Photoinitiating resin composition, method for preparing the same, and use thereof

Abstract

The application provides a photo-initiated resin composition, a preparation method and application thereof. The preparation method of the photo-initiated resin composition comprises the following steps: S1, mixing an acrylate monomer and a photo-initiator, and obtaining a first mixture after first stirring; S2, adding a non-reactive silicone into the first mixture, and obtaining the resin composition after second stirring; the acrylate monomer is 30-70 parts by weight, the photo-initiator is 1-5 parts by weight, and the non-reactive silicone is 5-35 parts by weight. Through the carefully designed composition formula and preparation process, the preparation of the resin composition without precipitation, low viscosity and easy to peel off from various interfaces after curing is realized.

Description

Technical Field

[0001] This invention relates to the field of resins for 3D printing, and more specifically, to a photoinitiating resin composition, its preparation method, and its application. Background Technology

[0002] For orthodontic applications, traditional manufacturing plants use plaster casting for production. Taking orthodontic appliances as an example, workers need to evenly apply a separating agent to the plaster model so that the appliance, which is then cured on it, can be separated from the plaster model.

[0003] Currently, the use of 3D printing technology to produce dental products, such as dental molds, is common. When using existing processes for separating orthodontic appliances, a separating agent still needs to be applied to the dental mold to facilitate separation of the appliance from the mold. While 3D printing model resins exist that can be separated directly without a separating agent, these resin compositions inevitably contain colorant fillers, such as titanium dioxide, for ease of use. This results in a plaster-like white resin model after curing. However, these fillers tend to precipitate during the storage of the 3D printing model resin, affecting print quality and requiring an additional pre-shaking process, making it unsuitable for large-scale use.

[0004] Therefore, how to provide a new resin composition that combines the characteristics of being separable without the need for a separating agent after curing with the characteristics of low viscosity and no precipitation is one of the important technical problems that need to be solved in this field. Summary of the Invention

[0005] The main objective of this invention is to provide a photoinitiating resin composition, its preparation method, and its application, in order to solve the problems in the prior art where the resin composition used for 3D printing dental models has excessively high viscosity, is difficult to separate after curing, and may cause filler precipitation during preparation and application.

[0006] To achieve the above objectives, a first aspect of the present invention provides a method for preparing a photoinitiating resin composition, comprising: step S1, mixing an acrylate monomer and a photoinitiator, and obtaining a first mixture after a first stirring; step S2, adding a non-reactive organosilicon to the first mixture, and obtaining a resin composition after a second stirring; wherein, by weight, the acrylate monomer is 30 to 70 parts, the photoinitiator is 1 to 5 parts, and the non-reactive organosilicon is 5 to 35 parts.

[0007] In some embodiments, the non-reactive organosilicon is a linear polysilane, and the linear polysilane has the structure shown in Formula I:

[0008]

[0009] Wherein, R and R' are each independently one or more combinations of hydrogen, C1-C6 alkyl, C1-C6 alkoxy, phenyl, phenoxy, C1-C6 alkyl-substituted phenyl and C1-C6 alkyl-substituted phenoxy, and n is any integer from 50 to 1200; preferably, R is methyl or p-methylphenyl, R' is hydrogen, and n is any integer from 200 to 800.

[0010] In some embodiments, the non-reactive organosilicon is: Where n is 600; and / or,

[0011] Where n is 600.

[0012] In some embodiments, the acrylate monomer is selected from one or more of alkyl (meth)acrylates, hydroxy (meth)acrylates, (meth)acrylates with aromatic rings and / or aliphatic rings, diol diacrylates, alkoxylated acrylates, dioxopentanoates, and alkoxylated bisphenol A di(meth)acrylates. Preferably, the acrylate monomer is selected from acrylamide, methacryloylmorpholine, cyclotrimethylolpropane methyl acetal acrylate, hydroxyethyl acrylate, hydroxyethyl methacrylate, dicyclopentene acrylate, and tetrahydrofurfuryl propylene. Acrylates, Laurate, 2-Phenoxyethyl Methacrylate, 3,3,5-Trimethylcyclohexane Methacrylate, Tricyclodecanediethanol Diacrylate, Tricyclodecanediethanol Dimethacrylate, Ethoxybisphenol A Diacrylate, Ethoxybisphenol A Dimethacrylate, Diethylene Glycol Diacrylate, Triethylene Glycol Diacrylate, Polyethylene Glycol (200) Diacrylate, Polyethylene Glycol (400) Diacrylate, Polyethylene Glycol (600) Diacrylate, 1,4-Butanediol Diacrylate, 1,6-Dihexyl Diol diacrylate, dipropylene glycol diacrylate, tripropylene glycol diacrylate, trimethylolpropane triacrylate, pentaerythritol triacrylate, ditrimethylolpropane tetraacrylate, dipentaerythritol pentaacrylate, dipentaerythritol hexaacrylate, (2-hydroxyethyl) isocyanurate triacrylate, isoborneol acrylate, and isoborneol methacrylate; and / or, the photoinitiator is a free radical photoinitiator; preferably, the photoinitiator is selected from benzoyl carbamate, 2,4,6-(trimethylbenzoyl)diphenylphosphine oxide, phenylbis(2-hydroxyethyl)-diphenylphosphine oxide, etc. One or more of the following: 4,6-trimethylbenzoyl), ethyl 2,4,6-trimethylbenzoylphenylphosphonate, diphenylethanol ketone, 2-hydroxy-2-methyl-1-phenyl-1-propanone, 1-hydroxycyclohexylphenyl ketone, α,α'-dimethylbenzoyl ketal, α,α-diethoxyacetophenone, 2-hydroxy-2-methyl-p-hydroxyethyl ether phenylacetone-1, 2-methyl-1-(4-methylthiophenyl)-2-morpholinoacetone-1, and 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)butanone-1.

[0013] In some embodiments, the stirring speed of the first stirring is 600 r / min to 800 r / min, and the stirring time is 20 min to 30 min; and / or, the stirring speed of the second stirring is 800 r / min to 1000 r / min, and the stirring time is 20 min to 30 min.

