5 part, 0.6 part, 0.8 part, 1 part, etc., preferably 0.1 to 0.3 part, and more preferably 0.2 part.

[0109] As an alternative embodiment, the light stabilizer includes any one or a combination of at least two of carbon black, titanium dioxide, zinc oxide, zinc barium, 2,2,6,6-tetramethylpiperidine, light stabilizer 770, light stabilizer 944, light stabilizer 292, light stabilizer 791, light stabilizer 783, or light stabilizer 700.

[0110] In a second aspect, the present invention provides a method for preparing the photocurable 3D printing resin as described in the first aspect, and the preparation method includes:

[0111] (1) Mixing the raw materials in the photocurable 3D printing resin according to the ratio, and stirring to obtain a mixed material;

[0112] (2) curing the mixed material through a 3D printing device to obtain a cured product; wherein the curing process includes simultaneous photocuring and thermal curing;

[0113] (3) The cured product is subjected to heat treatment to obtain the light-curing 3D printing resin.

[0114] In the present invention, step (2) first performs secondary photocuring (referring to the curing treatment of photocuring and heat curing performed simultaneously) at a certain temperature, which helps to improve the reaction rate and degree of model photocuring. In addition, it has better transmission depth and thermal effect in the long-wave infrared band, which helps to cure the model more fully and thoroughly. Further, step (3) performs oven heat treatment at a certain temperature to deblock the multi-cured blocked polyurethane acrylate to form active isocyanate groups, thereby reacting with the chain extender to further increase the molecular weight, thereby improving the mechanical properties.

[0115] As an optional embodiment, in step (1), the stirring speed is 500-2000r / min, for example, it can be 500r / min, 520r / min, 540r / min, 550r / min, 560r / min, 580r / min, 600r / min, 620r / min, 640r / min, 680r / min, 700r / min, 720r / min, 750r / min, 800r / min, 850r / min, 900r / min, 950r / min, 1000r / min, 1200r / min, 1400r / min, 1500r / min, 1600r / min, 1800r / min, 2000r / min, etc.

[0116] As an optional embodiment, in step (1), the shear line speed of the stirring is 10 to 25 m / s, for example, it can be 10 m / s, 12 m / s, 14 m / s, 15 m / s, 16 m / s, 18 m / s, 20 m / s, 22 m / s, 24 m / s, 25 m / s, etc.

[0117] As an optional embodiment, in step (1), the stirring temperature is 30-70°C, for example, it can be 30°C, 35°C, 40°C, 45°C, 50°C, 55°C, 60°C, 65°C, 70°C, etc.

[0118] As an optional embodiment, in step (1), the stirring time is 2 to 6 hours, for example, it can be 2 hours, 2.5 hours, 3 hours, 3.5 hours, 4 hours, 4.5 hours, 5 hours, 5.5 hours, 6 hours, etc.

[0119] As an alternative embodiment, in step (2), the light wavelength for the curing treatment is 200 to 1500 nm, such as 200 nm, 300 nm, 400 nm, 500 nm, 600 nm, 700 nm, 800 nm, 900 nm, 1000 nm, 1100 nm, 1200 nm, 1300 nm, 1400 nm, 1500 nm, etc.

[0120] As an alternative embodiment, in step (2), the light intensity for the curing treatment is 30 to 200 mw / cm 2 , such as 30 mw / cm 2 , 40 mw / cm 2 , 50 mw / cm 2 , 60 mw / cm 2 , 70 mw / cm 2 , 80 mw / cm 2 , 90 mw / cm 2 , 100 mw / cm 2 , 110 mw / cm 2 , 120 mw / cm 2 , 130 mw / cm 2 , 140 mw / cm 2 , 150 mw / cm 2 , 160 mw / cm 2 , 170 mw / cm 2 , 180 mw / cm 2 , 190 mw / cm 2 , 200 mw / cm 2 etc.

