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CN-119060249-B - Photoinitiated resin composition, preparation method and application thereof

CN119060249BCN 119060249 BCN119060249 BCN 119060249BCN-119060249-B

Abstract

The invention provides a photoinitiated resin composition, a preparation method and application thereof. The preparation method of the photoinitiated resin composition comprises the steps of S1, mixing an acrylic ester monomer and a photoinitiator, obtaining a first mixture after first stirring, S2, adding non-reactive organic silicon into the first mixture, and obtaining the resin composition after second stirring, wherein the acrylic ester monomer is 30-70 parts, the photoinitiator is 1-5 parts, and the non-reactive organic silicon is 5-35 parts by weight. The invention realizes the preparation of the resin composition which has no sediment, low viscosity and is easy to be peeled from various interfaces after solidification through the well-designed composition formula and the preparation process.

Inventors

  • ZHANG CHUNHUI
  • LIU YILANG
  • Wang xiaosha

Assignees

  • 广州黑格智造信息科技有限公司

Dates

Publication Date
20260512
Application Date
20240929

Claims (19)

  1. 1. A process for preparing a photoinitiating resin composition, characterized in that, the preparation method of the photoinitiated resin composition comprises the following steps: Step S1, mixing an acrylic ester monomer and a photoinitiator, and obtaining a first mixture after first stirring; Step S2, adding non-reactive organic silicon into the first mixture, and obtaining the resin composition after second stirring; According to the weight parts, the acrylic ester monomer is 30-70 parts, the photoinitiator is 1-5 parts, and the non-reactive organosilicon is 5-35 parts; the non-reactive silicone is a linear polysilane, and the linear polysilane has a structure shown in formula I: I is a kind of Wherein R is methyl or p-methylphenyl, R' is hydrogen, and n is any integer from 200 to 800.
  2. 2. The method of preparing a photoinitiated resin composition according to claim 1, wherein the non-reactive silicone is: wherein n is 600, and/or, Wherein n is 600.
  3. 3. The method for producing a photoinitiated resin composition according to claim 1, The acrylate monomer is selected from one or more of alkyl (methyl) acrylate, hydroxyl (methyl) acrylate, (methyl) acrylate with aromatic ring and/or aliphatic ring, diol diacrylate, oxyalkylated acrylate, acrylic acid dioxanyl ester and oxyalkylated bisphenol A di (methyl) acrylate, and/or, The photoinitiator is a free radical photoinitiator.
  4. 4. The method for preparing a photoinitiated resin composition according to claim 3, wherein the acrylate monomer is selected from the group consisting of acryloylmorpholine, methacryloylmorpholine, cyclotrimethylolpropane methylacrylate, hydroxyethyl acrylate, hydroxyethyl methacrylate, dicyclopentene acrylate, tetrahydrofurfuryl acrylate, lauric acid acrylate, 2-phenoxyethyl methacrylate, 3, 5-trimethylcyclohexane methacrylate, tricyclodecanedimethanol diacrylate, tricyclodecanedimethanol dimethacrylate, ethoxylated bisphenol a diacrylate, ethoxylated bisphenol a dimethacrylate, diethylene glycol diacrylate, triethylene glycol diacrylate, 1, 4-butanediol diacrylate, 1, 6-dihexylene glycol diacrylate, dipropylene glycol diacrylate, tripropylene glycol diacrylate, trimethylolpropane triacrylate, pentaerythritol triacrylate, trimethylolpropane tetraacrylate, dipentaerythritol pentaacrylate, dipentaerythritol hexaacrylate, (2-hydroxyethyl) isocyanuric acid triacrylate, isobornyl acrylate, and isobornyl methacrylate.
  5. 5. The method for preparing a photoinitiated resin composition according to claim 3, wherein the photoinitiator is selected from one or more of benzoyl formate, 2,4,6 (trimethylbenzoyl) diphenyl phosphine oxide, phenylbis (2, 4, 6-trimethylbenzoyl), ethyl 2,4, 6-trimethylbenzoylphenylphosphonate, benzophenone, 2-hydroxy-2-methyl-1-phenyl-1-propanone, 1-hydroxycyclohexylphenyl methanone, α' -dimethylbenzoyl ketal, α -diethoxyacetophenone, 2-hydroxy-2-methyl-p-hydroxyethyl ether phenyl propanone-1, 2-methyl-1- (4-methylthiophenyl) -2-morpholinophenone-1, and 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) butanone-1.
  6. 6. A process for producing a photoinitiated resin composition according to any of claims 1 to 3, The stirring speed of the first stirring is 600 r/min-800 r/min, the time is 20 min-30 min, and/or, The stirring speed of the second stirring is 800-1000 r/min, and the time is 20-30 min.
  7. 7. A method of preparing a photoinitiated resin composition according to any of claims 1 to 3, further comprising adding a pigment to the first mixture in step S2, and obtaining the resin composition after the second stirring.
