CN111116966A - Photosensitive resin containing bulk phase micro-nano bubbles and preparation method thereof - Google Patents

Abstract

The embodiment of the invention discloses photosensitive resin containing bulk micro-nano bubbles, which is particularly suitable for dental and jewelry casting and used for 3D printing, and comprises the following components in percentage by volume (v/v): 70-99% of photosensitive resin and 1-30% of micro-nano bubbles. Compared with the existing 3D printing resin, the photosensitive resin containing the bulk phase micro-nano bubbles provided by the embodiment of the invention is particularly suitable for a 3D printing technology, the combustion is sufficient, no residual ash or residue is generated after the combustion, and the bulk phase micro-nano bubbles are contained, so that the volume cannot expand in the heating process, and the cast shell cannot be cracked. The embodiment of the invention also provides a preparation method of the photosensitive resin containing the bulk micro-nano bubbles.

Description

Photosensitive resin containing bulk phase micro-nano bubbles and preparation method thereof

Technical Field

The invention relates to the technical field of resin materials, in particular to photosensitive resin containing bulk micro-nano bubbles and a preparation method thereof.

Background

3D printing is an emerging rapid prototyping technology, which is listed as one of the signs of the third industrial revolution. The academic circles refer to incremental manufacturing, additive manufacturing, rapid prototyping and rapid manufacturing, and refer to a digital manufacturing technology for rapidly printing out product prototypes or parts according to three-dimensional models of products based on the principle of discrete material layer-by-layer stacking forming. The 3D printing technology integrates systematic and comprehensive technologies of multidisciplinary knowledge such as computer software, materials, machinery, control and the like, and all the composition technologies are mutually promoted and mutually restricted. Compared with the traditional material reduction manufacturing, the additive manufacturing has obvious advantages, can realize high-complexity products which are difficult to manufacture by the traditional method, has economical efficiency and rapid processing capability, and is beneficial to manufacturing in extremely small batches and special fields.

Currently, 3D printing materials mainly include polymer materials, metal materials, ceramic materials, and the like. Photosensitive resins are an important class of polymeric materials that can be shaped by rapid conversion from a liquid to a solid under the influence of light (ultraviolet or visible light). As one of the earliest developed and commercialized 3D printing technologies, the photocuring rapid prototyping technology has attracted attention by virtue of its advantages of high prototyping precision, high printing speed, mature process, and the like. The photocuring 3D printing technology using photosensitive resin as a raw material mainly includes a stereolithography technology (SLA), a digital light processing technology (DLP), a visible light forming technology (LCD), a three-dimensional inkjet printing technology (3DP), a recently developed Direct Ink Writing (DIW) technology, and the like.

With the continuous development and maturity of 3D printing equipment and process, the limitation of materials for 3D printing has become an important factor restricting the development of 3D printing technology. Therefore, the research and development of novel 3D printing materials gradually become the key of 3D printing innovation breakthrough and is a necessary way for expanding the application field of 3D printing technology. Generally, in addition to realizing high performance and functionalization of photosensitive resin, parameters such as viscosity, polymerization speed, curing shrinkage rate and the like of a material system are adjusted so that the photosensitive resin can be printed efficiently and with high precision, which is the most basic requirement for 3D printing of photosensitive resin. Through methods of molecular structure modification, composition formula optimization, functional material compounding and the like, the performance of the photosensitive resin for 3D printing can be effectively improved, functionalization can be realized, and the basic requirements of a photocuring 3D printing technology on material performance can be met.