[0121] As an alternative embodiment, in step (2), the temperature for the curing treatment is 40 to 50 °C, such as 40 °C, 41 °C, 42 °C, 43 °C, 44 °C, 45 °C, 46 °C, 47 °C, 48 °C, 49 °C, 50 °C, etc., and preferably 50 °C.

[0122] As an alternative embodiment, in step (2), the time for the curing treatment is 5 to 30 min, such as 5 min, 6 min, 7 min, 8 min, 9 min, 10 min, 12 min, 14 min, 15 min, 16 min, 18 min, 20 min, 22 min, 24 min, 25 min, 26 min, 28 min, 30 min, etc., preferably 5 to 15 min, and more preferably 10 min.

[0123] As an alternative embodiment, in step (3), the temperature of the heat treatment is 80 to 130 °C, for example, it can be 80 °C, 85 °C, 90 °C, 95 °C, 100 °C, 105 °C, 110 °C, 115 °C, 120 °C, 125 °C, 130 °C, etc., preferably 100 to 120 °C, and more preferably 110 °C.

[0124] As an alternative embodiment, in step (3), the time of the heat treatment is 1 to 3 h, for example, it can be 1 h, 1.2 h, 1.4 h, 1.5 h, 1.6 h, 1.8 h, 2 h, 2.2 h, 2.4 h, 2.5 h, 2.6 h, 2.8 h, 3 h, etc.

[0125] In a third aspect, the present invention provides an application of the photocurable 3D printing resin as described in the first aspect in the preparation of materials for aerospace, automotive manufacturing, construction, or medical use.

[0126] The present invention will be further illustrated below by specific examples and comparative examples. However, it should be understood that these examples are only for more detailed illustration and should not be construed as limiting the present invention in any form.

[0127] Preparation Example 1

[0128] This preparation example provides a multi-curing blocked polyurethane acrylate. The raw materials for preparing the multi-curing blocked polyurethane acrylate include, by molar ratio:

[0129]

[0130] The multi-curing blocked polyurethane acrylate is prepared by the following preparation method:

[0131] After weighing and mixing dimethyl hydroxy silicone oil and toluene diisocyanate (TDI) in the above ratio, catalyst BCAT-E25A is added, and the mixture is stirred at a shear line speed of 15 m / s at a temperature of 60 °C for 2 h. Then, ethyl 3-(2-trimethylacetamido-3-pyridyl)acrylate with the above content is added for blocking, and after continuing to stir for 2 h, the multi-curing blocked polyurethane acrylate is prepared.

[0132] Preparation Example 2

[0133] This preparation example provides a multi-curing blocked polyurethane acrylate. The raw materials for preparing the multi-curing blocked polyurethane acrylate include, by molar ratio:

[0134]

[0135] The multi-curing blocked polyurethane acrylate is prepared by the following preparation method:

[0136] After weighing and mixing dimethylhydroxy silicone oil and hexamethylene diisocyanate (HDI) in the above proportions, catalyst BCAT-T100R was added, and the mixture was stirred at a shear line speed of 15 m / s at 60 °C for 2 h. Then, ethyl 3-(2-trimethylacetamido-3-pyridyl)acrylate with the above content was added for capping, and after continuous stirring for 2 h, the multiple-curing blocked polyurethane acrylate was prepared.

[0137] Preparation Example 3

[0138] This preparation example provides a multiple-curing blocked polyurethane acrylate. The raw materials for preparing the multiple-curing blocked polyurethane acrylate include, by weight:

[0139]

[0140] The multiple-curing blocked polyurethane acrylate was prepared by the following preparation method:

[0141] After weighing and mixing dimethylhydroxy silicone oil and dicyclohexylmethane-4,4'-diisocyanate (HMDI) in the above proportions, catalyst BX-EM14 was added, and the mixture was stirred at a shear line speed of 15 m / s at 60 °C for 2 h. Then, ethyl 3-(2-trimethylacetamido-3-pyridyl)acrylate with the above content was added for capping, and after continuous stirring for 2 h, the multiple-curing blocked polyurethane acrylate was prepared.

