Radiation curable resin composition and method of making same

Abstract

The application discloses a radiation-curable resin composition and a preparation method thereof, and the preparation method comprises the following steps: dispersing an acrylic monomer with a mass fraction of 20%-50% to dissolve an auxiliary agent with a mass fraction of 0.1%-1% and an initiator with a mass fraction of 1%-5%; adding silica slurry with a mass fraction of 5%-30% and a viscosity of 800 mPa·s to 5000 mPa·s to carry out dispersion treatment again; and adding an acrylic prepolymer resin with a mass fraction of 30%-60% to carry out final dispersion treatment to obtain the radiation-curable resin composition, so as to solve the problems of resin color paste agglomeration, sedimentation, color floating, delamination and the like in the prior art.

Description

Technical Field

[0001] This application relates to the field of 3D printing technology, and in particular to a radiation-curable resin composition and its preparation method. Background Technology

[0002] 3D printing technology is a type of rapid prototyping technology that typically uses liquid photosensitive resin, photosensitive polymers, and other materials as the molding material. The model is divided into multiple cross-sections, and then the solid is built by printing layer by layer. Photopolymer 3D printing equipment offers high molding precision and has wide applications in customized products, medical devices, prostheses, and other fields.

[0003] Due to the photopolymerization process, the viscosity of photosensitive resin for 3D printing must be between 150 mPa·s and 800 mPa·s. Because of this low viscosity, fillers and pigments in the photosensitive resin mixture are particularly prone to agglomeration, precipitation, or sedimentation during storage and placement, leading to unusable resin or color differences and delamination during printing. Summary of the Invention

[0004] In view of the shortcomings of the above-mentioned related technologies, the purpose of this application is to provide a radiation-curable resin composition and its preparation method, so as to solve the problems of resin pigment agglomeration, sedimentation, floating color, and stratification in the prior art.

[0005] To achieve the above and other related objectives, the first aspect of this application provides a method for preparing a radiation-curable resin composition, the method comprising the following steps: dispersing 20%-50% by mass of acrylic monomer to dissolve 0.1%-1% by mass of an additive and 1%-5% by mass of an initiator; adding 5%-30% by mass of a silica slurry with a viscosity between 800 mPa·s and 5000 mPa·s for further dispersion treatment; and adding 30%-60% by mass of acrylic prepolymer resin for final dispersion treatment to obtain the radiation-curable resin composition.

[0006] A second aspect of this application also provides a radiation-curable resin composition comprising: 20%-50% by mass of acrylic monomer; 0.1%-1% by mass of additives; 1%-5% by mass of initiator; 5%-30% by mass of fumed silica slurry; the viscosity of the fumed silica slurry being between 800 mPa·s and 5000 mPa·s; and 30%-60% by mass of acrylic prepolymer resin.

[0007] In summary, the radiation-curable resin composition and its preparation method provided in this application prepare the resin composition by adding a certain mass fraction and a preset viscosity of silica slurry, thereby achieving the effect that the resin composition will not show pigment sedimentation even after a long period of static time. Attached Figure Description

[0008] The specific features involved in this application are shown in the appended claims. A better understanding of the features and advantages of the invention can be achieved by referring to the exemplary embodiments and accompanying drawings described in detail below. A brief description of the drawings is as follows:

[0009] Figure 1 The flowchart shown is a method for preparing the radiation-curable resin composition of this application in one embodiment.

[0010] Figure 2 The flowchart shown is a method for preparing the radiation-curable resin composition of this application in another embodiment.

[0011] Figure 3 This diagram shows the initial state of resin compositions #1 and #2 before they were stored in the dark.

[0012] Figure 4 The diagram shows the surface state of resin compositions #1 and #2 after being stored in the dark for 72 hours.

[0013] Figure 5 The diagram shows the bottom state of the No. 1 and No. 2 resin compositions after they have been stored in the dark for 72 hours. Detailed Implementation

[0014] The following specific embodiments illustrate the implementation of this application. Those skilled in the art can easily understand other advantages and effects of this application from the content disclosed in this specification.

[0015] In the following description, reference is made to the accompanying drawings, which illustrate several embodiments of the present application. It should be understood that other embodiments may also be used, and mechanical, structural, electrical, and operational changes may be made without departing from the spirit and scope of this disclosure. The following detailed description should not be considered limiting, and the scope of the embodiments of the present application is defined only by the claims of the published patents. The terminology used herein is for the purpose of describing particular embodiments only and is not intended to limit the present application.

[0016] The technical solutions of the embodiments of this application will be clearly and completely described below with reference to the accompanying drawings. Obviously, the described embodiments are only a part of the embodiments of this application, and not all of the embodiments. Based on the embodiments of this application, all other embodiments obtained by those of ordinary skill in the art without creative effort are within the scope of protection of this application.

[0017] In existing technologies, the common method for preparing radiation-curable resins involves first dissolving and dispersing agents and initiators using acrylic monomers, then adding acrylic prepolymer resin for dispersion. If printing colored 3D components is required, a pigment of the selected color or value is added finally to obtain the resin material for 3D printing. As mentioned in the background section, this method of preparing photocurable 3D printing resin materials can meet 3D printing needs if prepared and used immediately with almost no residue. However, if the prepared photocurable 3D printing resin material cannot be used up during the current printing or needs to be stored for a long time, the filler and pigment in the resin mixture are particularly prone to agglomeration or precipitation due to the low viscosity of the resin. This results in unusable resin material or problems such as pigment agglomeration, sedimentation, floating color, and stratification during printing, leading to waste. Therefore, this application provides a radiation-curable resin composition and its preparation method to solve the above-mentioned problems of agglomeration, sedimentation, floating color, and stratification.

[0018] In this application, the term "comprising" generally means including the explicitly specified features, but does not exclude other elements.

[0019] In this application, the term "about" generally refers to a variation within a range of 0.5% to 10% above or below a specified value, such as a variation within a range of 0.5%, 1%, 1.5%, 2%, 2.5%, 3%, 3.5%, 4%, 4.5%, 5%, 5.5%, 6%, 6.5%, 7%, 7.5%, 8%, 8.5%, 9%, 9.5%, or 10% above or below a specified value.

[0020] In this application, the term "dispersion" refers to the process of uniformly distributing various mixtures by means of, for example, acrylic monomers, additives, photoinitiators, or fumed silica or fumed silica slurries (described later) and acrylic prepolymer resins, or color pastes, through, for example, stirring or centrifugal motion. In specific embodiments, filler mixtures can be incorporated into resins using various mixing and dispersion systems, such as dissolvers, planetary mixers, paddle mixers, rotor-stator dispersers, or mixers operating on the principle of a dual asymmetric centrifuge (DAC). On a laboratory scale, DAC mixers can rapidly and easily disperse particles and simultaneously degas them, even in highly viscous matrices.