For example, a conventional jewelry making process typically includes the following steps: (1) designing a concept; (2) engraving a wax plate and pressing a rubber mold; (3) injecting wax into the rubber mold; (4) completing the wax pattern; (5) planting wax trees; (6) weighing wax trees, and calculating the amount of cast metal; (7) pouring gypsum; (8) baking gypsum; (9) taking out the plaster mold; (10) casting metal by a centrifugal process; (11) frying, washing and cleaning the gypsum mold; (12) shearing the casting; (13) barrel polishing; (14) calendering; (15) polishing with a polishing machine, and the like. The technical requirements of the craftsman in the steps (2), (3) and (4) are high, for example, the craftsman is required to manually carve a wax plate according to the design drawing in the step (2), and then the silver plate is poured out by using a lost wax casting method, and the rubber mold is required to be pressed by the silver plate for batch production of the wax plate. The process is the highest requirement in the jewelry making process, the prepared silver plate is smooth and has no trace, each part has reasonable structure, and the position size of the embedded jewel is accurate and correct.

The traditional denture processing mode is mainly that a denture metal inner crown is manufactured through a traditional manual technology, and firstly, a plaster model is poured according to a mouth impression of a patient; then, manufacturing a wax pattern of the porcelain tooth according to the gypsum model; then entering a lost wax casting process of the metal inner crown, and mainly comprising four steps of casting way installation, embedding, lost wax and casting; and finally, finishing the manufacture of the porcelain tooth through surface treatment and surface finishing processes.

The steps (2), (3) and (4) in the traditional jewelry manufacturing process and the steps of manufacturing porcelain tooth wax patterns in the traditional false tooth processing can be completely replaced by a 3D printing technology, so that the manufacturing difficulty is reduced, the defects of size or detail mismatch or casting caused by artificial factors such as the skill level and the like are avoided, the process can be completed in a large batch at one time, and a large amount of labor cost and time are saved.

However, the conventional 3D printing resin used in dental or jewelry casting is expensive, and it is necessary to completely burn out the resin as a wax material for casting, and it is impossible to fail to support the embedded shell by expansion during the heat sintering process, and it is impossible to store any sintering ash or residue after sintering, or various casting defects such as voids, surface roughness, burrs, pores, etc. are generated in the cast workpiece. The workpiece manufactured by the conventional 3D printing photosensitive resin is integrally formed by the photosensitive resin, namely, the workpiece is formed by an organic matter which is chemically crosslinked, the crosslinked photosensitive resin is difficult to completely burn out, trace residues after sintering have an accumulation effect along with the increase of the total volume of a sintered workpiece, and casting defects exist more after casting, the main reason is that the organic matter cannot be completely burnt out, failure and rework are finally caused, and unnecessary cost is increased.

Disclosure of Invention

An object of an embodiment of the present invention is to provide a photosensitive resin containing bulk micro-nano bubbles for 3D printing, which is particularly suitable for dental and jewelry casting. Compared with the existing 3D printing resin, the photosensitive resin containing the bulk phase micro-nano bubbles provided by the embodiment of the invention is particularly suitable for a 3D printing technology, the combustion is sufficient, no residual ash or residue is generated after the combustion, and the bulk phase micro-nano bubbles are contained, so that the volume cannot expand in the heating process, and the cast shell cannot be cracked. The embodiment of the invention also provides a preparation method of the photosensitive resin containing the bulk micro-nano bubbles.

Compared with the traditional manual preparation process, the technical scheme of the invention is particularly suitable for 3D printing, and has the advantages of high efficiency, good repeatability, batch preparation, avoidance of dependence on manual technology maturity and the like; the photosensitive resin containing the bulk phase micro-nano bubbles provided by the embodiment of the invention eliminates the defects of the existing 3D printing casting material, so that the surface of the casting sample piece is smooth, no air holes or holes exist, the compactness of the sample piece is high, the product manufacturing power is high, the material cost is low, and the material preparation method is simple.

In order to achieve the above object, an embodiment of the present invention provides a photosensitive resin containing bulk micro-nano bubbles, which includes, in volume percent (v/v): 70-99% of photosensitive resin and 1-30% of micro-nano bubbles.