[0142] Preparation Example 4

[0143] This preparation example provides a multiple-curing blocked polyurethane acrylate. The difference from Preparation Example 1 is only that dimethylhydroxy silicone oil was replaced with polyethylene glycol (PEG-800) of equal weight, and the other steps were the same as those in Preparation Example 1.

[0144] Preparation Example 5

[0145] This preparation example provides a multiple-curing blocked polyurethane acrylate. The difference from Preparation Example 1 is only that dimethylhydroxy silicone oil was replaced with polypropylene glycol (PPG-800) of equal weight, and the other steps were the same as those in Preparation Example 1.

[0146] Comparative Preparation Example 1

[0147] This preparation example provides a multiple-curing blocked polyurethane acrylate. The difference from Preparation Example 1 is only that ethyl 3-(2-trimethylacetamido-3-pyridyl)acrylate was replaced with ethyl 2-(tert-butylamino)acrylate of equal weight, and the other steps were the same as those in Preparation Example 1.

[0148] Example 1

[0149] This embodiment provides a photocurable 3D printing resin. The preparation raw materials of the photocurable 3D printing resin include, by weight:

[0150]

[0151]

[0152] The preparation method of the photocurable 3D printing resin comprises the following steps:

[0153] (1) Add the above materials into a stirring and dispersing kettle, adjust the rotation speed to 800 r / min, that is, provide a shear linear velocity of 15 m / s, control the temperature at 40 °C, and stir and disperse for 4 h to obtain a mixed material;

[0154] (2) Print a three-dimensional mechanical test model with a photocurable 3D printer, clean it with 75% medical alcohol, dry it with a compressed air gun, and cure it in a curing box at a wavelength of 200 - 1500 nm, 100 mw / cm 2 and 50 °C for 10 min to obtain a cured product;

[0155] (3) Place the cured product in an oven and heat-treat it at 110 °C for 2 h to obtain the photocurable 3D printing resin.

[0156] Example 2

[0157] This embodiment provides a photocurable 3D printing resin. The preparation raw materials of the photocurable 3D printing resin include, by weight:

[0158]

[0159]

[0160] The preparation method of the photocurable 3D printing resin comprises the following steps:

[0161] (1) Add the above materials into a stirring and dispersing kettle, adjust the rotation speed to 800 r / min, that is, provide a shear linear velocity of 15 m / s, control the temperature at 40 °C, and stir and disperse for 4 h to obtain a mixed material;

[0162] (2) Print a three-dimensional mechanical test model with a photocurable 3D printer, clean it with 75% medical alcohol, dry it with a compressed air gun, and cure it in a curing box at a wavelength of 200 - 1500 nm, 100 mw / cm 2 and 50 °C for 10 min to obtain a cured product;

[0163] (3) Place the cured product in an oven and heat-treat it at 110 °C for 2 h to obtain the photocurable 3D printing resin.

[0164] Example 3

[0165] This example provides a photocurable 3D printing resin. The preparation raw materials of the photocurable 3D printing resin include, by weight:

[0166]

[0167] The preparation method of the photocurable 3D printing resin includes the following steps:

[0168] (1) Add the above materials into a stirring and dispersing kettle, adjust the rotation speed to 800 r / min, that is, provide a shear line speed of 15 m / s, control the temperature at 40 °C, and stir and disperse for 4 h to obtain a mixed material;

[0169] (2) Print a three-dimensional mechanical test model through a photocurable 3D printer, clean it with 75% medical alcohol, dry it with a compressed air gun, and cure it in a curing box at a wavelength of 200 - 1500 nm, 100 mw / cm 2 ², and 50 °C for 10 min to obtain a cured product;

[0170] (3) Place the cured product in an oven and heat-treat it at 110 °C for 2 h to obtain the photocurable 3D printing resin.

