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CN110330328B - Low-overcuring calcium phosphate ceramic slurry for photocuring forming and preparation method thereof - Google Patents

Low-overcuring calcium phosphate ceramic slurry for photocuring forming and preparation method thereof Download PDF

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CN110330328B
CN110330328B CN201910265185.1A CN201910265185A CN110330328B CN 110330328 B CN110330328 B CN 110330328B CN 201910265185 A CN201910265185 A CN 201910265185A CN 110330328 B CN110330328 B CN 110330328B
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resin monomer
calcium phosphate
photocuring
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CN110330328A (en
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戴红莲
黄孝龙
马遇乐
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Wuhan University of Technology WUT
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    • B33—ADDITIVE MANUFACTURING TECHNOLOGY
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    • C04B35/626—Preparing or treating the powders individually or as batches ; preparing or treating macroscopic reinforcing agents for ceramic products, e.g. fibres; mechanical aspects section B
    • C04B35/63—Preparing or treating the powders individually or as batches ; preparing or treating macroscopic reinforcing agents for ceramic products, e.g. fibres; mechanical aspects section B using additives specially adapted for forming the products, e.g.. binder binders
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    • C08F222/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a carboxyl radical and containing at least one other carboxyl radical in the molecule; Salts, anhydrides, esters, amides, imides, or nitriles thereof
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    • C08F222/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a carboxyl radical and containing at least one other carboxyl radical in the molecule; Salts, anhydrides, esters, amides, imides, or nitriles thereof
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Abstract

The invention relates to a low-hypercuring calcium phosphate ceramic slurry for light-cured molding and a preparation method thereof, which mainly comprises 70-80wt% of ceramic powder, 0.5-2wt% of dispersant, 10-25wt% of light-cured resin monomer and 0.05-0.5wt% of auxiliary agent according to mass percentage. The preparation method is mainly that the calcium phosphate ceramic powder, the light-cured resin, the dispersant, the photoinitiator and the ultraviolet absorber are ball-milled and stirred to obtain slurry. The slurry has the characteristics of low viscosity, high solid content, low over-curing amount and the like. Can be used in the field of additive manufacturing of biological ceramics.