The bubbles as referred to herein refer to gas-filled cavities in a liquid (e.g., a resin), and the basic condition for generating bubbles is that the internal pressure of the bubbles in the liquid is not less than the ambient pressure. The surface of the bubble possesses a composition that is different from the properties of the liquid. Bubbles can be broadly classified into macroscopic bubbles, micro bubbles, and nano bubbles according to size order of magnitude. Large bubbles generally rise to the surface to be disintegrated rapidly due to large buoyancy, but the bubbles with the diameter smaller than 1 mu m, namely bulk micro-nano bubbles, can stably exist in liquid (such as resin) for a long time due to the existence of an unknown mechanism at present. Under the condition of a bulk phase (generally referred to as a liquid phase environment), the shape of the bubbles is in a complete sphere shape, and the bubbles with the diameter equal to or less than 1 mu m are bulk micro-nano bubbles. The production method of the micro-nano bubbles comprises the following steps: solution substitution method, direct dropping method, temperature difference method, ultrasonic method, decompression method, electrolysis method, mechanical method, etc., and these production methods for generating micro-nano bubbles are known to those skilled in the art.

In a non-limiting embodiment, the bulk micro-nano bubbles used in the technical solution of the present invention are prepared by a mechanical method, but other preparation methods are not excluded.

Further, the photosensitive resin comprises the following components in percentage by mass (w/w): 0.1-2% of photoinitiator, 0.05-2% of ultraviolet absorbent, 0.001-0.5% of colorant, 0.05-2% of surfactant, 0.01-0.05% of defoaming agent, 20-70% of active diluent containing active functional group f more than or equal to 1 and 20-65% of active oligomer containing active functional group f more than or equal to 1.

According to the invention, a large amount of bulk micro-nano bubbles are added on the basis of photosensitive resin, the bubbles can stably exist in the photosensitive resin, the bulk micro-nano bubbles can occupy a large proportion (1% -30%) by adjusting the component types and proportions of the photosensitive resin, and meanwhile, the bulk micro-nano bubbles can stably exist in the photosensitive resin for a long time and do not have large bubbles with the size of more than 1 micrometer.

The photosensitive resin used in the technical scheme of the invention can be photosensitive resin used for 3D printing technology in the prior art, namely, bulk micro-nano bubbles can be directly added on the basis of the prior photosensitive resin. However, in order to obtain the desired properties of the resin for 3D printing suitable for 3D printing technology, particularly suitable for dental and jewelry casting, such as the ability to contain and uniformly disperse bulk micro-nano bubbles in a large volume ratio, and the properties of sufficient combustion without remaining ash or residue after combustion, the photosensitive resin used is preferably the above photosensitive resin.

Further, the photoinitiator is one or more of a free radical photoinitiator, a cationic photoinitiator, a visible light initiator and a macromolecular photoinitiator.

Further, the applicable wavelength of the photoinitiator is 200nm to 520mn, preferably 355nm to 468 nm. For example 355nm, 365nm, 385nm, 405nm, 420nm, 468 nm.

By way of non-limiting example, the free radical photoinitiator is: a class I cleavage-type free radical photoinitiator comprising: methyl benzoylformate (general reference: MBF; CAS No. 15206-55-0), benzoin dimethyl ether (general reference: BDK; CAS No. 24650-42-8), 2-hydroxy-methylphenylpropane-1-one (general reference: 1173; CAS No. 7473-98-5), 1-hydroxy-cyclohexyl-phenylketone (general reference: 184; CAS No. 947-19-3), 2-methyl-2- (4-morpholinyl) -1- [4- (methylthio) phenyl ] -1-propanone (general reference: 907; CAS No. 71868-10-5), 2,4, 6-trimethylbenzoyl-diphenylphosphine oxide (general reference: TPO; CAS No. 75980-60-8), Ethyl 2,4, 6-trimethylbenzoylphosphonate (generic trademark: TPO-L; CAS No: 84434-11-7), 2-phenylbenzyl-2-dimethylamine-1- (4-morpholinobenzylphenyl) butanone (generic trademark: 369; CAS No: 119313-12-1), 2-hydroxy-4' - (2-hydroxyethoxy) -2-methylpropiophenone (generic trademark: 2959; CAS No: 106797-53-9), a-diethoxyacetophenone (generic trademark: DEAP; CAS No: 6175-45-7); a class II hydrogen abstraction-type free radical photoinitiator comprising: benzophenone (general brand: BP; CAS number: 119-61-9), tetraethyl michelson (general brand: EMK; CAS number: 90-93-7), 4-methylbenzophenone (general brand: MBZ; CAS number: 134-84-9), 4-chlorobenzophenone (general brand: CBZ; CAS number: 134-85-0), methyl benzoylbenzoate (general brand: OMBB; CAS number: 606-28-0), 4-phenylbenzophenone (general brand: PBZ; CAS number: 2128-93-0), ethyl 4-dimethylaminobenzoate (general brand: EDB; CAS number: 10287-53-3), isooctyl p-dimethylaminobenzoate (general brand: EHA; CAS number: 21245-02-3), Isopropyl thioxanthone (ITX; CAS No: 5495-84-1), 2, 4-diethyl thioxanthone (EDTX; CAS No: 82799-44-8);