[0021] In this application, "min" is an abbreviation for minute, used to represent minutes; for example, a stirring speed of 1200 rpm, as described later, means the number of revolutions of the paddle in a paddle mixer or the number of revolutions of the rotor in a rotor-stator disperser per minute, for example, 1200 revolutions. Another example is a duration of 10 min, which means a time length of 10 minutes. Similarly, "4h" means 4 hours.

[0022] This application discloses a method for preparing a radiation-curable resin composition. Please refer to [link to relevant documentation]. Figure 1 The figure shows a flowchart of a method for preparing the radiation-curable resin composition of this application in one embodiment. As shown, the preparation method includes the following steps:

[0023] First, perform step S10, using acrylic monomer dispersion to dissolve the additives and initiator.

[0024] In the examples, 20%-50% by mass of acrylic monomer was used to disperse and dissolve 0.1%-1% by mass of additives and 1%-5% by mass of initiator.

[0025] In one embodiment, the mass fraction of the acrylic monomer dispersed to dissolve the auxiliary agent and the initiator is about 20%-50%, for example, it can be 20%, 21%, 22%, 23%, 24%, 25%, 26%, 27%, 28%, 29%, 30%, 31%, 32%, 33%, 34%, 35%, 36%, 37%, 38%, 39%, 40%, 41%, 42%, 43%, 44%, 45%, 46%, 47%, 48%, 49%, or 50%.

[0026] In a preferred embodiment, the mass fraction of the acrylic monomer dispersed to dissolve the auxiliary agent and the initiator is about 30%-50%, for example, it can be 30%, 31%, 32%, 33%, 34%, 35%, 36%, 37%, 38%, 39%, 40%, 41%, 42%, 43%, 44%, 45%, 46%, 47%, 48%, 49%, or 50%.

[0027] In this application, the "monomer" in the acrylic monomer is a low-molecular-weight reactive compound that can combine to form an oligomer or polymer. In this application, all compounds having at least one free-radical polymerizable olefinic double bond can be used as monomers.

[0028] The "monomers" can be distinguished by the number of their free radical polymerizable olefinic double bonds. For example, a monomer with one free radical polymerizable olefinic double bond is monofunctional (monomer I); a monomer with several free radical polymerizable non-conjugated olefinic double bonds is polyfunctional (monomer II), and monomer II has cross-linking properties.

[0029] In some embodiments, the monomer I is preferably selected from the group consisting of:

[0030] Ia) α,β-ene esters of unsaturated C3-C4 carboxylic acids;

[0031] Ib) Vinyl (hetero)aromatics;

[0032] Ic)α,β-enes are unsaturated mono- and dicarboxylic acids, carboxylic anhydrides and carboxylic amides;

[0033] Monoesters and diesters of α,β-ene unsaturated C4-C6 dicarboxylic acids; and

[0034] Allyl esters and vinyl esters of carboxylic acids (Ie).

[0035] More preferably, the monomer I is selected from groups Ia), Ib), and Ic).

[0036] Among them, suitable monomers I from group Ia) include:

[0037] - (meth)acrylates of straight-chain, branched and cyclic alkanols having 1 to 22 carbon atoms in the alkanol residues, such as methyl (meth)acrylate, ethyl (meth)acrylate, n-butyl (meth)acrylate, tert-butyl (meth)acrylate, ethylhexyl (meth)acrylate, isodecanyl methacrylate, isobornyl (meth)acrylate and 4-tert-butylcyclohexyl (meth)acrylate.

[0038] -Aromatic and heteroaromatic (meth)acrylates, such as benzyl (meth)acrylate, 2-hydroxy-3-phenoxypropyl (meth)acrylate, phenoxyethyl (meth)acrylate, phenyl (meth)acrylate, pentabromobenzyl (meth)acrylate, pentabromophenyl (meth)acrylate, 2,4,6-tribromophenyl (meth)acrylate, 9H-carbazole-9-ethyl (meth)acrylate, 2-hydroxypropyl-2-([meth]acryloyloxy)ethyl phthalate, 1-naphthyl (meth)acrylate, and 1-pyrene methyl (meth)acrylate.

[0039] Alkyl methacrylates substituted with hydroxy-, alkoxy-, carboxyl-, amino-, epoxy-, sulfonyl-, silyl-, and halogen-, as well as heterocyclic (meth)acrylates, such as 2-hydroxyethyl, 2-hydroxypropyl, 3-hydroxypropyl, 2-hydroxybutyl, 3-hydroxybutyl, 5-hydroxybutyl, and hydroxyethylcaprolactone. lcaprolactone), 3-chloro-2-hydroxypropyl, 2-methoxyethyl, 2-ethoxyethyl, 2-butoxyethyl, di(ethylene glycol)methyl ether, di(ethylene glycol)ethyl ether, di(ethylene glycol)-2-ethylhexyl ether, tri(ethylene glycol)methyl ether, ethylene glycol dicyclopentenyl ether, ethyl diethylene glycol, ethyl triethylene glycol, butyl diethylene glycol, 2-carboxyethyl, 2-(dimethylamino)ethyl, 2-(diethylamino)ethyl, 2-(diisopropylamino)ethyl, 2-(tert-butylamino)ethyl, 3-(dimethylamino)propyl, 2-[ [(Butylamino)carbonyl]oxy]ethyl, glycidyl, 2-(methylthio)ethyl, 3-(trimethoxysilyl)propyl, 2-(trimethylsilyloxy)ethyl, 3-[tri(trimethylsilyloxy)silyl]propyl, trimethylsilyl, 2-chloroethyl, 2,2,2-trifluoroethyl, tetrahydrofurfuryl and 2-N-morpholinoethyl-(meth)acrylate, and 4-(meth)acryloylmorpholine, mono-2-([meth]acryloyloxy)ethyl succinate and mono-2-([meth]acryloyloxy)ethyl maleate.

[0040] Suitable monomers I from group Ib) include, for example, styrene, 4-acetoxystyrene, 2-bromostyrene, 3-bromostyrene, 4-bromostyrene, 4-tert-butoxystyrene, 4-tert-butylstyrene, 2-chlorostyrene, 3-chlorostyrene, 4-chlorostyrene, 2,6-dichlorostyrene, 3,4-dimethoxystyrene, 2,4-dimethylstyrene, 2,5-dimethylstyrene, 4-ethoxystyrene, 3-methylstyrene, 4-methylstyrene, 4-vinylanisole, 3-vinylbenzyl chloride, 4-vinylbenzyl chloride, 9-vinylanthracene, 4-vinylbiphenyl, 2-vinylnaphthalene, 9-vinylcarbazole, N-vinylphthalimide, 2-vinylpyridine, 4-vinylpyridine, and 1-vinyl-2-pyrrolidone.