  8. 8. The method for producing a photoinitiated resin composition according to claim 7, wherein the pigment includes one or more of complex blue, pigment red, carbon black, pigment yellow and pigment violet, and the pigment is 0.5 parts to 1.0 parts by weight.
  9. 9. The method for producing a photoinitiated resin composition according to any one of claims 1 to 3, further comprising adding 15 parts to 40 parts of an acrylate oligomer to the first mixture in step S2.
  10. 10. The method for preparing a photoinitiated resin composition according to claim 9, wherein the acrylate monomer is 30-70 wt%, the photoinitiator is 1-5 wt%, the non-reactive silicone is 5-35 wt% and the acrylate oligomer is 15-40 wt%.
  11. 11. A photoinitiated resin composition prepared by the method for preparing the photoinitiated resin composition according to any one of claims 1 to 10, or the resin composition comprises, by weight, 30 to 70 parts of an acrylate monomer, 1 to 5 parts of a photoinitiator, and 5 to 35 parts of a non-reactive silicone; the non-reactive silicone is a linear polysilane, and the linear polysilane has a structure shown in formula I: I is a kind of Wherein R is methyl or p-methylphenyl, R' is hydrogen, n is any integer from 200 to 800, and/or, The acrylate monomer is selected from one or more of alkyl (methyl) acrylate, hydroxyl (methyl) acrylate, (methyl) acrylate with aromatic ring and/or aliphatic ring, diol diacrylate, oxyalkylated acrylate, acrylic acid dioxanyl ester and oxyalkylated bisphenol A di (methyl) acrylate, and/or, The photoinitiator is a free radical photoinitiator.
  12. 12. The photoinitiated resin composition according to claim 11, wherein the acrylate monomer is selected from the group consisting of acryloylmorpholine, methacryloylmorpholine, cyclotrimethylolpropane methylacrylate, hydroxyethyl acrylate, hydroxyethyl methacrylate, dicyclopentene acrylate, tetrahydrofurfuryl acrylate, lauric acid acrylate, 2-phenoxyethyl methacrylate, 3, 5-trimethylcyclohexane methacrylate, tricyclodecanedimethanol diacrylate, tricyclodecanedimethanol dimethacrylate, ethoxylated bisphenol a diacrylate, ethoxylated bisphenol a dimethacrylate, diethylene glycol diacrylate, triethylene glycol diacrylate, 1, 4-butanediol diacrylate, 1, 6-dihexylene glycol diacrylate, dipropylene glycol diacrylate, tripropylene glycol diacrylate, trimethylolpropane triacrylate, pentaerythritol triacrylate, trimethylol propane tetraacrylate, dipentaerythritol pentaacrylate, dipentaerythritol hexaacrylate, (2-hydroxyethyl) isocyanurate triacrylate, isobornyl acrylate, and isobornyl methacrylate.
  13. 13. The photoinitiated resin composition according to claim 11, wherein the photoinitiator is selected from one or more of the group consisting of benzoyl formate, 2,4,6 (trimethylbenzoyl) diphenyl phosphine oxide, phenyl bis (2, 4, 6-trimethylbenzoyl), ethyl 2,4, 6-trimethylbenzoylphenylphosphonate, benzophenone, 2-hydroxy-2-methyl-1-phenyl-1-propanone, 1-hydroxycyclohexylphenyl methanone, α' -dimethylbenzoyl ketal, α -diethoxyacetophenone, 2-hydroxy-2-methyl-p-hydroxyethyl etherylacetone-1, 2-methyl-1- (4-methylthiophenyl) -2-morpholinophenone-1, and 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) butanone-1.
  14. 14. The photoinitiated resin composition according to claim 11, wherein the resin composition further comprises 15 to 40 parts of an acrylate oligomer.
  15. 15. The photoinitiated resin composition according to claim 11, wherein the acrylate monomer is 30-70 wt%, the photoinitiator is 1-5 wt%, the non-reactive silicone is 5-35 wt% and the acrylate oligomer is 15-40 wt%.
  16. 16. The photoinitiated resin composition according to claim 11, wherein the viscosity of the photoinitiated resin composition at 25 ℃ is 180 mPa-s to 300 mPa-s, the photoinitiated resin composition is cured by photoinitiation to obtain a resin, and the short beam shear adhesion strength of the resin is 1.2mPa to 1.9mPa.
  17. 17. Use of a photoinitiated resin composition according to any of claims 11 to 16 as a dental model resin composition for 3D printing and for the preparation of a dental model.
  18. 18. The use according to claim 17, wherein the photoinitiated resin composition is 3D printed to obtain a 3D printed dental model, after which the 3D printed dental model is powdered to produce a dental product.
  19. 19. The use according to claim 18, wherein, The powder paving comprises the following steps: step A, wax enclosing and undercut filling are carried out on the 3D printing dental model after solidification, and a first product is obtained; Step B, paving powder on the first product by a sprinkling method, and arranging a retainer and/or a jaw pad on the first product to obtain a second product; Step C, treating the second product at 0.1-0.3 MPa and 40-50 ℃ for 10-20 min to obtain a third product; And D, placing the third product at 20-30 ℃ for 5-15 min, and then removing the retainer and/or the jaw pad arranged on the third product to obtain the dental product.