[0014] In some embodiments, step S2 further includes adding the pigment to the first mixture and then stirring it a second time to obtain a resin composition; preferably, the pigment includes one or more of complex blue, pigment red, carbon black, pigment yellow and pigment purple, and the pigment is 0.5 to 1.0 parts by weight.

[0015] In some embodiments, step S2 further includes adding 15 to 40 parts of acrylate oligomer to the first mixture.

[0016] In some embodiments, the resin composition comprises, by weight percentage, 30% to 70% acrylate monomer, 1% to 5% photoinitiator, 5% to 35% non-reactive organosilicon, and 15% to 40% acrylate oligomer.

[0017] A second aspect of the present invention provides a photoinitiating resin composition prepared by the method described above; or, by weight, the resin composition comprises 30 to 70 parts of acrylate monomer, 1 to 5 parts of photoinitiator, and 5 to 35 parts of non-reactive organosilicon; preferably, the non-reactive organosilicon is a linear polysilane, and the linear polysilane has the structure shown in Formula I:

[0018]

[0019] Wherein, R and R' are each independently a combination of one or more of hydrogen, C1-C6 alkyl, C1-C6 alkoxy, phenyl, phenoxy, C1-C6 alkyl-substituted phenyl, and C1-C6 alkyl-substituted phenoxy, and n is any integer from 50 to 1200; and / or, the acrylate monomer is selected from one or more of (meth)acrylate alkyl esters, (meth)acrylate hydroxy esters, (meth)acrylates with aromatic rings and / or aliphatic rings, diol diacrylates, alkoxylated acrylates, dioxopropyl acrylates, and alkoxylated bisphenol A di(meth)acrylates; preferably, the acrylate monomer is selected from acrylamide, methacrylamide, cyclotrimethylolpropionate, etc. Propane methyl acetal acrylate, hydroxyethyl acrylate, hydroxyethyl methacrylate, dicyclopentene acrylate, tetrahydrofurfuryl acrylate, laurate acrylate, 2-phenoxyethyl methacrylate, 3,3,5-trimethylcyclohexane methacrylate, tricyclodecanediethanol diacrylate, tricyclodecanediethanol dimethacrylate, ethoxylated bisphenol A diacrylate, ethoxylated bisphenol A dimethacrylate, diethylene glycol diacrylate, triethylene glycol diacrylate, polyethylene glycol (200) diacrylate, polyethylene glycol (400) diacrylate, polyethylene glycol (600) diacrylate, 1,4-butanediol diacrylate, 1,6-dihexanediol diacrylate Dipropylene glycol diacrylate, tripropylene glycol diacrylate, trimethylolpropane triacrylate, pentaerythritol triacrylate, dimethylolpropane tetraacrylate, dipentaerythritol pentaacrylate, dipentaerythritol hexaacrylate, (2-hydroxyethyl) isocyanurate triacrylate, isoborneol acrylate, and isoborneol methacrylate; and / or, the photoinitiator is a free radical photoinitiator, preferably selected from benzoyl carbamate, 2,4,6-(trimethylbenzoyl)diphenylphosphine oxide, phenylbis(2,4,6-trimethylbenzoyl), ethyl 2,4,6-trimethylbenzoylphenylphosphonate, benzoethanol ketone, 2-hydroxy-2-methyl-1-phenyl-1-hydroxyethyl-2-hydroxyethyl-2-methyl-1-phenyl ... One or more of the following: acetone, 1-hydroxycyclohexylphenyl ketone, α,α'-dimethylbenzoyl ketal, α,α-diethoxyacetophenone, 2-hydroxy-2-methyl-p-hydroxyethyl ether phenylacetone-1, 2-methyl-1-(4-methylthiophenyl)-2-morpholinoacetone-1, and 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)butanone-1; preferably, the resin composition further comprises 15 to 40 parts of acrylate oligomer; more preferably, by weight percentage, the resin composition comprises 30% to 70% acrylate monomer, 1% to 5% photoinitiator, 5% to 35% non-reactive organosilicon, and 15% to 40% acrylate oligomer.

[0020] In some embodiments, the viscosity of the photoinitiating resin composition at 25°C is 180 mPa·s to 300 mPa·s, and the resin obtained after photoinitiating curing of the photoinitiating resin composition has a short beam shear bond strength of 1.2 MPa to 1.9 MPa.

[0021] A third aspect of the present invention provides an application of the above-described photoinitiating resin composition as a dental model resin composition for 3D printing and for preparing dental models.

[0022] In some embodiments, a 3D-printed dental model is obtained by 3D printing a photoinitiating resin composition. Then, powder is spread onto the 3D-printed dental model to manufacture a dental product. Preferably, the powder spreading includes: Step A, surrounding the cured 3D-printed dental model with wax and filling undercuts to obtain a first product; Step B, spreading powder onto the first product using a dripping method, and placing a retainer and / or jaw pad on the first product to obtain a second product; Step C, treating the second product at 0.1MPa–0.3MPa and 40°C–50°C for 10–20 minutes to obtain a third product; Step D, placing the third product at 20°C–30°C for 5–15 minutes, and then removing the retainer and / or jaw pad to obtain the dental product.

[0023] By applying the technical solution of this invention, and through a carefully designed composition formulation and preparation process, a resin composition that is free of precipitation, has low viscosity, and is easy to peel off from various interfaces after curing is achieved. The addition of non-reactive organosilicon not only makes the resin composition white but also reduces its viscosity, improves its fluidity, and effectively reduces adhesion between the cured resin model and the mold, making the separation and processing of the cured resin more convenient. Detailed Implementation

[0024] It should be noted that, unless otherwise specified, the embodiments and features described in this application can be combined with each other. The present invention will now be described in detail with reference to the embodiments.