[0171] Example 4

[0172] This example provides a photocurable 3D printing resin. The preparation raw materials of the photocurable 3D printing resin include, by weight:

[0173]

[0174] The preparation method of the photocurable 3D printing resin includes the following steps:

[0175] (1) Add the above materials into a stirring and dispersing kettle, adjust the rotation speed to 800 r / min, that is, provide a shear line speed of 15 m / s, control the temperature at 40 °C, and stir and disperse for 4 h to obtain a mixed material;

[0176] (2) Print a three-dimensional mechanical test model through a photocurable 3D printer, clean it with 75% medical alcohol, dry it with a compressed air gun, and cure it in a curing box at a wavelength of 200 - 1500 nm, 100 mw / cm 2 ², and 50 °C for 10 min to obtain a cured product;

[0177] (3) Place the cured product in an oven and heat-treat it at 110 °C for 2 h to obtain the photocurable 3D printing resin.

[0178] Example 5

[0179] This embodiment provides a photocurable 3D printing resin. The preparation raw materials of the photocurable 3D printing resin include, by weight:

[0180]

[0181] The preparation method of the photocurable 3D printing resin comprises the following steps:

[0182] (1) Add the above materials into a stirring and dispersing kettle, adjust the rotation speed to 800 r / min, that is, provide a shear linear velocity of 15 m / s, control the temperature at 40 °C, and stir and disperse for 4 h to obtain a mixed material;

[0183] (2) Print a three-dimensional mechanical test model with a photocurable 3D printer, clean it with 75% medical alcohol, dry it with a compressed air gun, and cure it in a curing box with a wavelength of 200 - 1500 nm, 100 mw / cm 2 , and at 50 °C for 10 min to obtain a cured product;

[0184] (3) Place the cured product in an oven and heat-treat it at 110 °C for 2 h to obtain the photocurable 3D printing resin.

[0185] Example 6

[0186] This embodiment provides a photocurable 3D printing resin. The difference from Example 1 is only that the re-curing blocked polyurethane acrylate provided in Preparation Example 1 is replaced with the re-curing blocked polyurethane acrylate provided in Preparation Example 2, and other settings are exactly the same as those in Example 1.

[0187] Example 7

[0188] This embodiment provides a photocurable 3D printing resin. The difference from Example 1 is only that the re-curing blocked polyurethane acrylate provided in Preparation Example 1 is replaced with the re-curing blocked polyurethane acrylate provided in Preparation Example 3, and other settings are exactly the same as those in Example 1.

[0189] Example 8

[0190] This embodiment provides a photocurable 3D printing resin. The difference from Example 1 is only that the re-curing blocked polyurethane acrylate provided in Preparation Example 1 is replaced with the re-curing blocked polyurethane acrylate provided in Preparation Example 4, and other settings are exactly the same as those in Example 1.

[0191] Example 9

[0192] This embodiment provides a photocurable 3D printing resin. The difference from Example 1 is only that the re-curing blocked polyurethane acrylate provided in Preparation Example 1 is replaced with the re-curing blocked polyurethane acrylate provided in Preparation Example 5, and other settings are exactly the same as those in Example 1.

[0193] Example 10

[0194] This example provides a photocurable 3D printing resin, which is only different from Example 1 in that isobornyl acrylate is not added, and the content of hexafluorobutyl methacrylate is increased to 35 parts, and other settings are exactly the same as those in Example 1.

[0195] Example 11

[0196] This example provides a photocurable 3D printing resin, which is only different from Example 1 in that hexafluorobutyl methacrylate is not added, and the content of isobornyl acrylate is increased to 35 parts, and other settings are exactly the same as those in Example 1.

[0197] Example 12

[0198] This example provides a photocurable 3D printing resin, which is only different from Example 1 in that dimethylhydroxysiloxane is replaced with an equal weight of diethyltoluenediamine, and other settings are exactly the same as those in Example 1.

[0199] Example 13

[0200] This example provides a photocurable 3D printing resin, which is only different from Example 1 in that dimethylhydroxysiloxane is replaced with an equal weight of bis(sec-butylamino)diphenylmethane, and other settings are exactly the same as those in Example 1.