[0041] Suitable monomers I from group Ic) include, for example, (meth)acrylic acid, maleic acid, itaconic acid, maleic anhydride, itaconic anhydride, crotonic anhydride, N-ethyl-, N-isopropyl-, N-tert-butyl-, N,N-dimethyl-, N,N-diethyl-, N-hydroxymethyl-, N-hydroxyethyl-, N-(3-methoxypropyl)-, N-(butoxymethyl)-, N-(isobutoxymethyl)-, N-phenyl-, N-diphenylmethyl-, N-(triphenylmethyl)- and N-[3-(dimethylamino)propyl](meth)acrylamide.

[0042] Suitable monomers I from group Id) include, for example, diesters of maleic acid and itaconic acid with methanol, ethanol, n-butanol, isobutanol and 2-ethylhexanol.

[0043] Suitable monomers from group Ie) include, for example, vinyl and allyl acetate esters, and the corresponding propionate, butyrate, valerate, hexanoate, decanoate and laurate esters.

[0044] As a multifunctional monomer II, it can be used for:

[0045] IIa) (Meth)acrylates of polyols;

[0046] IIb) Vinyl and allyl ethers of polyols; and

[0047] IIc) Allyl-, vinyl- or (meth)acryloyl-disubstituted or polysubstituted heterocyclic and (hetero)aromatic compounds.

[0048] Suitable multifunctional monomers II from group IIa) include, for example, ethylene glycol di(meth)acrylate, 1,3-butanediol di(meth)acrylate, 1,4-butanediol di(meth)acrylate, 1,6-hexanediol di(meth)acrylate, 1,10-decanediol di(meth)acrylate, di(ethylene glycol) di(meth)acrylate, tri(ethylene glycol) di(meth)acrylate, tetra(ethylene glycol) di(meth)acrylate, di(propylene glycol) di(meth)acrylate, tri(propylene glycol) di(meth)acrylate, tricyclodecanediethanol di(meth)acrylate, 2-hydroxy-1,3-di(meth)acryloyloxypropane, glycerol di(meth)acrylate, and glycerol 1,3-diglyceryl alcohol di(meth)acrylate. di(meth)acrylate), neopentyl glycol di(meth)acrylate, diurea di(meth)acrylate, ethoxylated trimethylolpropane methyl ether di(meth)acrylate, trimethylolpropane tri(meth)acrylate, ethoxylated trimethylolpropane tri(meth)acrylate (EO degree = 3-20), propoxylated trimethylolpropane tri(meth)acrylate, pentaerythritol tri(meth)acrylate, propoxylated glycerol tri(meth)acrylate, di(trimethylolpropane tetra(meth)acrylate, pentaerythritol tetra(meth)acrylate, di(pentaerythritol)penta(meth)acrylate, and di(pentaerythritol)hexa(meth)acrylate.

[0049] Suitable multifunctional monomers II from group IIb) include, for example, 1,4-butanediol divinyl ether, 1,6-hexanediol divinyl ether, di(ethylene glycol) divinyl ether, bis[4-(ethoxy)butyl] adipate, bis[4-(ethyloxy)butyl] succinate, bis[4-(ethoxy)butyl] isophthalate, bis[4-(ethoxy)butyl] terephthalate, bis[4-(ethoxy)butyl]-1,6-hexanedicarbamate, 1,4-cyclohexanediethanol divinyl ether, tris[4-(ethoxy)butyl] trimellitate, allyl ether, and trimethylolpropane diallyl ether.

[0050] Suitable polyfunctional monomers II from group IIc) include, for example, divinylbenzene, 2,4,6-triallyloxy-1,3,5-triazine, 1,3,5-triallyl-1,3,5-triazine-2,4,6(1H,3H,5H)-trione, tris[2-(acryloyloxy)ethyl]isocyanurate, 1,3,5-triacryloylhexahydro-1,3,5-triazine, 2,2'-diallylbisphenol-A, 2,2'-diallylbisphenol-A diacetate ether, 1,4-phenylene di(meth)acrylate, ethoxylated bisphenol-A di(meth)acrylate (EO degree = 2-30), and bisphenol-A di(meth)acrylate glycerol. Bisphenol-A di(meth)acrylate, propoxylated bisphenol-A di(meth)acrylate, bisphenol-A di(meth)acrylate, and ethoxylated bisphenol-F di(meth)acrylate.

[0051] The radiation-curable resin composition includes additives, and in some embodiments, the additives include one or more mixtures of defoamers, wetting and dispersing agents, and leveling agents.

[0052] In one embodiment, the mass fraction of the auxiliary agent used is approximately 0.1%-1%, for example, it can be 0.1%, 0.2%, 0.3%, 0.4%, 0.5%, 0.6%, 0.7%, 0.8%, 0.9%, or 1%.

[0053] In a preferred embodiment, the mass fraction of the adjuvant used is about 0.1%-0.5%, for example, it can be 0.1%, 0.2%, 0.3%, 0.4%, or 0.5%.

[0054] In one embodiment, the defoamer includes polysiloxane, non-silicone polymer, dimethylpolysiloxane, or organic polymer, etc.

[0055] In other embodiments, the defoamer includes non-silicone defoamers, polyether defoamers, silicone defoamers, or polyether-modified silicone defoamers, etc.

[0056] In one example, the non-silicone defoamer is primarily an organic compound such as alcohols, fatty acids, fatty acid esters, phosphate esters, mineral oils, and amides.

[0057] In another example, the polyether-type defoamer is, for example, a copolymer of ethylene oxide or propylene oxide.

[0058] In yet another example, the main component of the silicone-type defoamer is polydimethylsiloxane (also known as silicone oil).

[0059] In another example, the polyether-modified silicone defoamer is mainly a silicone ether copolymer obtained by grafting polyether segments or polysiloxane segments.

[0060] In one embodiment, the wetting and dispersing agent includes copolymers containing acidic groups, high molecular weight block copolymers containing pigment affinity groups, or structured acrylic copolymers, etc.

[0061] In one embodiment, the leveling agent includes polyether-modified polysiloxane, polyacrylate, or polysiloxane, etc.