[0025] As described in the background art, existing resin compositions used for 3D printing dental models suffer from problems such as excessively high viscosity, difficulty in separation after curing, and potential filler precipitation during preparation and application. To address these technical problems, a first aspect of the present invention provides a method for preparing a photoinitiating resin composition, comprising: step S1, mixing an acrylate monomer and a photoinitiator, followed by a first stirring to obtain a first mixture; step S2, adding a non-reactive organosilicon to the first mixture, followed by a second stirring to obtain a resin composition; by weight, the acrylate monomer is 30 to 70 parts, the photoinitiator is 1 to 5 parts, and the non-reactive organosilicon is 5 to 35 parts. For example, 35 parts of acrylate monomer, 2 parts of photoinitiator, and 10 parts of non-reactive organosilicon. For example, 50 parts of acrylate monomer, 3 parts of photoinitiator, and 15 parts of non-reactive organosilicon. For example, 60 parts of acrylate monomer, 4 parts of photoinitiator, and 20 parts of non-reactive organosilicon. For example, the composition is 65 parts acrylate monomer, 5 parts photoinitiator, and 30 parts non-reactive organosilicon.

[0026] The above-described preparation method, through a carefully designed composition formulation and preparation process, achieves the preparation of a resin composition that is precipitation-free, low-viscosity, and easily peelable from various interfaces after curing. In particular, in existing technologies, to achieve a plaster-like white finish in the final cured resin, it is unavoidable to add color fillers such as titanium dioxide. These fillers precipitate during the storage of the 3D printed model resin, affecting print quality and requiring an additional shaking process, making it unsuitable for large-scale use. This invention creatively adds non-reactive organosilicon to the composition. Firstly, it achieves a white effect without the need for additional white filler, and because no white filler is added, the problem of white filler settling is eliminated. Simultaneously, the addition of non-reactive organosilicon significantly reduces the viscosity of the resin composition, improving its fluidity and thus enhancing printing efficiency in 3D printing. More importantly, the lower viscosity makes it easier to clean the low-viscosity resin adhering to the dental mold surface more thoroughly. Furthermore, non-reactive organosilicon, due to its more stable structure and chemical properties, does not damage the resin structure obtained after curing, thereby better protecting printing accuracy and the mechanical properties of the cured resin.

[0027] Specifically, in the above preparation method, the photoinitiator is first dissolved in the acrylate monomer, and then, in step S2, the non-reactive organosilicon is uniformly mixed into the mixture formed by the acrylate monomer and the photoinitiator. Compared with the method of adding all components at once and mixing them, the above addition preparation method can improve the mixing uniformity between the components, especially more effectively promoting the dispersion of non-reactive organosilicon in the system, thereby preparing a resin composition with good overall performance, especially with lower viscosity, lower surface energy after curing, and easier separation from various surfaces.

[0028] Meanwhile, in order to better leverage the synergistic effect between the components, the inventors conducted numerous experiments to optimize the dosage of each component as described above, thereby obtaining a resin composition with lower viscosity, better fluidity, and easier peeling after curing.

[0029] In several typical embodiments, the non-reactive organosilicon is a linear polysilane, and the linear polysilane has the structure shown in Formula I:

[0030]

[0031] Wherein, R and R' are each independently one or more combinations of hydrogen, C1-C6 alkyl, C1-C6 alkoxy, phenyl, phenoxy, C1-C6 alkyl-substituted phenyl, and C1-C6 alkyl-substituted phenoxy, and n is any integer from 50 to 1200, for example, n is 80, 100, 200, 300, 400, 500, 600, 700, 800, 900, 1000; preferably, R is methyl or p-methylphenyl, R' is hydrogen, and n is any integer from 200 to 800, for example, n is 250, 300, 350, 400, 450, 500, 550, 600, 650, 700, 750. The inventors designed the types and structures of non-reactive organosilicones through extensive experiments, and finally optimized the above-mentioned structure that can reduce the viscosity of the resin composition.

[0032] In practical applications, R can also be one or more combinations of C1-C6 alkenyl, hydroxyl, acetoxy, chlorine, hydrogen, C1-C6 alkyl, phenyl, and C1-C6 alkyl-substituted phenyl groups; R' can also be one or more combinations of ether, hydrogen, C1-C6 alkyl, phenyl, and C1-C6 alkyl-substituted phenyl groups. When non-reactive organosilicones possessing the above structures are used as a component of a resin composition, they can also impart low viscosity and easy separation after curing to the resulting resin composition.

[0033] In some embodiments, R is methyl or p-methylphenyl, R' is hydrogen, and n is any integer from 200 to 800, for example, n is 250, 300, 350, 400, 450, 500, 550, 600, 650, 700, or 750. Adding a non-reactive organosilicon having the above structure as a component to the resin composition can more effectively reduce its viscosity and the surface energy of the cured resin, thereby obtaining a model resin product that is easier to separate from the mold.

[0034] In several more typical embodiments, in order to further reduce the viscosity of the resulting resin composition, improve the peelability of the cured resin, and also enable the non-reactive silicone to be better compatible with and diluted with other components in the resin composition formulation, so as to improve the overall performance of the resin composition, the inventors, through extensive experiments, have preferred the following: Where n is 600; and / or, Where n is 600.

[0035] In some embodiments, the acrylate monomer is selected from one or more of alkyl (meth)acrylates, hydroxy (meth)acrylates, (meth)acrylates with aromatic rings and / or aliphatic rings, diol diacrylates, alkoxylated acrylates, dioxopentoxide acrylates, and alkoxylated bisphenol A di(meth)acrylates. Preferably, the acrylate monomer is selected from acrylamide, methacrylamide, cyclotrimethylolpropane methyl acetal acrylate, hydroxyethyl acrylate, hydroxyethyl methacrylate, dicyclopentene acrylate, tetrahydrofurfuryl acrylate, laurate acrylate, 2-phenoxyethyl methacrylate, 3,3,5-trimethylcyclohexane methacrylate, tricyclodecanediethanol diacrylate, and tricyclodecane. Dimethyl methacrylate, bisphenol A diacrylate ethoxylate, bisphenol A dimethacrylate ethoxylate, diethylene glycol diacrylate, triethylene glycol diacrylate, polyethylene glycol (200) diacrylate, polyethylene glycol (400) diacrylate, polyethylene glycol (600) diacrylate, 1,4-butanediol diacrylate, 1,6-dihexanediol diacrylate, dipropylene glycol diacrylate, tripropylene glycol diacrylate, trimethylolpropane triacrylate, pentaerythritol triacrylate, dimethylolpropane tetraacrylate, dipentaerythritol pentaacrylate, dipentaerythritol hexaacrylate, (2-hydroxyethyl) isocyanurate triacrylate, isobornyl acrylate, and isobornyl methacrylate. The selection of these monomers further enhances the structural properties and mechanical strength of the resin composition after photocuring.