[0201] Example 14

[0202] This example provides a photocurable 3D printing resin, which is only different from Example 1 in that in step (2), curing is carried out in a curing oven at a wavelength of 200 - 1500 nm, 30 mw / cm 2 , 40 °C for 30 min; in step (3), heat treatment is carried out at 80 °C for 3 h; other settings are exactly the same as those in Example 1.

[0203] Example 15

[0204] This example provides a photocurable 3D printing resin, which is only different from Example 1 in that in step (2), curing is carried out in a curing oven at a wavelength of 200 - 1500 nm, 200 mw / cm 2 , 60 °C for 5 min; in step (3), heat treatment is carried out at 130 °C for 1 h; other settings are exactly the same as those in Example 1.

[0205] Example 16

[0206] This example provides a photocurable 3D printing resin, which is only different from Example 1 in that in step (2), thermal curing is not carried out, and curing is carried out at a wavelength of 200 - 1500 nm, 100 mw / cm 2, cure in a curing oven at 25°C for 1 h; other settings are exactly the same as those in Example 1.

[0207] Example 17

[0208] This example provides a photocurable 3D printing resin, which is different from Example 1 only in that in step (2), photocuring is not carried out, and thermal curing is carried out in a curing oven at 50°C for 1 h; other settings are exactly the same as those in Example 1.

[0209] Example 18

[0210] This example provides a photocurable 3D printing resin, which is different from Example 1 only in that the heat treatment in step (3) is no longer carried out, and other settings are exactly the same as those in Example 1.

[0211] Comparative Example 1

[0212] This comparative example provides a photocurable 3D printing resin, which is different from Example 1 only in that the re-curable blocked polyurethane acrylate provided in Preparation Example 1 is replaced with the re-curable blocked polyurethane acrylate provided in Comparative Preparation Example 1, and other settings are exactly the same as those in Example 1.

[0213] Comparative Example 2

[0214] This comparative example provides a photocurable 3D printing resin, which is different from Example 1 only in that the multi-curable blocked polyurethane acrylate is no longer added, the content of CN989NS is increased to 35 parts, the content of isobornyl acrylate is increased to 45 parts, and the content of hexafluorobutyl methacrylate is increased to 10 parts, and other settings are exactly the same as those in Example 1.

[0215] Comparative Example 3

[0216] This comparative example provides a photocurable 3D printing resin, which is different from Example 1 only in that the low water absorption resin CN989NS is no longer added, the content of the multi-curable blocked polyurethane acrylate provided in Preparation Example 1 is increased to 45 parts, the content of isobornyl acrylate is increased to 35 parts, and the content of hexafluorobutyl methacrylate is increased to 10 parts, and other settings are exactly the same as those in Example 1.

[0217] Comparative Example 4

[0218] This comparative example provides a photocurable 3D printing resin, which is different from Example 1 only in that the low water absorption monomer is no longer added, the content of the multi-curable blocked polyurethane acrylate provided in Preparation Example 1 is increased to 50 parts, and the content of the low water absorption resin CN989NS is increased to 40 parts, and other settings are exactly the same as those in Example 1.

[0219] Comparative Example 5

[0220] This comparative example provides a photocurable 3D printing resin, which is only different from Example 1 in that no chain extender is added, and the content of the multi-curing blocked polyurethane acrylate provided in Preparation Example 1 is increased to 50 parts, and other settings are exactly the same as those in Example 1.

[0221] Test Example 1

[0222] Test samples: The photocurable 3D printing resins provided in Examples 1 to 18 and the photocurable 3D printing resins provided in Comparative Examples 1 to 5.

[0223] Test method:

[0224] (1) Water absorption rate: Refer to T / CAMDI 087;

[0225] (2) Solubility: Refer to T / CAMDI 087;

[0226] (3) According to the ASTM G154 standard, the irradiance is set to 0.5 W / m 2 , soak the specimen in water, accelerate aging at 50 °C for 30 days, and test the changes in performance before and after aging to evaluate the anti-aging performance of the material.