Description

Photoinitiated resin composition, preparation method and application thereof Technical Field The invention relates to the field of resin for 3D printing, in particular to a photoinitiated resin composition, a preparation method and application thereof. Background For orthodontic applications, conventional processing plants employ gypsum over-molding to produce them. Taking the appliance as an example, a worker needs to uniformly spread a layer of separating agent on the plaster model, so that the appliance solidified on the separating agent can be separated from the plaster model. Currently, it is common to produce dental products, such as dental models, using 3D printing techniques. When using existing processes for separating appliances, it is still necessary to apply a separating agent to the dental model to facilitate the separation of the appliance from the dental model. At present, there is a 3D printing model resin which can be directly separated without a separating agent, but in the resin composition, a color-developing filler such as titanium pigment is inevitably added for the purpose of convenient use, so that a resin model obtained by final curing presents a white color of a gypsum, and the filler can be precipitated in the storage process of the 3D printing model resin, thereby not only affecting the printing quality, but also needing to increase a process of shaking in advance, and being not suitable for large-scale use. Based on this, it is one of the important technical problems to be solved in the art how to provide a novel resin composition which combines the property of being separable without using a separating agent after curing with the property of having low viscosity and no precipitation. Disclosure of Invention The invention mainly aims to provide a photoinitiated resin composition, a preparation method and application thereof, and aims to solve the problems that the viscosity of the resin composition for 3D printing dental model in the prior art is too high, separation is difficult after solidification, and filler precipitation possibly occurs in the preparation and application processes. In order to achieve the aim, the first aspect of the invention provides a preparation method of a photoinitiated resin composition, which comprises the steps of S1, mixing an acrylic ester monomer and a photoinitiator, obtaining a first mixture after first stirring, S2, adding non-reactive organic silicon into the first mixture, and obtaining the resin composition after second stirring, wherein the acrylic ester monomer is 30-70 parts, the photoinitiator is 1-5 parts, and the non-reactive organic silicon is 5-35 parts by weight. In certain embodiments, the non-reactive silicone is a linear polysilane, and the linear polysilane has a structure of formula I: Wherein R and R 'are each independently one or more of hydrogen, C1-C6 alkyl, C1-C6 alkoxy, phenyl, phenoxy, C1-C6 alkyl substituted phenyl and C1-C6 alkyl substituted phenoxy, 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. In certain embodiments, the non-reactive silicone is: wherein n is 600, and/or, Wherein n is 600. In certain embodiments, the acrylate monomer is selected from one or more of alkyl (meth) acrylates, hydroxy (meth) acrylates, aromatic and/or alicyclic (meth) acrylates, glycol diacrylates, alkoxylated acrylates, dioxolanes acrylates, and alkoxylated bisphenol a di (meth) acrylates, preferably the acrylate monomer is selected from the group consisting of acryloylmorpholine, methacryloylmorpholine, cyclotrimethylolpropane methylacrylate, hydroxyethyl acrylate, hydroxyethyl methacrylate, dicyclopentene acrylate, tetrahydrofurfuryl acrylate, lauric acid acrylate, 2-phenoxyethyl methacrylate, 3, 5-trimethylcyclohexane methacrylate, tricyclodecanedimethanol diacrylate, tricyclodecanedimethanol 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-dihexylene glycol diacrylate, dipropylene glycol diacrylate, tripropylene glycol dimethacrylate, trimethylolpropane, pentaerythritol dimethacrylate, pentaerythritol dimethacrylate, and pentaerythritol dimethacrylate; and/or the number of the groups of groups, the photoinitiator is a free radical photoinitiator, preferably the photoinitiator is selected from one or more of benzoyl formate, 2,4,6 (trimethyl benzoyl) diphenyl phosphine oxide, phenyl bis (2, 4, 6-trimethyl benzoyl), ethyl 2,4, 6-trimethyl benzoyl phenylphosphonate, diphenyl ethanone, 2-hydroxy-2-methyl-1-phenyl-1-acetone, 1-hydroxy cyclohexyl phenyl methanone, alpha' -dimethyl benzil ketal, alpha-diethoxy acetophenone, 2-hydroxy-2-methyl-p-hydroxyethyl etherylphenyl acetone-1, 2-methyl-1- (4-methylthiophe