[0036] In practical applications, in addition to the types mentioned above, acrylate monomers can also be selected from lauryl acrylate, glycidyl methacrylate, tetrahydrofuran methyl acrylate, phenoxyethyl acrylate, and phenoxyethyl methacrylate.

[0037] And / or, the photoinitiator is a free radical photoinitiator; preferably, the photoinitiator is selected from one or more of benzoyl carbamate, 2,4,6-(trimethylbenzoyl)diphenylphosphine oxide, phenylbis(2,4,6-trimethylbenzoyl), ethyl 2,4,6-trimethylbenzoylphenylphosphonate, benzoethanol ketone, 2-hydroxy-2-methyl-1-phenyl-1-propanone, 1-hydroxycyclohexylphenyl ketone, α,α'-dimethylbenzoyl ketal, α,α-diethoxyacetophenone, 2-hydroxy-2-methyl-p-hydroxyethyl ether phenylacetone-1, 2-methyl-1-(4-methylthiophenyl)-2-morpholinoacetone-1, and 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)butanone-1. The selection of the above photoinitiators optimizes the curing speed and curing wavelength of the resin composition, making it better suited for various 3D printing equipment and achieving a fast and efficient curing process.

[0038] In addition, in practical applications, photoinitiators can also be selected from other types of benzoin and its derivatives, benzoyl and its derivatives, acetophenone derivatives, α-hydroxy ketone derivatives, α-amino ketone derivatives, benzoyl carbamates, and acylphosphine oxides, etc.

[0039] In several typical embodiments, the stirring speed of the first stirring is 600 r / min to 800 r / min, and the stirring time is 20 min to 30 min. Through extensive experiments, the inventors optimized the mixing conditions of the acrylate monomer and the photoinitiator, and found that the above stirring conditions can better promote the uniform mixing of the two, more effectively avoid inconsistent curing due to uneven mixing, or prepolymerization due to overly vigorous mixing conditions, thereby significantly improving the performance of the resin composition during preparation and after curing.

[0040] In some embodiments, adapted to the conditions of the first stirring described above, the inventors further optimized the stirring speed of the second stirring to be 800 r / min to 1000 r / min and the stirring time to be 20 min to 30 min through extensive experiments. This stirring speed can further improve the dispersion uniformity of the components in the resin composition, especially the dispersion degree of non-reactive organosilicon, thereby obtaining a resin composition with lower viscosity and easier separation from various surfaces after curing.

[0041] In several typical embodiments, step S2 further includes adding the pigment to the first mixture and then stirring it a second time to obtain a resin composition, so as to obtain a resin composition with lower surface energy, better antibacterial properties, or better color performance after curing. Preferably, the pigment includes one or more of complex blue, pigment red, carbon black, pigment yellow, and pigment violet. These pigments can all dissolve in the resin composition provided by the present invention without producing precipitation and can play a good color-developing role. The pigment is 0.5 to 1.0 parts by weight, for example, 0.6 parts, 0.7 parts, 0.8 parts, or 0.9 parts.

[0042] In some embodiments, step S2 further includes adding 15 to 40 parts of acrylate oligomer, such as 20, 25, 30, or 35 parts, to the first mixture to significantly improve the peelability and molding stability of the resin composition after curing. More preferably, the acrylate oligomer is selected from one or more of Sartoma SR991, Demas BR970, and Sartoma SR996. Theoretically, the type and specific model of the acrylate oligomer can be chosen from those commonly used in the art or similar fields. However, the aforementioned models, optimized by the inventors through extensive experimentation, are better suited to the resin composition system, resulting in a resin composition with better dispersion uniformity, lower viscosity, easier peelability after curing, and better mechanical properties.

[0043] In some embodiments, the resin composition, by weight percentage, comprises 30%–70% acrylate monomer, 1%–5% photoinitiator, 5%–35% non-reactive silicone, and 15%–40% acrylate oligomer. This content ratio and formulation design result in a resin composition with better overall performance after curing. For example, the composition may contain 68% acrylate monomer, 2% photoinitiator, 10% non-reactive silicone, and 20% acrylate oligomer. Alternatively, it may contain 57% acrylate monomer, 3% photoinitiator, 15% non-reactive silicone, and 25% acrylate oligomer. Another example is 46% acrylate monomer, 4% photoinitiator, 20% non-reactive silicone, and 30% acrylate oligomer. Yet another example is 30% acrylate monomer, 5% photoinitiator, 30% non-reactive silicone, and 35% acrylate oligomer.

[0044] Furthermore, in practical applications, ester compounds can be added to help improve the curing speed and surface smoothness of the resin composition, resulting in a smoother resin surface for the printed model.

[0045] A second aspect of the present invention provides a photoinitiating resin composition prepared by the method described above; or, by weight, the resin composition comprises 30 to 70 parts of acrylate monomer, 1 to 5 parts of photoinitiator, and 5 to 35 parts of non-reactive organosilicon; preferably, the non-reactive organosilicon is a linear polysilane, and the linear polysilane has the structure shown in Formula I:

[0046]