[0227] The specific test results are shown in Table 1:

[0228] Table 1

[0229]

[0230] As shown in Table 1, the water absorption rate of the photocurable 3D printing resin of the present invention is ≤65 μg / mm 3 , and the solubility is ≤5.3 μg / mm 3 ; before the above aging operation, the tensile strength attenuation of the photocurable 3D printing resin is 55-98%, the tensile strength is 21-61 MPa, the tensile elastic modulus is 729-2352 MPa, and the elongation at break is 13-89%; after the above aging operation, the tensile strength attenuation of the photocurable 3D printing resin can still be maintained at 57-99%, the tensile strength can still be maintained at 18-63 MPa, the tensile elastic modulus can still be maintained at 812-2319 MPa, and the elongation at break can still be maintained at 9-66%.

[0231] In particular, Examples 1 to 3 are the preferred technical solutions of the present invention, and the water absorption rate of the photocurable 3D printing resin is ≤32 μg / mm 3 , and the solubility is ≤1.6 μg / mm 3; Before the above aging operation, the tensile attenuation of the photocurable 3D printing resin is 55-65%, the tensile strength is 53-58 MPa, the tensile elastic modulus is 2000-2400 MPa, and the elongation at break is 55-98%; after the above aging operation, the tensile attenuation of the photocurable 3D printing resin can still be maintained at 68%-98%, the tensile strength can still be maintained at 56-63 MPa, the tensile elastic modulus can still be maintained at 2100-2400 MPa, and the elongation at break can still be maintained at 49%-66%.

[0232] In summary, the photocurable 3D printing resin prepared by the present invention has the advantages of excellent mechanical properties, low viscosity, and fast printing speed. This fully demonstrates that the present invention introduces a resin with multiple curing functions, that is, a resin containing both photocurable groups and thermosetting groups, and at the same time introduces a chain extender. Through secondary curing and heat treatment, the molecular weight and crosslinking density of the resin are further increased, thereby improving the stress relaxation resistance of the material. In addition, (meth)acrylate resins and monomers with low water absorption, light absorbers, antioxidants, and light stabilizers are introduced to improve the aging resistance of the material.

[0233] Finally, it should be noted that the above embodiments are only used to illustrate the technical solutions of the present invention, and are not intended to limit them; although the present invention has been described in detail with reference to the foregoing embodiments, those of ordinary skill in the art should understand that they can still modify the technical solutions described in the foregoing embodiments, or perform equivalent replacements on some or all of the technical features; and these modifications or replacements do not cause the essence of the corresponding technical solutions to deviate from the scope of the technical solutions of the embodiments of the present invention.

Claims

1. A photocurable 3D printing resin, characterized in that, The raw materials for preparing the photocurable 3D printing resin include, by weight parts: The multi-curing blocked polyurethane acrylate is a polyurethane acrylate blocked by ethyl 3-(2-trimethylacetamido-3-pyridyl)acrylate; The low water absorption resin includes low water absorption acrylate resin and / or low water absorption methacrylate resin, and the water absorption rate of the low water absorption resin < 2%; The low water absorption monomer includes low water absorption acrylate monomer and / or low water absorption methacrylate monomer, and the water absorption rate of the low water absorption monomer < 2%.