[0062] The radiation-curable resin composition contains an initiator. In one embodiment, the initiator used has a mass fraction of about 1% to 5%, for example, 1%, 1.1%, 1.2%, 1.3%, 1.4%, 1.5%, 1.6%, 1.7%, 1.8%, 1.9%, 2%, 2.1%, 2.2%, 2.3%, 2.4%, 2.5%, 2.6%, 2.7%, 2.8%, 2.9%, 3%, 3.1%, 3.2%, 3.3%, 3.4%, 3.5%, 3.6%, 3.7%, 3.8%, 3.9%, 4%, 4.1%, 4.2%, 4.3%, 4.4%, 4.5%, 4.6%, 4.7%, 4.8%, 4.9%, or 5%.

[0063] In this application, the initiator, also referred to as a photoinitiator, is a compound that, after absorbing electromagnetic radiation (typically in the UV wavelength range of approximately 320 nm-420 nm), decays in a photolysis reaction and thus forms reactive substances that can initiate chemical reactions, primarily polymerization reactions. These reactive substances are free radicals or cations. In this application, a free radical-forming photoinitiator is used. In principle, any compound that forms free radicals when exposed to suitable radiation can be used as a photoinitiator.

[0064] In some embodiments of this application, the group of suitable photoinitiators particularly includes:

[0065] 1. α-Hydroxyaryl ketones, such as 2-hydroxy-2-methylphenylacetone and 1-hydroxycyclohexylphenyl ketone.

[0066] 2. α-Aminoaryl ketones, such as 2-methyl-4'-(methylthio)-2-morpholinobenzophenone and 2-benzyl-2-(dimethylamino)-4'-morpholinobutylbenzophenone.

[0067] 3. α-Alkoxyaryl ketones, such as 2,2-dimethoxy-2-phenylacetophenone, 2-isopropoxy-2-phenylacetophenone, and 2-n-butoxy-2-phenylacetophenone.

[0068] 4. Phosphorus oxides, such as diphenyl-(2,4,6-trimethylbenzoyl)phosphine oxide, ethyl (2,4,6-trimethylbenzoyl)phenylphosphine sulfate, and phenyl-bis-(2,4,6-trimethylbenzoyl)phosphine oxide.

[0069] In a preferred embodiment, the photoinitiator is a phosphine oxide group photoinitiator that can be activated by radiation in the wavelength range of 355 to 405 nm.

[0070] In step S10 above, the acrylic monomer dispersion to dissolve the additive and the initiator is achieved by dispersing the acrylic monomer containing the additive and the initiator using either a paddle mixer or a rotor-stator disperser, so that the additive and the initiator dissolve in the acrylic monomer.

[0071] In this embodiment, a paddle mixer or rotor-stator disperser with a rotation speed of 600-800 rpm is used to disperse the acrylic monomers containing the additives and the initiator, and the duration of this process is 60-80 min.

[0072] In one embodiment, for example, a paddle mixer with a rotation speed of about 700 rpm is used to disperse the acrylic monomers added with the additives and the initiator, and this process lasts for about 70 minutes.

[0073] Next, step S11 is performed, in which 5%-30% by mass of silica slurry is added and further dispersed. The viscosity of the silica slurry is between 800 mPa·s and 5000 mPa·s.

[0074] In some embodiments, the mass fraction of the added silica slurry is 5%-30%, for example, 5%, 6%, 7%, 8%, 9%, 10%, 11%, 12%, 13%, 14%, 15%, 16%, 17%, 18%, 19%, 20%, 21%, 22%, 23%, 24%, 25%, 26%, 27%, 28%, 29%, or 30%.

[0075] In some preferred embodiments, the mass fraction of the added silica slurry is 5%-20%, for example, 5%, 6%, 7%, 8%, 9%, 10%, 11%, 12%, 13%, 14%, 15%, 16%, 17%, 18%, 19%, or 20%.

[0076] In some embodiments, the viscosity of the added silica slurry is between 800 mPa·s and 5000 mPa·s. In some embodiments, the viscosity of the added silica slurry is, for example, 800 mPa·s, 1000 mPa·s, 1200 mPa·s, 1400 mPa·s, 1600 mPa·s, 1800 mPa·s, 2000 mPa·s, 2200 mPa·s, 2400 mPa·s, 2600 mPa·s, 2800 mPa·s, 3000 mPa·s, 3200 mPa·s, 3400 mPa·s, 3600 mPa·s, 3800 mPa·s, 4000 mPa·s, 4200 mPa·s, 4400 mPa·s, 4600 mPa·s, 4800 mPa·s, or 5000 mPa·s.

[0077] In some preferred embodiments, the viscosity of the added silica slurry is between 1500 mPa·s and 2000 mPa·s. In some embodiments, the viscosity of the added silica slurry is, for example, 1500 mPa·s, 1600 mPa·s, 1700 mPa·s, 1800 mPa·s, 1900 mPa·s, or 2000 mPa·s.

[0078] Before performing step S11 above, the fumed silica slurry needs to be prepared in advance. In the embodiment, the fumed silica slurry is prepared by adding 5%-20% fumed silica to 80%-95% acrylic monomer by mass and stirring repeatedly.

[0079] In one embodiment, the acrylic monomer used to prepare the silica slurry is, for example, TPGDA (tripropylene glycol diacrylate or 2-acrylate-(1-methyl-1,2-ethylidene)bis(β-methoxyethyl) ester).

[0080] In another embodiment, the acrylic monomer used to prepare the silica slurry is, for example, TMPTA (trimethylolpropane triacrylate, molecular formula: (CH2=CHCOOCH2)3-CCH2CH3).

[0081] In another embodiment, the acrylic monomer used to prepare the silica slurry is, for example, DPGDA (dipropylene glycol diacrylate, chemical formula C12H18O5).

[0082] In yet another embodiment, the acrylic monomer used to prepare the silica slurry is, for example, ACMO (acryloylmorpholine).

[0083] In some embodiments of step S11 above, the acrylic monomers used to prepare the silica slurry are, for example, one or a mixture of UV-curable monomers such as TPGDA (tripropylene glycol diacrylate), TMPTA (trimethylolpropane triacrylate), DPGDA (dipropylene glycol diacrylate), or ACMO (acryloylmorpholine).

[0084] In some embodiments of step S11 above, the gaseous silicon includes dimethyldichlorosilane (chemical formula: Si(CH3)2Cl2), hexamethyldisilazane (chemical formula: [(CH3)3Si]2NH), octamethylcyclotetrasiloxane (chemical formula: [(CH3)2SiO]4), octylsilane, or fumed silica treated with polydimethylsiloxane (PDMS).