[0047] Wherein, R and R' are each independently a combination of one or more of hydrogen, C1-C6 alkyl, C1-C6 alkoxy, phenyl, phenoxy, C1-C6 alkyl-substituted phenyl, and C1-C6 alkyl-substituted phenoxy, and n is any integer from 50 to 1200; and / or, the acrylate monomer is selected from one or more of (meth)acrylate alkyl esters, (meth)acrylate hydroxy esters, (meth)acrylates with aromatic rings and / or aliphatic rings, diol diacrylates, alkoxylated acrylates, dioxopropyl acrylates, and alkoxylated bisphenol A di(meth)acrylates; preferably, the acrylate monomer is selected from acrylamide morpholine, methacrylamide morpholine, etc. Phosphorus, Cyclotrimethylolpropane methyl acetal acrylate, Hydroxyethyl acrylate, Hydroxyethyl methacrylate, Dicyclopentene acrylate, Tetrahydrofurfuryl acrylate, Laurate acrylate, 2-Phenoxyethyl methacrylate, 3,3,5-Trimethylcyclohexane methacrylate, Tricyclodecanediethanol diacrylate, Tricyclodecanediethanol dimethacrylate, Ethoxybisphenol A diacrylate, Ethoxybisphenol A dimethacrylate, Diethylene glycol diacrylate, Triethylene glycol diacrylate, Polyethylene glycol (200) diacrylate, Polyethylene glycol (400) diacrylate, Polyethylene glycol (600) diacrylate, 1,4-Butanediol diacrylate 1,6-Dihexanediol diacrylate, dipropylene glycol diacrylate, tripropylene glycol diacrylate, trimethylolpropane triacrylate, pentaerythritol triacrylate, ditrimethylolpropane tetraacrylate, dipentaerythritol pentaacrylate, dipentaerythritol hexaacrylate, (2-hydroxyethyl) isocyanurate triacrylate, isoborneol acrylate, and isoborneol methacrylate; and / or, the photoinitiator is a free radical photoinitiator, preferably selected from benzoyl carbamate, 2,4,6-(trimethylbenzoyl)diphenylphosphine oxide, phenylbis(2,4,6-trimethylbenzoyl), ethyl 2,4,6-trimethylbenzoylphenylphosphonate, diphenyl The resin composition comprises one or more of the following: ethanol ketone, 2-hydroxy-2-methyl-1-phenyl-1-propanone, 1-hydroxycyclohexylphenyl ketone, α,α'-dimethylbenzoyl ketal, α,α-diethoxyacetophenone, 2-hydroxy-2-methyl-p-hydroxyethyl ether phenylacetone-1, 2-methyl-1-(4-methylthiophenyl)-2-morpholinoacetone-1, and 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)butanone-1; preferably, the resin composition further comprises 15 to 40 parts of acrylate oligomer; more preferably, the acrylate oligomer is selected from one or more of Sartoma SR991, Demas BR970, and Sartoma SR996.

[0048] In some embodiments, the resin composition comprises, by weight percentage, 30% to 70% acrylate monomer, 1% to 5% photoinitiator, 5% to 35% non-reactive organosilicon, and 15% to 40% acrylate oligomer.

[0049] The resulting resin composition has lower viscosity and better flowability, which is more conducive to improving the surface precision after curing. At the same time, the resin obtained after curing can be separated from the mold or any surface without any separating agent.

[0050] In some embodiments, the viscosity of the photoinitiating resin composition at 25°C is 180 mPa·s to 300 mPa·s, and the resin obtained after photoinitiating curing has a short beam shear bond strength of 1.2 MPa to 1.9 MPa. That is, the resulting resin composition has a lower viscosity, and the resin obtained after photoinitiating curing is also easier to separate from the surface on which it is located.

[0051] A third aspect of the present invention provides an application of the above-described photoinitiating resin composition as a resin composition for 3D printing dental models. The resulting resin composition has low viscosity, is easy to separate after curing, and does not experience filler precipitation or other problems during preparation and application. Therefore, it is suitable for the preparation of 3D printed dental models, exhibiting higher printing efficiency and accuracy during the 3D printing process. It is also easier to separate from the surface, facilitates post-processing, and is more suitable for large-scale industrial applications.

[0052] In some embodiments, a 3D-printed dental model is obtained by 3D printing a photoinitiating resin composition. The 3D-printed dental model is then sequentially cleaned, cured, and coated with powder to obtain a dental model. Preferably, the powder coating includes: Step A, surrounding the cured 3D-printed dental model with wax and filling undercuts to obtain a first product; Step B, coating the first product with powder using a dripping method, and placing a retainer and / or jaw pad on the first product to obtain a second product; Step C, treating the second product at 0.1MPa–0.3MPa and 40°C–50°C for 10–20 minutes to obtain a third product; Step D, placing the third product at 20°C–30°C for 5–15 minutes, and then removing the retainer and / or jaw pad to obtain the dental model.

[0053] In the specific dental model manufacturing process, the above-mentioned photoinitiating resin composition is poured into the tray of the 3D printer for printing to obtain a 3D printed dental model, and then cleaned within 12 hours according to the steps and parameters in the table below.

[0054] Cleaning solvent Cleaning method Isopropanol 2 min (rough wash) + 30 s blow dry + 1 min (fine wash) + 30 s blow dry 95% medical alcohol 1 minute (rough wash) + 30 seconds of blow-drying + 1 minute (fine wash) + 30 seconds of blow-drying 75% medical alcohol 1 minute (rough wash) + 30 seconds of blow-drying + 1 minute (fine wash) + 30 seconds of blow-drying

[0055] After cleaning, the model is cured. Then, the 3D-printed dental model is coated with self-curing resin powder to obtain a dental model that meets the usage requirements. During the powder coating process, the 3D-printed model is first surrounded by wax and undercuts are filled. Filling undercuts means filling the undercuts (concave parts) on the tooth model. Then, the powder is coated on the model using the dripping method to create retainers and / or jaw pads, which are then placed on the powder-coated model. The powder-coated model with retainers and / or jaw pads is then placed in a pressure cooker with 0.2 MPa pressure (the water in the cooker must completely submerge the model) and boiled at 45°C for 15 minutes. Afterward, the resulting model is left at room temperature for 10 minutes. Once cooled to room temperature, the retainers and / or jaw pads are removed from the model using a tool (such as a wax knife).

[0056] The present application will be further described in detail below with reference to specific embodiments, which should not be construed as limiting the scope of protection claimed in the present application.

[0057] Unless otherwise defined, all technical terms used herein have the same meaning as commonly understood by those skilled in the art. The technical terms used herein are for the purpose of describing particular embodiments only and are not intended to limit the scope of the invention.