2. The photocurable 3D printing resin according to claim 1, wherein The raw materials for preparing the multi-curing blocked polyurethane acrylate include, by molar ratio: And / or, the diol includes any one or a combination of at least two of dimethyl hydroxy silicone oil, hydroxyl-terminated polybutadiene, hydroxyl-terminated polybutylene adipate, polypropylene glycol or polyethylene glycol; And / or, the isocyanate includes any one or a combination of at least two of hexamethylene diisocyanate, toluene diisocyanate, diphenylmethane diisocyanate, xylylene diisocyanate, isophorone diisocyanate or dicyclohexylmethane-4,4'-diisocyanate; And / or, the catalyst includes any one or a combination of at least two of organic zinc, bismuth catalyst or mixed catalyst; And / or, the catalyst includes any one or a combination of at least two of BCAT-E16, BCAT-E20, BCAT-E25A, BCAT-E28A, BCAT-T100R, BCAT-E20CX, ZCAT-EY18, ZCAT-EZ22, ZCAT-T50, BX-EM14 or BX-EM23; And / or, the multi-curing blocked polyurethane acrylate is prepared by the following method: after mixing the diol and the isocyanate, adding the catalyst and performing a first stirring; then adding ethyl 3-(2-trimethylacetamido-3-pyridyl)acrylate for blocking and continuing the second stirring to obtain the multi-curing blocked polyurethane acrylate; And / or, the temperature of the first stirring is 50-80°C, the shear line speed of the first stirring is 10-25 m / s, and the time of the first stirring is 1-5 h; And / or, the temperature of the second stirring is 50-90°C, the shear line speed of the second stirring is 10-25 m / s, and the time of the second stirring is 1.5-3 h.

3. The photocurable 3D printing resin according to claim 1, wherein The low water absorption resin satisfies the following parameters: water solubility at 20°C < 10 g / L, -60°C < Tg < 450°C, molecular weight < 8000 g / mol; The low water absorption monomer satisfies the following parameters: water solubility at 20°C < 10 g / L, -60°C < Tg < 300°C, molecular weight < 1000 g / mol; And / or, the low water absorption resin includes any one or a combination of at least two of CN1963NS, CN1964NS, CN1993CG, CN2920, CN2921, CN310NS, CN3211, CN8003NS, CN8010NS, CN8881NS, CN8883NS, CN8887NS, CN8889NS, CN8890NS, CN8891NS, CN8896NS, CN9001NS, CN9011, CN9014NS, CN9021NS, CN9062, CN959, CN9290, CN959, CN964NS, CN969NS, CN983NS, CN989NS, CN991NS, CN2203NS, CN2261NS, CN2282, CN2303NS, CN2302, CN2304, BR-930D, BR-941D, BR-952, BR-970BT, BR-970H, BR-990, BR-371MS, BR-372, BR-541MS, BR-571, BR-741, BR-744BT, BR-744SD, BR-742MS, BR-541S, BR-571, BR-582I10, BR-202, BR-541MB or BR-571MB; And / or, the low water absorption monomer includes any one or a combination of at least two of hexafluorobutyl methacrylate, dodecafluoroheptyl acrylate, tridecafluorooctyl methacrylate, perfluoroalkyl ethyl acrylate, dicyclopentenyl acrylate, 4-tert-butylcyclohexyl acrylate, o-phenylphenoxyethyl acrylate, dicyclopentenyl ethoxylated methacrylate, dicyclopentanyl methacrylate, trimethylolpropane formal acrylate, isobornyl methacrylate, isobornyl acrylate, dipropylene glycol diacrylate, (2) ethoxylated bisphenol A dimethacrylate, (4) ethoxylated bisphenol A dimethacrylate, tricyclodecane dimethanol diacrylate, dimethylaminoethyl methacrylate, trimethylolpropane triacrylate, ethoxylated trimethylolpropane triacrylate or tris(2-hydroxyethyl) isocyanurate triacrylate; 4. The photocurable 3D printing resin according to claim 1, wherein The chain extender includes any one or a combination of at least two of polytetrahydrofuran, polycaprolactone, dimethyl hydroxy silicone oil, polybutylene adipate, N-aminoethyl aminopropyl trimethoxysilane, aminoethyl aminopropyl triethoxysilane, isophorone diamine, diethyl toluene diamine, 4,4'-methylene-bis(3-chloro-2,6-diethylaniline) or bis(sec-butylamino) diphenyl methane; And / or, the initiator includes any one or a combination of at least two of phenylbis(2,4,6-trimethylbenzoyl)phosphine oxide, 1-hydroxycyclohexyl phenyl ketone, 2-hydroxy-2-methyl-1-phenyl-1-propanone, (2,4,6-trimethylbenzoyl)-diphenylphosphine oxide, 2-isopropylthioxanthone, ethyl (2,4,6-trimethylbenzoyl)phenylphosphonate, camphorquinone, bis(2,6-difluoro-3-pyrrolylphenyl)titanocene, 2-hydroxy-4'-(2-hydroxyethoxy)-2-methylpropiophenone, didodecylbenzenesulfonium salt, long-chain alkoxydiphenylsulfonium salt, triphenylsulfonium salt or phenylthiophenyldiphenylsulfonium salt.