[0085] Among them, the octylsilane is, for example, octyltrimethoxysilane (CAS: 3069-40-7, CH3(CH2)7Si(OCH3)3), octyltriethoxysilane (CAS: 2943-75-1, CH3(CH2)7Si(OCH2CH3)3), and isooctyltriethoxysilane (CAS: 35435-21-3, C 14 H 32 O3Si), n-octyltriethoxysilane (CAS: 2943-75-1, C 14 H 32 O3Si).

[0086] In this embodiment, the silica slurry is prepared through the following steps:

[0087] During the first time period of stirring acrylic monomers with a mass fraction of 80%-95% at the initial speed, 5%-20% by mass of gaseous silica is added.

[0088] In the embodiments, the reserved acrylic monomer has a mass fraction of 80%-95% (e.g., 80%, 81%, 82%, 83%, 84%, 85%, 86%, 87%, 88%, 89%, 90%, 91%, 92%, 93%, 94%, or 95%). In a preferred embodiment, the reserved acrylic monomer has a mass fraction of 90%.

[0089] In embodiments, the mass fraction of the spare gaseous silicon is 5%-20% (e.g., 5%, 6%, 7%, 8%, 9%, 10%, 11%, 12%, 13%, 14%, 15%, 16%, 17%, 18%, 19%, or 20%). In a preferred embodiment, the mass fraction of the spare gaseous silicon is 10%.

[0090] In this embodiment, gaseous silica is continuously added during a first period of stirring the acrylic monomer at an initial speed. Specifically, the process of adding gaseous silica lasts for a certain period of time, referred to as the first period, which is approximately 5-10 minutes (e.g., 5 minutes, 6 minutes, 7 minutes, 8 minutes, 9 minutes, or 10 minutes). The initial speed is approximately 200-500 rpm (e.g., approximately 200 rpm, 300 rpm, 400 rpm, or 500 rpm).

[0091] In one specific embodiment, taking a spare acrylic monomer with a mass fraction of 90%, a spare gaseous silica with a mass fraction of 10%, an initial duration of approximately 10 minutes, and an initial speed of approximately 300 rpm as an example:

[0092] First, gaseous silica is continuously added while the acrylic monomer is continuously stirred at a speed of 300 rpm for about 10 minutes. The term "continuous" means that the process of adding gaseous silica is uninterrupted for about 10 minutes, which can ensure that the gaseous silica is more evenly distributed in the acrylic monomer.

[0093] Then, a first acceleration and stirring for a second duration are performed; in this embodiment, the stirring speed for the first acceleration is 500-800 rpm (e.g., approximately 500 rpm, 600 rpm, 700 rpm, or 800 rpm). The second duration is 15-20 min (e.g., 15 min, 16 min, 17 min, 18 min, 19 min, or 20 min). For example, the stirring speed is accelerated to 700 rpm and stirred for 20 min.

[0094] Finally, a second acceleration and a third stirring duration are performed; in this embodiment, the stirring speed for the second acceleration is 800-1200 rpm (e.g., approximately 800 rpm, 900 rpm, 1000 rpm, 1100 rpm, or 1200 rpm). The third duration is 20-40 min (e.g., 20 min, 21 min, 22 min, 23 min, 24 min, 25 min, 26 min, 27 min, 28 min, 29 min, 30 min, 31 min, 32 min, 33 min, 34 min, 35 min, 36 min, 37 min, 38 min, 39 min, or 40 min). For example, accelerating the stirring speed to approximately 1200 rpm and continuing stirring for approximately 30 min yields a silica slurry with a viscosity between 800 mPa·s and 5000 mPa·s, ready for step S11 described above.

[0095] In the step of adding the fumed silica slurry prepared in the above steps, the selected fumed silica slurry has a mass fraction of 5%-30% and a viscosity between 800 mPa·s and 5000 mPa·s. Then, a dispersion treatment is performed. In this step, the fumed silica slurry is added to the acrylic monomer in which the additives and initiator have been dissolved, and dispersion treatment is still required. In some embodiments, for example, a paddle mixer with a rotation speed of approximately 800 rpm is used to disperse the acrylic monomer in which the above-mentioned fumed silica slurry has been added. This process lasts for 30-60 minutes, preferably 45 minutes.

[0096] Next, step S12 is performed, in which 30%-60% by mass of acrylic prepolymer resin is added for further dispersion treatment.

[0097] In some embodiments, the mass fraction of the added acrylic prepolymer resin is 30%-60% (e.g., it can be 30%, 31%, 32%, 33%, 34%, 35%, 36%, 37%, 38%, 39%, 40%, 41%, 42%, 43%, 44%, 45%, 46%, 47%, 48%, 49%, 50%, 51%, 52%, 53%, 54%, 55%, 56%, 57%, 58%, 59%, or 60%).

[0098] In some embodiments, the acrylic prepolymer resin includes aliphatic polyurethane acrylate, aliphatic polyurethane methacrylate, aromatic polyurethane acrylate, epoxy acrylate, or polyester acrylate.

[0099] In another embodiment, the acrylic prepolymer resin comprises two or more of the following: aliphatic polyurethane acrylate, aliphatic polyurethane methacrylate, aromatic polyurethane acrylate, epoxy acrylate, and polyester acrylate.

[0100] In one embodiment, the added acrylic prepolymer resin, with a mass fraction of 30%-60%, is an acrylic prepolymer resin that has undergone preheating treatment at a temperature of 60-80°C for 2-4 hours. In this embodiment, before performing step S12, the added acrylic prepolymer resin needs to be pretreated by heating the acrylic prepolymer resin to be used to a temperature of 60-80°C and maintaining it for 2-4 hours. Specifically, the prepared oven is heated to a temperature of 60-80°C, and then the acrylic prepolymer resin to be used is placed in the oven and maintained for 2-4 hours. In this way, preheating the acrylic prepolymer resin to be used can reduce its viscosity, which not only makes it easier to add to the acrylic monomers that have been added to the silica slurry in step S11, but also prevents the acrylic prepolymer resin from being difficult to disperse and dissolve in the mixture due to excessive viscosity, thus preventing uneven dispersion.

[0101] After adding fumed silica slurry to acrylic monomers containing dissolved additives and initiators and dispersing it, the acrylic prepolymer resin is added and dispersed again to obtain the radiation-curable resin composition. In one embodiment, 30%-60% by mass of acrylic prepolymer resin is added and dispersed to obtain the radiation-curable resin composition.

[0102] Step S12 includes two dispersion stages: first, a paddle mixer with a rotation speed of approximately 500-600 rpm is used for the first stage of dispersion; then, the speed is increased to 800-1000 rpm for the second stage of dispersion. The first and second stage dispersion processes last approximately 60-90 minutes. For example, if the total time for both stages is 90 minutes, then the first stage lasts approximately 45 minutes, and the second stage lasts approximately 45 minutes. Through steps S10 to S12, the radiation-curable resin composition described in this application can be obtained.