[0058] Example 1

[0059] A method for preparing a photoinitiating resin composition:

[0060] The photoinitiator resin composition was formulated based on the following proportions: dipropylene glycol diacrylate (acrylate monomer): 58%; ethyl acrylate oligomer Sartoma SR991: 30%; non-reactive organosilicon: 10%; 2,4,6-(trimethylbenzoyl)diphenylphosphine oxide (photoinitiator): 2%.

[0061] The structural formula of the non-reactive organosilicon is: n is 600.

[0062] Step S1: Stir the mixture of 2,4,6-(trimethylbenzoyl)diphenylphosphine oxide and dipropylene glycol diacrylate at a speed of 700 r / min for 25 min to completely dissolve the 2,4,6-(trimethylbenzoyl)diphenylphosphine oxide and obtain the first mixture;

[0063] Step S2: Continue to add acrylate oligomers and non-reactive organosilicon to the first mixture, and continue stirring at 900 r / min for 25 min to obtain a photoinitiating resin composition.

[0064] The resulting composition is white after curing.

[0065] Example 2

[0066] A method for preparing a photoinitiating resin composition:

[0067] The only difference between this embodiment and Embodiment 1 is that 0.5% of complex blue was added as a pigment in step S2, while the amount of dipropylene glycol diacrylate was correspondingly reduced to 47.5%.

[0068] The resulting composition turns blue after curing.

[0069] Example 3

[0070] A method for preparing a photoinitiating resin composition:

[0071] The only difference between this embodiment and Embodiment 1 is that an equal weight of another type of non-reactive organosilicon is used to replace the original non-reactive organosilicon in Embodiment 1. The structural formula of this other type of non-reactive organosilicon is:

[0072] n is 600.

[0073] Example 4

[0074] A method for preparing a photoinitiating resin composition:

[0075] The only difference between this embodiment and Embodiment 1 is that the rotational speed in step S1 is changed to 600 r / min and the time is changed to 30 min; the rotational speed in step S2 is changed to 1000 r / min and the time is changed to 20 min.

[0076] Example 5

[0077] A method for preparing a photoinitiating resin composition:

[0078] The only difference between this embodiment and Embodiment 1 is that the rotation speed in step S1 is changed to 800 r / min and the time is changed to 20 min; the rotation speed in step S2 is changed to 800 r / min and the time is changed to 30 min.

[0079] Example 6

[0080] A method for preparing a photoinitiating resin composition:

[0081] The only difference between this embodiment and Embodiment 1 is that the rotational speed in step S1 is changed to 500 r / min and the time is changed to 40 min; the rotational speed in step S2 is changed to 1200 r / min and the time is changed to 10 min.

[0082] Example 7

[0083] A method for preparing a photoinitiating resin composition:

[0084] The only difference between this embodiment and Embodiment 1 is that the rotation speed in step S1 is changed to 900 r / min and the time is changed to 10 min; the rotation speed in step S2 is changed to 600 r / min and the time is changed to 40 min.

[0085] Example 8

[0086] A method for preparing a photoinitiating resin composition:

[0087] The only difference between this embodiment and Example 1 is that the type of acrylate monomer is changed to acrylmorpholine, the type of photoinitiator is changed to 2-hydroxy-2-methyl-1-phenyl-1-propanone, and the type of acrylate oligomer is changed to Sartoma SR996. All other conditions and parameters remain unchanged.

[0088] Example 9

[0089] A method for preparing a photoinitiating resin composition:

[0090] The only difference between this embodiment and Example 1 is that the type of acrylate monomer is changed to trimethylolpropane triacrylate, the type of photoinitiator is changed to 1-hydroxycyclohexylphenyl ketone, and the type of acrylate oligomer is changed to Demas BR970. All other conditions and parameters remain unchanged.

[0091] Comparative Example 1

[0092] A method for preparing a photoinitiating resin composition:

[0093] The only difference between this comparative example and Example 1 is that no non-reactive organosilicon was added, and the amounts of other components were adjusted accordingly: dipropylene glycol diacrylate: 63%; ethyl acrylate oligomer Sartoma SR991: 35%; 2,4,6-(trimethylbenzoyl)diphenylphosphine oxide (photoinitiator): 2%.

[0094] The resulting resin composition is transparent after curing, making it difficult to apply in practice.

[0095] Comparative Example 2

[0096] A method for preparing a photoinitiating resin composition:

[0097] The only difference between this comparative example and Example 1 is the amount of each component. Specifically, based on the total weight of the photoinitiating resin composition as 100%, the composition is as follows: dipropylene glycol diacrylate: 35%; ethyl acrylate oligomer Sartoma SR991: 40%; non-reactive organosilicon: 24.0%; 2,4,6-(trimethylbenzoyl)diphenylphosphine oxide: 0.5%; and 0.5% titanium dioxide was added to make the resin composition appear white after curing.

[0098] Comparative Example 3

[0099] A method for preparing a photoinitiating resin composition:

[0100] The only difference between this comparative example and Example 1 is the amount of each component. Specifically, based on the total weight of the photoinitiating resin composition as 100%, the ingredients are prepared as follows: dipropylene glycol diacrylate: 70%; ethyl acrylate oligomer Sartoma SR991: 18%; non-reactive organosilicon: 4%; 2,4,6-(trimethylbenzoyl)diphenylphosphine oxide: 8%.

[0101] Comparative Example 4

[0102] A method for preparing a photoinitiating resin composition:

[0103] The only difference between this comparative example and Example 1 is the preparation method. Specifically, a mixture of 2,4,6-(trimethylbenzoyl)diphenylphosphine oxide, dipropylene glycol diacrylate, acrylate oligomers, and non-reactive organosilicon was stirred at 700 r / min for 25 min to directly obtain a photoinitiating resin composition.

[0104] That is, the comparative example does not involve two-step mixing, but instead uses a one-step method to directly mix and stir all components to obtain the photoinitiating resin composition.

[0105] Comparative Example 5

[0106] A method for preparing a photoinitiating resin composition:

[0107] The only difference between this comparative example and Example 1 is that the non-reactive organosilicon in the components is replaced with an equal weight of silane coupling agent, γ-aminopropyltriethoxysilane (KH-570).