Description

Low-overcuring calcium phosphate ceramic slurry for photocuring forming and preparation method thereof
Technical Field
The invention belongs to the technical field of medical material additive manufacturing, and particularly relates to low-over-cured calcium phosphate ceramic slurry for photocuring molding and a preparation method thereof.
Background
The 3D printing technology provides a possibility for solving the complex structure and individualization of the bone implant, the ultraviolet light curing technology has attracted wide attention as one of the ceramic 3D printing technologies having the highest resolution of the ceramic light curing technology, and the ultraviolet light curing technology can be classified into SLA (laser stereolithography) and DLP (surface projection stereolithography) according to the difference of the light source delivery technologies. Both techniques are based on slice model data to selectively cure photosensitive materials to build up parts layer by layer. However, there are many restrictions when the technology is used in the field of ceramic 3D printing, and one of them is that the printing resolution is greatly reduced due to the large refractive index difference between the ceramic material and the light-cured resin, and the ultraviolet light scattering caused by the large refractive index difference cannot meet the bone implantation field with the fine internal structure requirement.
Although certain researches are carried out on ceramic stereolithography materials in China, such as CN106747360A, CN106810215A, CN107129283A, CN105566860A and the like, an effective solution is not provided for the scattering problem all the time, and the application of the ceramic 3D printing technology in the field of bone implantation is hindered.
Disclosure of Invention
Aiming at the problems, the invention provides low-over-curing calcium phosphate ceramic slurry for photocuring molding and a preparation method thereof.
The technical scheme adopted by the invention for solving the technical problems is as follows: the low-over-curing calcium phosphate ceramic slurry for photocuring molding comprises, by mass, 70-80wt% of ceramic powder, 0.5-2wt% of a dispersant, 10-25wt% of a photocuring resin monomer and 0.05-0.5wt% of an auxiliary agent.
According to the scheme, the ceramic powder comprises one or the mixture of any two of tricalcium phosphate, hydroxyapatite, tetracalcium phosphate, octacalcium phosphate, calcium hydrophosphate, brushite and bioglass.
According to the scheme, the dispersing agent is one or a mixture of two of phosphate, ammonium polyacrylate and polyacrylate.
According to the scheme, the light-cured resin monomer is a combination of a low-refractive-index resin monomer and a high-refractive-index resin.
According to the scheme, the low-refractive-index resin monomer is any one or a mixture of more of lauryl acrylate, tricyclodecyl dimethanol diacrylate, propoxylated neopentyl glycol diacrylate, alkoxylated pentaerythritol tetraacrylate, ethoxylated trimethylolpropane triacrylate, polyethylene glycol diacrylate, tripropylene glycol diacrylate, methoxy polyethylene glycol (350) monoacrylate, methoxy propoxylated neopentyl glycol monoacrylate and 1, 6-ethylene glycol diacrylate.
According to the scheme, the high-refractive-index resin monomer is one or a mixture of two of alkoxylated bisphenol A di (methyl) acrylate and o-phenylphenoxyethyl acrylate.
According to the scheme, the auxiliary agent comprises the following components in percentage by mass: 96-97.6wt% of photoinitiator and 2.4-4wt% of ultraviolet absorber.
According to the scheme, the photoinitiator is any one or more of 2-hydroxy-2-methyl-phenyl acetone-1, 1-hydroxy-cyclohexyl benzophenone, 2-hydroxy-2-methyl-p-hydroxyethyl ether phenyl acetone-1 and 2,4,6- (trimethylbenzoyl) diphenyl phosphine oxide.
According to the scheme, the ultraviolet light absorber is any one or mixture of more of benzotriazoles, triazines and hindered amines.
The preparation method of the low-hypercuring calcium phosphate ceramic slurry for the photocuring forming is characterized by comprising the following steps:
a) preparing a light-cured resin premix: adding the photocuring resin monomer, the photoinitiator, the dispersant and the ultraviolet absorbent in required proportion into a ball milling tank, and uniformly mixing and stirring to obtain a premixed solution;
b) adding calcium phosphate ceramic powder in required proportion step by step, and ball milling to uniformly disperse the calcium phosphate ceramic powder to obtain slurry.
The refractive index difference between resin and powder is reduced, scattering can be greatly reduced, but the high-refractive index light-cured resin monomer generally has higher viscosity and must be matched with the low-refractive index light-cured resin monomer with low viscosity for use, the ultraviolet absorbent is an auxiliary agent capable of uniformly absorbing ultraviolet light, a certain ultraviolet absorbent is uniformly dispersed in the ceramic slurry, when the ultraviolet light is selectively irradiated on the slurry layer, the ultraviolet light is uniformly distributed in the slurry layer under the scattering and penetrating actions, the whole ultraviolet absorbent has large middle and small periphery, large upper part and small lower part and approximately Gaussian distribution, and the whole ultraviolet absorbent uniformly absorbs a part of the ultraviolet light, so that the ultraviolet light of the part far away from the middle part is reduced to be below the limit energy of light-cured resin curing and can not be cured, thereby the curing range is reduced, the resolution ratio is improved, and the principle of the ultraviolet light-cured resin monomer is shown in figure 1.
Compared with the prior art for preparing the photocuring ceramic slurry, the preparation method has the following advantages:
1) the calcium phosphate ceramic slurry for photocuring forming has low viscosity, so that the slurry can easily obtain a flat extension layer under the action of a scraper, and good surface quality is ensured.
2) The calcium phosphate ceramic slurry for photocuring molding contains a certain ultraviolet absorber and a high-refractive-index photocuring resin monomer, so that the scattering influence of the ceramic is greatly improved, good longitudinal and transverse resolution is ensured, and the requirement of a biological ceramic support on a fine structure is met.
Drawings
FIG. 1 is a schematic diagram of a UV absorber over cure range reduction concept;