[0103] In one embodiment, for example, in step S10 above, 31.6% by mass of acrylic monomer is used to disperse and dissolve 0.4% by mass of additive and 3% by mass of initiator; in step S11 above, 20% by mass of silica slurry is added and further dispersed, wherein the viscosity of the silica slurry is 2000 mPa·s; in step S11 above, 45% by mass of acrylic prepolymer resin is added and further dispersed, finally obtaining the radiation-curable resin composition described in this application, thereby enabling the prepared resin composition to achieve the effect of no pigment sedimentation even after long-term static resin composition.

[0104] Please see Figure 2 The figure shows a flowchart of the method for preparing the radiation-curable resin composition of this application in another embodiment. As shown in the figure, the method for preparing the radiation-curable resin composition of this application further includes step S13 of adding color paste and dispersing it to adjust the color of the material to be printed and cured.

[0105] In this embodiment, the mass fraction of the pigment added in step S13 is approximately 0.1%-0.6%, for example, it can be 0.1%, 0.2%, 0.3%, 0.4%, 0.5%, or 0.6%.

[0106] Depending on different printing needs, the color paste may include a variety of single colors or colors obtained by mixing two or more single colors. In some embodiments, the color paste includes one or more of the following: carbon black paste, titanium dioxide paste, golden red paste, permanent yellow paste, phthalocyanine blue paste, or manganese violet paste.

[0107] In one embodiment, for example, in step S10 above, 31% by mass of acrylic monomer is used to disperse and dissolve 0.4% by mass of additive and 3% by mass of initiator; in step S11 above, 20% by mass of silica slurry is added and further dispersed, wherein the viscosity of the silica slurry is 2000 mPa·s; in step S12 above, 45% by mass of acrylic prepolymer resin is added and further dispersed; in step S13 above, 0.6% by mass of color paste is added, and finally the radiation-curable resin composition described in this application is obtained, thereby enabling the prepared resin composition to achieve the effect of no color paste sedimentation even after long-term static resin composition.

[0108] To further illustrate the effects of the radiation-curable resin composition prepared by the method of this application, please refer to [link to relevant documentation]. Figure 3 The diagram shows the initial state of resin compositions #1 and #2 before they were stored in the dark. Figure 3 (a) and Figure 3 (b) The container labeled 1# contains a conventional radiation-curable (photocurable) resin composition; Figure 3 (a) and Figure 3 (b) The container labeled 2# contains a radiation-curable resin composition prepared by the method of this application; it appears as follows: Figure 3 As shown, before being stored in the dark, the initial state of the resin composition in container #1 and container #2 was uniform in color, with no color paste sedimentation, floating color blooming, or layering.

[0109] After the resin compositions in container #1 and container #2 were stored in the dark for 72 hours, the following results were observed: Figure 4 The state shown Figure 4 The diagram shows the surface state of resin compositions #1 and #2 after being stored in the dark for 72 hours. Figure 4 (a) and Figure 4 (b) The container labeled 1# contains a conventional radiation-curable resin composition; Figure 4 (a) and Figure 4 (b) The container marked 2# contains a radiation-curable resin composition prepared by the method of this application; Figure 4In the diagram, (a) shows a first-angle schematic diagram of resin compositions 1# and 2# after being stored in the dark for 72 hours, and (b) shows a second-angle schematic diagram of resin compositions 1# and 2# after being stored in the dark for 72 hours. From the two comparative diagrams, it can be seen that after 72 hours of storage in the dark, resin compositions 1# and 2# show obvious color paste precipitation and sedimentation on the surface; resin composition 2#, prepared by the method of this application, does not show color paste precipitation, and its state is similar to its initial state. Figure 3 The states shown are basically the same.

[0110] After the resin compositions in container #1 and container #2 are stored in the dark for 72 hours, then... Figure 5 The state shown Figure 5 The diagram shows the bottom state of resin compositions #1 and #2 after being stored in the dark for 72 hours. Figure 5 (a) and Figure 5 (b) The container labeled 1# contains a conventional radiation-curable resin composition; Figure 5 (a) and Figure 5 (b) The container marked 2# contains a radiation-curable resin composition prepared by the method of this application; Figure 5 In the figures, (a) shows a bottom view of resin composition #1 after being stored in the dark for 72 hours, and (b) shows a bottom view of resin composition #2 after being stored in the dark for 72 hours. As shown, the states of resin compositions #1 and #2 after being stored in the dark for 72 hours show that resin composition #1 has obvious white slurry sedimentation at the bottom; resin composition #2 prepared by the method of this application has no impurities sedimentation at the bottom, and its state is similar to its initial state. Figure 3 The states shown are basically the same.

[0111] This application also provides a radiation-curable resin composition comprising: 20%-50% by mass of acrylic monomer; 0.1%-1% by mass of additives; 1%-5% by mass of initiator; 5%-30% by mass of fumed silica slurry; the viscosity of the fumed silica slurry being between 800 mPa·s and 5000 mPa·s; and 30%-60% by mass of acrylic prepolymer resin.

[0112] In some embodiments of this application, the mass fraction of the acrylic monomer is about 20%-50%, for example, it can be 20%, 21%, 22%, 23%, 24%, 25%, 26%, 27%, 28%, 29%, 30%, 31%, 32%, 33%, 34%, 35%, 36%, 37%, 38%, 39%, 40%, 41%, 42%, 43%, 44%, 45%, 46%, 47%, 48%, 49%, or 50%.

[0113] In a preferred embodiment, the mass fraction of the acrylic monomer is about 30%-50%, for example, it can be 30%, 31%, 32%, 33%, 34%, 35%, 36%, 37%, 38%, 39%, 40%, 41%, 42%, 43%, 44%, 45%, 46%, 47%, 48%, 49%, or 50%.

[0114] In this application, the "monomer" in the acrylic monomer is a low-molecular-weight reactive compound that can combine to form an oligomer or polymer. In this application, all compounds having at least one free-radical polymerizable olefinic double bond can be used as monomers.

[0115] The "monomers" can be distinguished by the number of their free radical polymerizable olefinic double bonds. For example, a monomer with one free radical polymerizable olefinic double bond is monofunctional (monomer I); a monomer with several free radical polymerizable non-conjugated olefinic double bonds is polyfunctional (monomer II), and monomer II has cross-linking properties.

[0116] For detailed examples of monomer I and monomer II, please refer to the relevant descriptions in step S10 above, which will not be repeated here.