the macromolecular photoinitiator comprises: macromolecular thioxanthone photoinitiators (CAS number: 1258512-68-3);

the cationic photoinitiator comprises: diazonium salts, diaryliodonium salts, triarylsulfonium salts, alkylsulfonium salts, iron arene salts, sulfonyloxy ketones and triarylsiloxy ethers, bis (4-tert-butylphenyl) iodonium hexafluorophosphate (CAS No.: 61358-25-6), bis (4-tert-butylphenyl) iodonium trifluoromethanesulfonate (CAS No.: 84563-54-2), cyclopropyldiphenylsulfonium tetrafluoroborate (CAS No.: 33462-81-6), diphenyliodonium hexafluorophosphate (CAS No.: 58109-40-3), diphenyliodonium hexafluoroarsenate (CAS No.: 62613-15-4), diphenyliodonium trifluoromethanesulfonate (CAS No.: 66003-76-7), 2- (3, 4-dimethoxystyryl) -4, 6-bis (trichloromethyl) -1,3, 5-triazine (CAS number: 42880-07-9), 2- [2- (furan-2-yl) vinyl ] -4, 6-bis (trichloromethyl) -1,3, 5-triazine (CAS number: 154880-05-4), tri-p-tolylsulfonium trifluoromethanesulfonate (CAS number: 127820-38-6);

the visible light initiator comprises: bis 2, 6-difluoro-3-pyrrolylphenyltitanocene (CAS number: 125051-32-3), camphorquinone (CAS number: 10373-78-1).

Any one or more of the above-listed photoinitiators may be used in combination.

Further, the ultraviolet absorbent is one or more of salicylate, benzophenone, benzotriazole, substituted acrylonitrile and triazine ultraviolet absorbent.

By way of non-limiting example, the ultraviolet light absorbers include: bis (1,2,2,6, 6-pentamethyl-4-piperidine) sebacate in admixture with 1-methyl-8- (1,2,2,6, 6-pentamethyl-4-piperidine) sebacate (CAS number: 41556-26-7), 2- (2 ' -hydroxy-3 ' -tert-butyl-5 ' -methylphenyl) -5-chlorobenzotriazole (CAS number: 3896-11-5), 2- (2H-benzotriazol-2-yl) -4, 6-di-tert-amylphenol (CAS number: 25973-55-1), 2- (2 ' -hydroxy-5 ' -tert-octylphenyl) benzotriazole (CAS number: 3147-75-9), bis (2,2,6, 6-tetramethyl-4-piperidyl) sebacate (CAS number: 52829-07-9), 2-hydroxy-4-n-octyloxybenzophenone (CAS number: 1843-05-6), 2-hydroxy-4-methoxybenzophenone (CAS No.: 131-57-7), 2-hydroxy-4-methoxy-5-sulfonic acid benzophenone (CAS No.: 4065-45-6), 2- (2 '-hydroxy-5' -methylphenyl) benzotriazole (CAS No.: 2440-22-4).