FIG. 2 is a schematic view of a single line cured cross-sectional scan of a slurry without the addition of a high refractive index resin monomer and an ultraviolet absorber;
FIG. 3 is a schematic drawing of a single line cured cross-sectional scan of the slurry of example 1;
FIG. 4 is a schematic drawing of a single line cured cross-sectional scan of the slurry of example 2;
FIG. 5 is a schematic drawing of a single line cured cross-sectional scan of the slurry of example 3;
FIG. 6 is a schematic drawing of a single line cured cross-sectional scan of the slurry of example 4;
FIG. 7 is a schematic drawing of a single line cured cross-sectional scan of the slurry of example 5.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention is further described in detail with reference to the following embodiments. It should be understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention. In addition, the technical features involved in the embodiments of the present invention described below may be combined with each other as long as they do not conflict with each other.
Example 1
Preparing a high-energy planetary ball mill, adding a proper amount of zirconia grinding balls, 14g of low light-cured monomer tricyclodecyl dimethanol diacrylate, 6g of high-refractive-index light-cured monomer ethoxylated bisphenol A di (meth) acrylate, 0.2g of photoinitiator 2-hydroxy-2-methyl-phenyl acetone-1, 0.8975g of phosphate ester dispersing agent and 0.005g of benzotriazole ultraviolet absorbent into a cleaned ball milling tank in sequence, and stirring to mix and dissolve the materials. Weighing 50g of beta-tricalcium phosphate and 12g of bioglass powder in a ball milling tank for three times, weighing 15.95g of beta-tricalcium phosphate and 4g of bioglass powder each time, and ball milling for 2 hours at the rotating speeds of 200r/min, 250r/min and 250/min in sequence. And obtaining the required slurry after the ball milling is finished. Single scan line experiments (scan speed 2m/s, power 450mw) showed that the depth and width of the slurry was reduced from 229.9 μm and 478 μm (FIG. 2) to 104 μm and 278.9 μm (FIG. 3), respectively, and the degree of overcuring was greatly reduced.
Example 2
Preparing a high-energy planetary ball mill, adding a proper amount of zirconia grinding balls with proper sizes, 14g of light-cured monomer 1, 6-ethylene glycol diacrylate, 6g of high-refractive-index light-cured monomer ethoxylated bisphenol A di (methyl) acrylate, 0.2g of photoinitiator 2-hydroxy-2-methyl-p-hydroxyethyl ether phenyl acetone-1, 1.2g of phosphate ester dispersing agent and 0.0057g of triazine ultraviolet absorbent into a ball milling tank in sequence, and stirring to mix and dissolve the materials. Weighing 48g of beta-tricalcium phosphate and 12g of bioglass powder in a ball milling tank for three times, weighing 16g of beta-tricalcium phosphate and 4g of bioglass powder each time, and ball milling for 1.5 hours at the rotating speeds of 200r/min, 200r/min and 250/min in sequence. And after the ball milling is finished, obtaining the slurry meeting the requirements. Single scan line experiments (scan speed 2m/s, power 450mw) showed that the depth and width of the cure of the slurry was reduced to 147 μm and 263.5 μm (as in FIG. 4), with a much reduced degree of overcuring.
Example 3
Preparing a high-energy planetary ball mill, sequentially adding a proper amount of zirconia grinding balls, 6g of light-cured monomer methoxy polyethylene glycol (350) monoacrylate, 14g of high-refractive-index light-cured monomer ethoxylated bisphenol A di (methyl) acrylate, 0.2g of photoinitiator 2-hydroxy-2-methyl-phenyl acetone-1, 1.05g of polyacrylate and 0.0066g of hindered amine ultraviolet absorber into a ball milling tank, and stirring to mix and dissolve the materials. Weighing 70g of hydroxyapatite in a ball milling tank for three times, weighing 23.3g of hydroxyapatite each time, and ball milling for 1h at the rotating speeds of 200r/min, 250r/min and 250/min in sequence. And after the ball milling is finished, obtaining the slurry meeting the requirements. Single scan line experiments (scan speed 2m/s, power 450mw) showed that the depth and width of the cure of the slurry was reduced to 202.9 μm and 66.3 μm (as in FIG. 5), with a much reduced degree of overcuring.
Example 4
Preparing a high-energy planetary ball mill, adding a proper amount of zirconia grinding balls with proper sizes, 10g of light-cured monomer tricyclodecyl dimethanol diacrylate, 10g of o-phenylphenoxyethyl acrylate, 0.2g of photoinitiator 2-hydroxy-2-methyl-phenyl acetone-1, 0.8975g of phosphate ester dispersing agent and 0.0057g of benzotriazole ultraviolet absorbent into a cleaned ball milling tank in sequence, and stirring to mix and dissolve the materials. Weighing 75g of tetracalcium phosphate powder in a ball milling tank for three times, weighing 25g each time, and carrying out ball milling for 2 hours at the rotating speeds of 200r/min, 250r/min and 250/min in sequence. And obtaining the required slurry after the ball milling is finished. Single scan line experiments (scan speed 2m/s, power 450mw) showed that the depth and width of the slurry cured was reduced to 114.7 μm and 296 μm (as in FIG. 6), with a much reduced degree of overcuring.
Example 5
Preparing a high-energy planetary ball mill, adding a proper amount of zirconia grinding balls, 6g of light-cured monomer methoxy polyethylene glycol (350) monoacrylate, 14g of o-phenylphenoxyethyl acrylate, 0.2g of photoinitiator 2-hydroxy-2-methyl-phenyl acetone-1, 1.05g of polyacrylate and 0.008g of hindered amine ultraviolet absorber into a ball milling tank in sequence, and stirring to mix and dissolve the materials. 70g of calcium hydrophosphate is weighed in a ball milling tank for three times, 23.3g of calcium hydrophosphate is weighed each time, and the ball milling is carried out for 1 hour at the rotating speeds of 200r/min, 250r/min and 250/min in sequence. And after the ball milling is finished, obtaining the slurry meeting the requirements. Single scan line experiments (scan speed 2m/s, power 450mw) showed that the depth and width of the cure of the slurry was reduced to 103.6 μm and 278.8 μm (as in FIG. 7), with a much reduced degree of overcuring.
It will be understood by those skilled in the art that the foregoing is only a preferred embodiment of the present invention, and is not intended to limit the invention, and that any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the scope of the present invention.