[0117] The radiation-curable resin composition includes additives, and in some embodiments, the additives include one or more mixtures of defoamers, wetting and dispersing agents, and leveling agents.

[0118] In one embodiment, the mass fraction of the auxiliary agent used is approximately 0.1%-1%, for example, it can be 0.1%, 0.2%, 0.3%, 0.4%, 0.5%, 0.6%, 0.7%, 0.8%, 0.9%, or 1%.

[0119] In a preferred embodiment, the mass fraction of the adjuvant used is about 0.1%-0.5%, for example, it can be 0.1%, 0.2%, 0.3%, 0.4%, or 0.5%.

[0120] In one embodiment, the defoamer includes polysiloxane, non-silicone polymer, dimethylpolysiloxane, or organic polymer, etc.

[0121] In one embodiment, the wetting and dispersing agent includes copolymers containing acidic groups, high molecular weight block copolymers containing pigment affinity groups, or structured acrylic copolymers, etc.

[0122] In one embodiment, the leveling agent includes polyether-modified polysiloxane, polyacrylate, or polysiloxane, etc.

[0123] The radiation-curable resin composition contains an initiator. In one embodiment, the initiator used has a mass fraction of about 1% to 5%, for example, 1%, 1.1%, 1.2%, 1.3%, 1.4%, 1.5%, 1.6%, 1.7%, 1.8%, 1.9%, 2%, 2.1%, 2.2%, 2.3%, 2.4%, 2.5%, 2.6%, 2.7%, 2.8%, 2.9%, 3%, 3.1%, 3.2%, 3.3%, 3.4%, 3.5%, 3.6%, 3.7%, 3.8%, 3.9%, 4%, 4.1%, 4.2%, 4.3%, 4.4%, 4.5%, 4.6%, 4.7%, 4.8%, 4.9%, or 5%.

[0124] In this application, the initiator, also referred to as a photoinitiator, is a compound that, after absorbing electromagnetic radiation (typically in the UV wavelength range of approximately 320 nm-420 nm), decays in a photolysis reaction and thus forms reactive substances that can initiate chemical reactions, primarily polymerization reactions. These reactive substances are free radicals or cations. In this application, a free radical-forming photoinitiator is used. In principle, any compound that forms free radicals when exposed to suitable radiation can be used as a photoinitiator.

[0125] In some embodiments of this application, examples of suitable photoinitiators can be found in the relevant descriptions of step S10 above, and will not be repeated here.

[0126] In a preferred embodiment, the photoinitiator is a phosphine oxide group photoinitiator that can be activated by radiation in the wavelength range of 355 to 405 nm.

[0127] In some embodiments, the mass fraction of the added silica slurry is 5%-30%, for example, 5%, 6%, 7%, 8%, 9%, 10%, 11%, 12%, 13%, 14%, 15%, 16%, 17%, 18%, 19%, 20%, 21%, 22%, 23%, 24%, 25%, 26%, 27%, 28%, 29%, or 30%.

[0128] In some preferred embodiments, the mass fraction of the added silica slurry is 5%-20%, for example, 5%, 6%, 7%, 8%, 9%, 10%, 11%, 12%, 13%, 14%, 15%, 16%, 17%, 18%, 19%, or 20%.

[0129] In some embodiments, the viscosity of the added silica slurry is between 800 mPa·s and 5000 mPa·s. In some embodiments, the viscosity of the added silica slurry is, for example, 800 mPa·s, 1000 mPa·s, 1200 mPa·s, 1400 mPa·s, 1600 mPa·s, 1800 mPa·s, 2000 mPa·s, 2200 mPa·s, 2400 mPa·s, 2600 mPa·s, 2800 mPa·s, 3000 mPa·s, 3200 mPa·s, 3400 mPa·s, 3600 mPa·s, 3800 mPa·s, 4000 mPa·s, 4200 mPa·s, 4400 mPa·s, 4600 mPa·s, 4800 mPa·s, or 5000 mPa·s.

[0130] In some preferred embodiments, the viscosity of the added silica slurry is between 1500 mPa·s and 2000 mPa·s. In some embodiments, the viscosity of the added silica slurry is, for example, 1500 mPa·s, 1600 mPa·s, 1700 mPa·s, 1800 mPa·s, 1900 mPa·s, or 2000 mPa·s.

[0131] The preparation method and process of the silica slurry are described in step S11 above and will not be repeated here.

[0132] In some embodiments, the mass fraction of the added acrylic prepolymer resin is 30%-60% (e.g., it can be 30%, 31%, 32%, 33%, 34%, 35%, 36%, 37%, 38%, 39%, 40%, 41%, 42%, 43%, 44%, 45%, 46%, 47%, 48%, 49%, 50%, 51%, 52%, 53%, 54%, 55%, 56%, 57%, 58%, 59%, or 60%).

[0133] In some embodiments, the acrylic prepolymer resin includes aliphatic polyurethane acrylate, aliphatic polyurethane methacrylate, aromatic polyurethane acrylate, epoxy acrylate, or polyester acrylate.

[0134] In another embodiment, the acrylic prepolymer resin comprises two or more of the following: aliphatic polyurethane acrylate, aliphatic polyurethane methacrylate, aromatic polyurethane acrylate, epoxy acrylate, and polyester acrylate.

[0135] In one embodiment, for example, in step S10 above, 31.6% by mass of acrylic monomer is used to disperse and dissolve 0.4% by mass of additive and 3% by mass of initiator; in step S11 above, 20% by mass of silica slurry is added and further dispersed, wherein the viscosity of the silica slurry is 2000 mPa·s; in step S11 above, 45% by mass of acrylic prepolymer resin is added and further dispersed, finally obtaining the radiation-curable resin composition described in this application, thereby enabling the prepared resin composition to achieve the effect of no pigment sedimentation even after long-term static resin composition.

[0136] The radiation-curable resin composition further includes a colorant. In embodiments, the colorant has a mass fraction of approximately 0.1%-0.6%, for example, 0.1%, 0.2%, 0.3%, 0.4%, 0.5%, or 0.6%.

[0137] Depending on different printing needs, the color paste may include a variety of single colors or colors obtained by mixing two or more single colors. In some embodiments, the color paste includes one or more of the following: carbon black paste, titanium dioxide paste, golden red paste, permanent yellow paste, phthalocyanine blue paste, or manganese violet paste.