Any one or more of the above-listed ultraviolet absorbers may be used in combination.

Further, the colorant is one or more of an organic pigment, an inorganic pigment and a dye.

As non-limiting examples, the organic pigments include azo pigments such AS disazo pigments, β -naphthol pigments, naphthol AS pigments, lake pigments, benzimidazolone pigments, azo condensation pigments, metal complex pigments, and non-azo pigments such AS phthalocyanine pigments, quinacridone pigments, thioindigo pigments, anthraquinone pigments, dioxazine pigments, triarylmethane pigments, 1, 4-pyrrolopyrroledione pigments, quinophthalone pigments.

Any one or more of the above listed colorants may be used in combination.

Further, the surfactant is one or more of a cationic surfactant, an anionic surfactant, an amphoteric surfactant and a nonionic surfactant; however, the cationic surfactant and the anionic surfactant are not used together. The use of both cationic and anionic surfactants results in precipitation deactivation.

As non-limiting examples, the cationic surfactant includes amine salt type, quaternary ammonium salt type, heterocyclic type cationic surfactants; the anionic surfactant comprises carboxylate, sulfonate and sulfate anionic surfactant; the amphoteric surfactant comprises amino acid type and betaine type amphoteric surfactants; the nonionic surfactant comprises long-chain fatty alcohol-polyoxyethylene ether, alkylphenol ethoxylates, fatty acid-polyoxyethylene ester, polyoxyethylene alkylamine, polyoxyethylene alkylamide, polyether nonionic surfactant and the like.

Among them, amphoteric surfactants are preferred. Examples of the amino acid type amphoteric surfactants include dodecylaminopropionates such as sodium dodecylaminopropionate. Examples of the betaine-type amphoteric surfactant include carboxylic acid-based betaines such as alkyl dimethyl betaine; sulfobetaines, such as alkyldimethylsulfoethylbetaine, alkyldimethylsulfopropylbetaine; and (3) a phosphate betaine, such as an alkyl dimethyl hydroxypropyl phosphate betaine.

Further, the defoaming agent is one or more of dimethyl siloxane defoaming agent, modified siloxane defoaming agent, vinyl ether defoaming agent and acrylate defoaming agent. Preferably, the defoaming agent is an oil-soluble defoaming agent which is composed of mineral oil and polyether, does not undergo emulsification, has good dispersibility in an oily system and is less affected by pH.

The photosensitive resin containing bulk micro-nano bubbles provided by the embodiment of the invention has a large proportion of bulk micro-nano bubbles and can ensure that the bulk micro-nano bubbles have a long-term stable dispersion effect in liquid photosensitive resin at the same time through the effective combination of specific contents and types of surfactants and antifoaming agents (namely 0.05 wt% -2 wt% of surfactant and 0.01 wt% -0.05 wt% of antifoaming agent).

Further, the reactive diluent containing the reactive functional group f is more than or equal to 1 and comprises the following components: one or more of acrylate reactive diluent, methacrylate reactive diluent, vinyl ether reactive diluent and epoxy reactive diluent. Acrylate reactive diluents are preferred.

As non-limiting examples, the acrylate reactive diluent includes one or more of fatty alcohols, diols, polypropylene glycols, polyethylene glycols, bisphenol a, trimethylolpropane, pentaerythritol reactive diluents.

Further, the active oligomer containing the active functional group f is more than or equal to 1: one or more of a urethane acrylate oligomer, a polyester acrylate oligomer, an epoxy acrylate oligomer, a polybutadiene acrylate oligomer, and a methacrylated acrylate oligomer.

As non-limiting examples, the reactive oligomer containing the reactive functional group f ≧ 1 includes one or more of aliphatic urethane acrylates, aromatic urethane acrylates, bisphenol A epoxy acrylates, epoxy novolac epoxy acrylates, polyester acrylates, and acrylics.