[0108] The resulting resin composition is transparent after curing, making it difficult to apply in practice.

[0109] Test methods

[0110] Viscosity of the photoinitiating resin composition: tested according to ASTM D2393-1986.

[0111] To check for precipitation issues in the photoinitiated resin composition, the test method is as follows: Pour the well-mixed finished resin into a 100ml test tube, place the test tube in an 80℃ oven and bake for 7 days. After 7 days, remove the test tube and visually observe whether there is any precipitation at the bottom of the test tube.

[0112] Short beam shear bond strength: Referring to GB-T 30969-2014, a modified short beam shear bond strength test was used to measure the bond strength between the sample and the self-curing resin. This was used to evaluate the "anti-adhesion ability" of the resulting resin model material to dental self-curing resin after the photoinitiating resin composition has cured. Specifically, the test strip was divided into two halves. One half was made by additive manufacturing and post-processing of the resin composition, placed in a mold, and a mixture of self-curing resin powder and liquid was poured in. After the self-curing resin solidified, the strip was demolded from the mold. In particular, the bonding surface of the half-strip printed from the model material was designed to be serrated to increase the bonding area between the two materials and improve the signal-to-noise ratio and confidence level of the test results. The complete tensile specimen, composed of the cured resin model material and the cured self-curing resin, was placed in a dental high-pressure polymerization oven. After polymerization was completed at 2 bar, 40°C, and 15 min, the specimen was cooled to room temperature and held for 5 to 10 min. Then, loading and testing were performed on a universal testing machine using the equipment parameters specified in GB-T30969-2014, and the shear bond strength of the short beam was calculated.

[0113] The resin compositions obtained in each example and comparative example were tested as described above, and the results are shown in Table 1.

[0114] Table 1

[0115] Is there any sediment? Viscosity at 25℃ / mPa·s Short beam shear bond strength / MPa Example 1 no 200±20 1.328±0.20 Example 2 no 200±20 1.326±0.10 Example 3 no 230±20 1.310±0.15 Example 4 no 210±20 1.446±0.10 Example 5 no 200±20 1.502±0.20 Example 6 no 270±20 1.838±0.40 Example 7 no 250±20 1.663±0.35 Example 8 no 220±20 1.457±0.15 Example 9 no 210±20 1.326±0.40 Comparative Example 1 no 310±20 13.269±0.42 Comparative Example 2 have 210±20 6.336±0.50 Comparative Example 3 no 300±20 11.215±0.20 Comparative Example 4 no 200±20 15.162±0.18 Comparative Example 5 no 230±20 13.429±0.32

[0116] As can be seen from the above description, the embodiments of the present invention have achieved the preparation of a resin composition with low viscosity, high fluidity, no precipitation, and easy separation of the resin obtained after curing.

[0117] It should be noted that the terms "first," "second," etc., used in the specification and claims of this application are used to distinguish similar objects and are not necessarily used to describe a specific order or sequence. It should be understood that such terms can be used interchangeably where appropriate so that the embodiments of this application described herein can be implemented, for example, in a sequence other than those described herein.

[0118] The above description is merely a preferred embodiment of the present invention and is not intended to limit the invention. Various modifications and variations can be made to the present invention by those skilled in the art. Any modifications, equivalent substitutions, improvements, etc., made within the spirit and principles of the present invention should be included within the scope of protection of the present invention.

Claims

1. A method for preparing a photoinitiating resin composition, characterized in that, The method for preparing the photoinitiator resin composition includes: Step S1: The acrylate monomer and the photoinitiator are mixed and stirred for the first time to obtain the first mixture; Step S2: Add non-reactive organosilicon to the first mixture, and after a second stirring, obtain the resin composition; By weight, the acrylate monomer is 30 to 70 parts, the photoinitiator is 1 to 5 parts, and the non-reactive organosilicon is 5 to 35 parts; The non-reactive organosilicon is a linear polysilane, and the linear polysilane has the structure shown in Formula I: Equation I Where R is methyl or p-methylphenyl, R' is hydrogen, and n is any integer from 200 to 800.

2. The method for preparing the photoinitiating resin composition according to claim 1, characterized in that, The non-reactive organosilicon is: Where n is 600; and / or, , where n is 600.

3. The method for preparing the photoinitiating resin composition according to claim 1, characterized in that, The acrylate monomer is selected from one or more of the following: alkyl (meth)acrylates, hydroxy (meth)acrylates, (meth)acrylates with aromatic rings and / or aliphatic rings, diol diacrylates, alkoxylated acrylates, dioxopentadiene acrylates, and alkoxylated bisphenol A di(meth)acrylates; and / or, The photoinitiator is a free radical type photoinitiator.

4. The method for preparing the photoinitiating resin composition according to claim 3, characterized in that, The acrylate monomers are selected from acrylamide, methacryloylmorpholine, cyclotrimethylolpropane methyl acetal acrylate, hydroxyethyl acrylate, hydroxyethyl methacrylate, dicyclopentene acrylate, tetrahydrofurfuryl acrylate, laurate acrylate, 2-phenoxyethyl methacrylate, 3,3,5-trimethylcyclohexane methacrylate, tricyclodecanediethanol diacrylate, tricyclodecanediethanol dimethacrylate, bisphenol A diacrylate, and bisphenol A dimethyl acrylate. Acrylates, diethylene glycol diacrylate, triethylene glycol diacrylate, 1,4-butanediol diacrylate, 1,6-dihexanediol diacrylate, dipropylene glycol diacrylate, tripropylene glycol diacrylate, trimethylolpropane triacrylate, pentaerythritol triacrylate, ditrimethylolpropane tetraacrylate, dipentaerythritol pentaacrylate, dipentaerythritol hexaacrylate, (2-hydroxyethyl) isocyanurate triacrylate, isobornyl acrylate, and isobornyl methacrylate.