[0138] In one embodiment, for example, in step S10 above, 31% by mass of acrylic monomer is used to disperse and dissolve 0.4% by mass of additive and 3% by mass of initiator; in step S11 above, 20% by mass of silica slurry is added and further dispersed, wherein the viscosity of the silica slurry is 2000 mPa·s; in step S12 above, 45% by mass of acrylic prepolymer resin is added and further dispersed; in step S13 above, 0.6% by mass of color paste is added, finally obtaining the radiation-curable resin composition described in this application, thereby enabling the prepared resin composition to achieve the effect of no color paste sedimentation even after long-term static resin composition. Please refer to [link to relevant documentation]. Figures 3 to 5 The comparison chart shows the effects.

[0139] In summary, the radiation-curable resin composition and its preparation method provided in this application prepare the resin composition by adding a certain mass fraction and a preset viscosity of silica slurry, thereby achieving a long-term (tested to be up to 72 hours) static resin composition without pigment sedimentation.

[0140] The above embodiments are merely illustrative of the principles and effects of this application and are not intended to limit this application. Any person skilled in the art can modify or alter the above embodiments without departing from the spirit and scope of this application. Therefore, all equivalent modifications or alterations made by those skilled in the art without departing from the spirit and technical concept disclosed in this application should still be covered by the claims of this application.

Claims

1. A method for producing a radiation-curable resin composition, characterized by, The preparation method comprises the following steps: The acrylic monomer dispersion with a mass fraction of 20%-50% is used to dissolve the auxiliary agent with a mass fraction of 0.1%-1% and the initiator with a mass fraction of 1%-5%; The pre-prepared aerosil slurry with a mass fraction of 5%-30% and a viscosity of 800-5000 mPa·s is added into the acrylic monomer and dispersed, and the aerosil slurry is prepared by continuously adding the fumed silica with a mass fraction of 5%-20% into the acrylic monomer with a mass fraction of 80%-95% and stirring according to the following procedure: The fumed silica is continuously added at an initial speed of 200-500 rpm and stirred for 5-10 min, then accelerated to 500-800 rpm and stirred for 15-20 min, and then accelerated to 800-1200 rpm and stirred for 20-40 min to obtain the aerosil slurry with a viscosity of 800-5000 mPa·s; the acrylic monomer is preferably one or more of TPGDA, TMPTA, DPGDA, and ACMO; Finally, the acrylic prepolymer resin with a mass fraction of 30%-60% is added for final dispersion treatment to obtain the radiation-curable resin composition, and the acrylic prepolymer is preheated at 60-80°C for 2-4 h before being added.

2. The production method according to claim 1, characterized by, The acrylic monomer dispersion with a mass fraction of 30%-50% is used to dissolve the auxiliary agent and the initiator.

3. The preparation method according to claim 1, characterized in that, The auxiliary agent comprises one or more of a defoaming agent, a wetting dispersant, and a leveling agent.

4. The method of claim 1, wherein, The fumed silica slurry with a viscosity of 1500-2000 mPa·s is added in a mass fraction of 5%-20%.

5. The production method according to claim 1 or 4, characterized by, The aerosil slurry is prepared by adding the fumed silica with a mass fraction of 5%-20% into the acrylic monomer with a mass fraction of 80%-90% and stirring multiple times.

6. The production method according to claim 5, wherein The aerosil slurry is prepared by adding the fumed silica with a mass fraction of 5%-15% into a mixture of one or more of the UV monomers TPGDA, TMPTA, DPGDA, or ACMO and stirring multiple times.

7. The preparation method according to claim 5, characterized in that, The fumed silica comprises dimethyldichlorosilane, hexamethyldisilazane, octamethylcyclotetrasiloxane, octylsilane, or polydimethylsiloxane-treated fumed silica.

8. The preparation method according to claim 5, characterized in that, The step of preparing the aerosil slurry comprises adding the fumed silica with a mass fraction of 5%-15% into the acrylic monomer with a mass fraction of 80%-90% at an initial speed for a first duration, performing a first acceleration and stirring for a second duration, and then performing a second acceleration and stirring for a third duration.

9. The production method according to claim 8, characterized by, In the step of adding the fumed silica with a mass fraction of 5%-15% into the acrylic monomer with a mass fraction of 80%-90% at an initial speed for a first duration, the fumed silica is continuously added into the acrylic monomer without interruption within the first duration.

10. The preparation method according to claim 8, characterized in that, The initial stirring speed is 300-400 rpm, the first accelerated stirring speed is 600-700 rpm, and the second accelerated stirring speed is 1000-1200 rpm.

11. The preparation method according to claim 8, characterized in that, The first time length is 10 min, the second time length is 20 min, and the third time length is 30 min.

12. The method of claim 1, wherein, The acrylic prepolymer resin with a mass fraction of 40-50% is preheated at a temperature of 60-80°C for 2-4 h.

13. The method of claim 12, wherein, The acrylic prepolymer resin comprises aliphatic polyurethane acrylate, aliphatic polyurethane methacrylate, aromatic polyurethane acrylate, epoxy acrylate, or polyester acrylate.

14. The method of claim 1, wherein, The step of adding and dispersing a color paste is further included.

15. The preparation method according to claim 14, characterized in that, The color paste comprises one or more of a mixture of carbon black paste, titanium white paste, golden red paste, permanent yellow paste, phthalocyanine blue paste, or manganese violet paste.

16. A radiation-curable resin composition prepared according to the method of any one of claims 1 to 15, characterized in that, The resin composition comprises: an acrylic monomer with a mass fraction of 20-50%; an auxiliary agent with a mass fraction of 0.1-1%; an initiator with a mass fraction of 1-5%; an aerated silica paste with a mass fraction of 5-30%; the viscosity of the aerated silica paste is 800 mPa·s to 5000 mPa·s; an acrylic prepolymer resin with a mass fraction of 30-60%.

17. The radiation-curable resin composition according to claim 16, characterized in that, The auxiliary agent comprises one or more of a defoaming agent, a wetting dispersant, and a leveling agent.

18. The radiation-curable resin composition according to claim 16, wherein The mass fraction of the aerated silica paste is 5-20%.

19. The radiation-curable resin composition according to claim 16, wherein The aerated silica comprises dimethyldichlorosilane, hexamethyldisilazane, octamethylcyclotetrasiloxane, octylsilane, or polydimethylsiloxane-treated fumed silica.

20. The radiation-curable resin composition according to claim 16, wherein The acrylic prepolymer resin comprises aliphatic polyurethane acrylate, aliphatic polyurethane methacrylate, aromatic polyurethane acrylate, epoxy acrylate, or polyester acrylate.

21. The radiation-curable resin composition according to claim 16, wherein The color paste is further included.

22. The radiation-curable resin composition according to claim 21, wherein The color paste comprises one or more of a mixture of carbon black paste, titanium white paste, golden red paste, permanent yellow paste, phthalocyanine blue paste, or manganese violet paste.

Images