The embodiment of the invention also provides a preparation method of the photosensitive resin containing the bulk micro-nano bubbles, which comprises the following steps:

(1) weighing the components according to the raw material ratio of the photosensitive resin;

(2) heating, sealing and stirring the mixture in a container at the stirring temperature of 40-95 ℃ for 0.5-12 h to obtain a photosensitive resin mixture;

(3) and adding and dispersing the bulk micro-nano bubbles into the photosensitive resin mixture, and performing 1-10 h to obtain the photosensitive resin containing the bulk micro-nano bubbles.

In one embodiment, step (3) is performed in a micro-nano bubble generating device that generates bubbles using a solution substitution method, a direct drop method, a temperature difference method, an ultrasonic method, a depressurization method, an electrolytic method, or a mechanical method. Among them, the bubble generation is preferably performed by a mechanical method.

The step (2) is performed with closed stirring to prevent the volatilization of the organic material from polluting the environment and to prevent impurities in the environment from entering the prepared material. Sufficient heating and stirring time is given to achieve sufficient dissolution and uniform mixing of the materials.

And (4) comprehensively determining the proportion of the micro-nano bubbles in the photosensitive resin containing the bulk micro-nano bubbles finally obtained in the step (3) by the addition of the surfactant and the defoaming agent and the preparation time of the micro-nano bubble generator.

The micro-nano bubble generator is a mature product in the prior art, for example, a ZJC-NM series micro-nano bubble generator of Shanghai Zhongjing environmental protection technology can be adopted; a micro-nano bubble generator series of the environmental protection technology limited of the Jinan Lang.

The photosensitive resin containing bulk micro-nano bubbles reduces the proportion of resin materials in a printing model due to the existence of a large proportion of bulk micro-nano bubbles, and can ensure that the subsequent heating and sintering are more sufficient; sintering residues do not exist after a large number of models are sintered simultaneously, and the method is suitable for large-scale casting production in factories; the reduction of the resin material proportion in the model also obviously reduces the material cost; due to the existence of the bubbles, in the sintering process, the material is collapsed to the bubble position instead of being expanded to the shell, so that the expansion crack of the embedded shell caused by the temperature rise expansion of the resin model is reduced, the failure times are reduced, and the success rate is improved; the reduction of the resin proportion also shortens the time required for completely sintering the model, and improves the production efficiency; the reduction of the resin proportion also reduces the pollution to the environment caused by combustion, and is an environment-friendly 3D printing photosensitive resin for casting; meanwhile, the micro-nano bubbles are extremely tiny, so that the surface precision of the printing model cannot be reduced, and the surface precision of the casting cannot be reduced. In conclusion, the photosensitive resin containing a large amount of bulk micro-nano bubbles has the advantages of saving labor and raw material cost, reducing environmental pollution, improving production efficiency and the like.

The embodiment of the invention has the following advantages:

1. by effectively combining a trace amount of surfactant and a defoaming agent and combining a micro-nano bubble generating device, the photosensitive resin for 3D printing containing a large amount of bulk micro-nano bubbles is prepared, the resin has bulk micro-nano bubbles with a large proportion content, and the bulk micro-nano bubbles have a long-term stabilizing effect in liquid photosensitive resin;

2. the proportion of resin materials in the model is reduced, so that the combustion is more sufficient, and sintering residues do not exist after a large number of models are sintered simultaneously;

3. the method is suitable for large-scale casting production in factories, and saves labor and material cost.

Detailed Description

The present invention is described in terms of particular embodiments, other advantages and features of the invention will become apparent to those skilled in the art from the following disclosure, and it is to be understood that the described embodiments are merely exemplary of the invention and that it is not intended to limit the invention to the particular embodiments disclosed. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.