5. The photocurable 3D printing resin according to claim 1, characterized in that, The raw materials for preparing the photocurable 3D printing resin further include, by weight: 0.01 to 1 part of an absorber; And / or, the absorber includes a triazine ultraviolet absorber and / or a benzophenone absorber; And / or, the triazine ultraviolet absorber includes any one or a combination of at least two of 2-[4,6-bis(2,4-dimethylphenyl)-1,3,5-triazin-2-yl]-5-(octyloxy)phenol, 2-(4,6-diphenyl-1,3,5-triazin-2)-5-n-hexyloxy or UV1990; And / or, the benzophenone absorber includes any one or a combination of at least two of 2-hydroxy-4-n-octyloxybenzophenone, 2,4-dihydroxybenzophenone or 2-hydroxy-4-methoxybenzophenone; And / or, the raw materials for preparing the photocurable 3D printing resin further include, by weight: 0.01 to 1 part of an antioxidant; And / or, the antioxidant includes any one or a combination of at least two of diphenylamine, p-phenylenediamine, dihydroquinoline, 2,6-di-tert-butyl-4-methylphenol, bis(3,5-di-tert-butyl-4-hydroxyphenyl)sulfide, pentaerythritol tetrakis[β-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate], thiodipropionic acid diester, didodecyl ester, ditetradecyl ester, distearyl ester, trioctyl ester, tridecyl ester, tris(dodecyl alcohol) ester or tris(hexadecyl alcohol) ester; And / or, the raw materials for preparing the photocurable 3D printing resin further include, by weight: 0.01 to 1 part of a light stabilizer; And / or, the light stabilizer includes any one or a combination of at least two of carbon black, titanium dioxide, zinc oxide, lithopone, 2,2,6,6-tetramethylpiperidine, light stabilizer 770, light stabilizer 944, light stabilizer 292, light stabilizer 791, light stabilizer 783 or light stabilizer 700.

6. A preparation method of the photocurable 3D printing resin according to any one of claims 1 to 5, characterized in that, The preparation method includes: Mixing the raw materials in the photocurable 3D printing resin according to the ratio and stirring to obtain a mixed material; Subjecting the mixed material to a curing treatment through a 3D printing device to obtain a cured product; wherein, the curing treatment includes simultaneous photocuring and thermal curing; Subjecting the cured product to a heat treatment to obtain the photocurable 3D printing resin.

7. The preparation method of the photocurable 3D printing resin according to claim 6, characterized in that, The rotation speed of the stirring is 500 - 2000 r / min, the shear linear velocity of the stirring is 10 - 25 m / s, the temperature of the stirring is 30 - 70 °C, and the time of the stirring is 2 - 6 h.

8. The preparation method of the photocurable 3D printing resin according to claim 6, wherein, The light wavelength for the curing treatment is 200 to 1500 nm, and the light intensity for the curing treatment is 30 to 200 mw / cm 2 , the temperature for the curing treatment is 40 to 50 °C, and the time for the curing treatment is 5 to 30 min.

9. The preparation method of the photocurable 3D printing resin according to claim 6, wherein, The temperature of the heat treatment is 80 - 130 °C, and the time of the heat treatment is 1 - 3 h.

10. Use of a photocurable 3D printing resin according to any one of claims 1 - 5 in the preparation of materials for aerospace, automotive manufacturing, building materials or medical materials.

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