5. The method for preparing the photoinitiating resin composition according to claim 3, wherein the photoinitiator is selected from one or more of benzoyl carbamate, 2,4,6-(trimethylbenzoyl)diphenylphosphine oxide, phenylbis(2,4,6-trimethylbenzoyl), ethyl 2,4,6-trimethylbenzoylphenylphosphonate, diphenylethanol ketone, 2-hydroxy-2-methyl-1-phenyl-1-propanone, 1-hydroxycyclohexylphenyl ketone, α,α'-dimethylbenzoyl ketal, α,α-diethoxyacetophenone, 2-hydroxy-2-methyl-p-hydroxyethyl ether phenylacetone-1, 2-methyl-1-(4-methylthiophenyl)-2-morpholinoacetone-1, and 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)butanone-1.

6. The method for preparing the photoinitiating resin composition according to any one of claims 1 to 3, characterized in that, The first stirring speed is 600 r / min to 800 r / min, and the stirring time is 20 min to 30 min; and / or, The stirring speed of the second stirring is 800 r / min to 1000 r / min, and the stirring time is 20 min to 30 min.

7. The method for preparing the photoinitiating resin composition according to any one of claims 1 to 3, characterized in that, Step S2 further includes adding pigment to the first mixture and then stirring it to obtain the resin composition.

8. The method for preparing the photoinitiating resin composition according to claim 7, characterized in that, The pigment includes one or more of complex blue, pigment red, carbon black, pigment yellow and pigment violet, and the pigment is 0.5 to 1.0 parts by weight.

9. The method for preparing the photoinitiating resin composition according to any one of claims 1 to 3, characterized in that, Step S2 further includes adding 15 to 40 parts of acrylate oligomer to the first mixture.

10. The method for preparing the photoinitiating resin composition according to claim 9, characterized in that, By weight percentage, the resin composition comprises 30% to 70% acrylate monomer, 1% to 5% photoinitiator, 5% to 35% non-reactive organosilicon, and 15% to 40% acrylate oligomer.

11. A photoinitiating resin composition, characterized in that, The resin composition is prepared by the method for preparing the photoinitiating resin composition according to any one of claims 1 to 10; or, by weight, the resin composition comprises 30 to 70 parts of acrylate monomer, 1 to 5 parts of photoinitiator, and 5 to 35 parts of non-reactive organosilicon. The non-reactive organosilicon is a linear polysilane, and the linear polysilane has the structure shown in Formula I: Equation I Where R is methyl or p-methylphenyl, R' is hydrogen, and n is any integer from 200 to 800; and / or, The acrylate monomer is selected from one or more of the following: alkyl (meth)acrylates, hydroxy (meth)acrylates, (meth)acrylates with aromatic rings and / or aliphatic rings, diol diacrylates, alkoxylated acrylates, dioxopentadiene acrylates, and alkoxylated bisphenol A di(meth)acrylates; and / or, The photoinitiator is a free radical type photoinitiator.

12. The photoinitiating resin composition according to claim 11, characterized in that, The acrylate monomers are selected from acrylamide, methacryloylmorpholine, cyclotrimethylolpropane methyl acetal acrylate, hydroxyethyl acrylate, hydroxyethyl methacrylate, dicyclopentene acrylate, tetrahydrofurfuryl acrylate, laurate acrylate, 2-phenoxyethyl methacrylate, 3,3,5-trimethylcyclohexane methacrylate, tricyclodecanediethanol diacrylate, tricyclodecanediethanol dimethacrylate, bisphenol A diacrylate, and bisphenol A dimethyl acrylate. Acrylates, diethylene glycol diacrylate, triethylene glycol diacrylate, 1,4-butanediol diacrylate, 1,6-dihexanediol diacrylate, dipropylene glycol diacrylate, tripropylene glycol diacrylate, trimethylolpropane triacrylate, pentaerythritol triacrylate, ditrimethylolpropane tetraacrylate, dipentaerythritol pentaacrylate, dipentaerythritol hexaacrylate, (2-hydroxyethyl) isocyanurate triacrylate, isobornyl acrylate, and isobornyl methacrylate.

13. The photoinitiating resin composition according to claim 11, characterized in that, The photoinitiator is selected from one or more of benzoyl carbamate, 2,4,6-(trimethylbenzoyl)diphenylphosphine oxide, phenylbis(2,4,6-trimethylbenzoyl), ethyl 2,4,6-trimethylbenzoylphenylphosphonate, benzoethanol ketone, 2-hydroxy-2-methyl-1-phenyl-1-propanone, 1-hydroxycyclohexylphenyl ketone, α,α'-dimethylbenzopyroxyl ketal, α,α-diethoxyacetophenone, 2-hydroxy-2-methyl-p-hydroxyethyl ether phenylacetone-1, 2-methyl-1-(4-methylthiophenyl)-2-morpholinoacetone-1, and 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)butanone-1.

14. The photoinitiating resin composition according to claim 11, characterized in that, The resin composition further includes 15 to 40 parts of acrylate oligomer.

15. The photoinitiating resin composition according to claim 11, characterized in that, By weight percentage, the resin composition comprises 30% to 70% acrylate monomer, 1% to 5% photoinitiator, 5% to 35% non-reactive organosilicon, and 15% to 40% acrylate oligomer.

16. The photoinitiating resin composition according to claim 11, characterized in that, The photoinitiating resin composition has a viscosity of 180 mPa·s to 300 mPa·s at 25°C. After photoinitiating and curing, the photoinitiating resin composition yields a resin with a short beam shear bond strength of 1.2 MPa to 1.9 MPa.

17. The use of the photoinitiating resin composition according to any one of claims 11 to 16 as a dental model resin composition for 3D printing and for preparing dental models.

18. The application according to claim 17, characterized in that, The photoinitiating resin composition is 3D printed to obtain a 3D printed dental model, and then powder is spread on the 3D printed dental model to manufacture dental products.

19. The application according to claim 18, characterized in that, The powder coating includes: Step A: The cured 3D printed dental model is surrounded by wax and filled with undercuts to obtain the first product; Step B: The first product is powdered using the dripping method, and a retainer and / or jaw pad is placed on the first product to obtain the second product; Step C: The second product is treated at 0.1MPa~0.3MPa and 40℃~50℃ for 10min~20min to obtain the third product; Step D: Place the third product at 20℃~30℃ for 5min~15min, then remove the retainer and / or the jaw pad placed on it to obtain the dental product.

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