Example 1

Weighing the following components in percentage by mass: 32G trimethylolpropane trimethacrylate (TMPTMA), 16G glycerol propylene oxide triacrylate (GPTA), 15G dipropylene glycol diacrylate (DPGDA), 16G CN2261 (polyester acrylate oligomer, Sartomer Sartomer), 20G BR-144 (urethane acrylate, Dymax), 0.4G 1-hydroxy-cyclohexyl-phenyl ketone (general name: 184; CAS No.: 947-19-3), 0.4G 2- (2 ' -hydroxy-3 ' -tert-butyl-5 ' -methylphenyl) -5-chlorobenzotriazole (CAS No.: 3896-11-5), 0.1G Lutensol TO-3 (Pasteur), 0.02G silicone antifoam BYK-065, 0.08G fluorescent Red G (Meirno chemical Co., Wenzhou; index: solvent Red 149), placing the above components into a corresponding container, stirring at 55 deg.C, controlling stirring speed at 100rpm within 30min, slowly increasing to 1000rpm, stirring for 5 hr until the mixture becomes uniform transparent liquid, weighing and stirring all the time in dark or yellow environment, and completely preparing photosensitive resin;

then putting the prepared photosensitive resin part into a bulk micro-nano generator, continuously stirring and foaming until the material is changed into uniform and semitransparent liquid, wherein the preparation time is 5 hours, taking out, placing and packaging to finally obtain stable 3D printing photosensitive resin containing a large amount of bulk micro-nano bubbles, and detecting that the material contains 20% v/v bulk micro-nano bubbles with the diameters within 1000nm, wherein the micro-nano bubbles in the material can stably exist in the system for 3 months;

the molded model printed by the material has no residue and ash after sintering, and the cast model has smooth surface, no air holes, no burrs, compact interior and no defects of cavities and the like.

Example 2

Weighing the following components in percentage by mass: 18g of 2 (2-ethoxyethoxy) ethyl acrylate (EOEOEA), 16g of glycerol propylene oxide triacrylate (GPTA), 15g of 2 (ethoxy) bisphenol A dimethacrylate (BPA2(EO) DMA), 14g of ethoxylated trimethylolpropane triacrylate (EO3TMPTA), 14g of CN2261 (polyester acrylate oligomer, Sartomer Sartomer), 10g of GENOMER 4690 (aliphatic urethane acrylate; Rahn Ruon trade, Inc.), 12g of XDT-1018 (dendrimer, Dymax), 0.3g of 1-hydroxy-cyclohexyl-phenyl ketone (general brand: 184; CAS number: CAS 947-19-3), 0.2g of ethyl 2,4, 6-trimethylbenzoylphosphonate (general brand: TPO-L; CAS number: 84434-11-7), 0.2g of 2- (2 '-hydroxy-5' -tert-octylphenyl) benzotriazole (CAS number: TPO-L) CAS number: 3147-75-9), 0.2g fatty alcohol polyoxyethylene ether (AEO), 0.03g acrylic defoamer BYK-354, 0.07g solvent orange 62 (Milzhou Meiluno chemical Co., Ltd; index number: solvent Orange 62), placing into a corresponding container, stirring at 65 ℃, controlling the stirring speed at 150rpm within the first 1h, then slowly increasing to 1200rpm, continuing to stir for 7h until the mixture becomes a uniform transparent liquid, weighing and stirring all the time in a dark or yellow environment, and completing the preparation of the photosensitive resin part;

then placing the prepared photosensitive resin into a bulk micro-nano generator, continuously stirring and foaming until the material is changed into uniform and semitransparent liquid, wherein the preparation time is 7 hours, taking out, placing and packaging to finally obtain stable 3D printing photosensitive resin containing a large amount of bulk micro-nano bubbles, and detecting that the material contains 25% v/v bulk micro-nano bubbles with the diameters within 1000nm, wherein the micro-nano bubbles in the material can stably exist in the system for 5 months;

the molded model printed by the material has no residue and ash after sintering, and the cast model has smooth surface, no air holes, no burrs, compact interior and no defects of cavities and the like.