Claims (4)

1. The low-over-curing calcium phosphate ceramic slurry for photocuring molding comprises the following components, by mass, 70-80% of ceramic powder, 0.5-2% of a dispersant, 10-25% of a photocuring resin monomer and 0.05-0.5% of an auxiliary agent, wherein the sum of the contents of the components is 100%; the light-cured resin monomer is a combination of a low-refractive-index resin monomer and a high-refractive-index resin monomer, the low-refractive-index resin monomer is any one or a mixture of more of lauryl acrylate, tricyclodecyl dimethanol diacrylate, propoxylated neopentyl glycol diacrylate, alkoxylated pentaerythritol tetraacrylate, ethoxylated trimethylol triacrylate, polyethylene glycol diacrylate, tripropylene glycol diacrylate, methoxy polyethylene glycol (350) monoacrylate, methoxy propoxy neopentyl glycol monoacrylate and 1, 6-ethylene glycol diacrylate, the high-refractive-index resin monomer is one or a mixture of two of alkoxylated bisphenol A di (meth) acrylate and o-phenylphenoxyethyl acrylate, and the auxiliary agent comprises the following components in mass fraction: 96-97.6wt% of photoinitiator and 2.4-4wt% of ultraviolet light absorber, wherein the photoinitiator is any one or a mixture of more of 2-hydroxy-2-methyl-phenyl acetone-1, 1-hydroxy-cyclohexyl benzophenone, 2-hydroxy-2-methyl-p-hydroxyethyl ether phenyl acetone-1, 2,4,6- (trimethylbenzoyl) diphenyl phosphine oxide, and the ultraviolet light absorber is any one or a mixture of more of benzotriazoles, triazines and hindered amines.
2. The low-overcuring calcium phosphate ceramic slurry for photocuring molding according to claim 1, wherein the ceramic powder comprises one or a mixture of any two of tricalcium phosphate, hydroxyapatite, tetracalcium phosphate, octacalcium phosphate, calcium hydrophosphate, brushite and bioglass.
3. The low-hypercuring calcium phosphate ceramic slurry for photocuring forming according to claim 1, wherein the dispersant is one or a mixture of two of phosphate, ammonium polyacrylate and polyacrylate.
4. The method for preparing a low-overcuring calcium phosphate ceramic slurry for photocuring forming according to claim 1, comprising the steps of:
a) preparing a light-cured resin premix: adding the photocuring resin monomer, the auxiliary agent and the dispersing agent in required proportion into a ball milling tank, and uniformly mixing and stirring to obtain a premixed solution;
b) adding the ceramic powder in required proportion step by step, and carrying out ball milling to uniformly disperse the ceramic powder to obtain slurry.
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