Although the invention has been described in detail above with reference to a general description and specific examples, it will be apparent to one skilled in the art that modifications or improvements may be made thereto based on the invention. Accordingly, such modifications and improvements are intended to be within the scope of the invention as claimed.

Claims (10)

1. A photosensitive resin containing bulk micro-nano bubbles is characterized by comprising the following components in percentage by volume (v/v): 70-99% of photosensitive resin and 1-30% of micro-nano bubbles.

2. The photosensitive resin containing bulk micro-nano bubbles according to claim 1, wherein the photosensitive resin comprises, in mass percent (w/w): 0.1-2% of photoinitiator, 0.05-2% of ultraviolet absorbent, 0.001-0.5% of colorant, 0.05-2% of surfactant, 0.01-0.05% of defoaming agent, 20-70% of active diluent containing active functional group f more than or equal to 1 and 20-65% of active oligomer containing active functional group f more than or equal to 1.

3. The photosensitive resin containing bulk micro-nano bubbles according to claim 2, wherein the photoinitiator is one or more of a free radical photoinitiator, a cationic photoinitiator, a visible light initiator and a macromolecular photoinitiator, and the applicable wavelength of the photoinitiator is 200 nm-520 mn.

4. The photosensitive resin containing bulk micro-nano bubbles according to claim 2, wherein the ultraviolet absorber is one or more of salicylate, benzophenone, benzotriazole, substituted acrylonitrile, triazine ultraviolet absorbers.

5. The photosensitive resin containing bulk micro-nano bubbles according to claim 2, wherein the surfactant is one or more of cationic surfactant, anionic surfactant, amphoteric surfactant and nonionic surfactant; but the cationic surfactant and the anionic surfactant are not used together; wherein the cationic surfactant comprises an amine salt type, quaternary ammonium salt type, heterocyclic type cationic surfactant; the anionic surfactant comprises carboxylate, sulfonate and sulfate anionic surfactant; the amphoteric surfactant comprises amino acid type and betaine type amphoteric surfactants; the nonionic surfactant comprises long-chain fatty alcohol-polyoxyethylene ether, alkylphenol ethoxylates, fatty acid-polyoxyethylene ester, polyoxyethylene alkylamine, polyoxyethylene alkylamide and polyether nonionic surfactant.

6. The photosensitive resin containing bulk micro-nano bubbles according to claim 2, wherein the defoaming agent is one or more of dimethyl siloxane defoaming agent, modified siloxane defoaming agent, vinyl ether defoaming agent and acrylate defoaming agent.

7. The photosensitive resin containing bulk micro-nano bubbles according to claim 2, wherein the reactive diluent containing the reactive functional group f is more than or equal to 1: one or more of acrylate reactive diluent, methacrylate reactive diluent, vinyl ether reactive diluent and epoxy reactive diluent.

8. The photosensitive resin containing bulk micro-nano bubbles according to claim 2, wherein the active oligomer containing active functional groups f ≥ 1 is: one or more of a urethane acrylate oligomer, a polyester acrylate oligomer, an epoxy acrylate oligomer, a polybutadiene acrylate oligomer, and a methacrylated acrylate oligomer.

9. The method for preparing photosensitive resin containing bulk micro-nano bubbles according to any one of claims 2 to 8, wherein the method comprises:

(1) weighing the components according to the raw material ratio of the photosensitive resin;

(2) heating, sealing and stirring the mixture in a container at the stirring temperature of 40-95 ℃ for 0.5-12 h to obtain a photosensitive resin mixture;

(3) and adding and dispersing the bulk micro-nano bubbles into the photosensitive resin mixture, and performing 1-10 h to obtain the photosensitive resin containing the bulk micro-nano bubbles.

10. The preparation method according to claim 9, wherein the step (3) is performed in a micro-nano bubble generating device that generates bubbles using a solution substitution method, a direct dropping method, a temperature difference method, an ultrasonic method, a decompression method, an electrolytic method, or a mechanical method.