TWI767467B - 3D Printed Compositions and Bone Implants - Google Patents

Abstract

A 3D printing composition includes an adhesive and a powder component. The powder component includes calcium sulfate and tricalcium phosphate, and the average particle size of the powder component is less than 150 μm, and based on the total amount of the powder component being 100 wt %, the content of the calcium sulfate ranges from 81 to 99 wt%, the content of the tricalcium phosphate ranges from 1 to 19 wt%. In addition, the present invention also provides a bone implant, which is prepared by mixing the 3D printing composition and a powder molding agent through a 3D printing process. By controlling the content of calcium sulfate and tricalcium phosphate in the 3D printing composition of the present invention, the bone implant prepared by using the 3D printing composition as a raw material has good compressive strength and is not easy to break .

Description

3D Printed Compositions and Bone Implants

The present invention relates to a 3D printing composition and a 3D printing molding, in particular to a 3D printing composition and a bone implant.

The recovery and regeneration of hard bone tissue defects is slow. In the prior art, in order to increase the speed of hard bone tissue repair and regeneration, a bone implant that can be metabolized by the human body can be placed in the damaged part of the bone, and the bone implant The released metabolites induce the growth of hard bone tissue, thereby achieving the purpose of repair and regeneration. However, the shape and appearance of the bone implants that need to be placed in the current treatment of bone tissue defects are different due to different damage conditions. Therefore, the current method of preparing bone implants is gradually turning to the digital file based on tomography scan. 3D printing process to prepare customized bone implants.

However, the compressive strength of the bone implants produced by the current 3D printing process is low, which makes the bone implants prone to produce small fragments during use, which may then be crushed or broken, resulting in the implantation of the bone. The inconvenience of placing objects into the damaged part of the bone.

Therefore, an object of the present invention is to provide a 3D printing composition.

Therefore, the 3D printing composition of the present invention includes an adhesive and a powder component.

The powder component includes calcium sulfate and tricalcium phosphate, and the average particle size of the powder component is less than 150 μm, and based on the total amount of the powder component being 100 wt %, the content of the calcium sulfate ranges from 81 to 99 wt%, the content of the tricalcium phosphate ranges from 1 to 19 wt%.

In addition, another object of the present invention is to provide a bone implant with good compressive strength.

Therefore, the bone implant of the present invention is prepared by mixing the above-mentioned 3D printing composition with a powder molding agent and through a 3D printing process.

The effect of the present invention is that: the 3D printing composition of the present invention controls the content of calcium sulfate and tricalcium phosphate within a specific range, so that the bone implant prepared by using the 3D printing composition as a raw material has good performance. Compressive strength and not easy to break.

The 3D printing composition of the present invention includes an adhesive and a powder component. The application of the 3D printing composition is not particularly limited, such as but not limited to being used as a raw material for preparing bone implants in the field of biomedicine. The bone implant of the present invention is prepared by mixing the 3D printing composition with a powder molding agent, and then going through a 3D printing process.

The components of the 3D printing composition are described in detail below.

The powder component includes calcium sulfate and tricalcium phosphate, and the average particle size of the powder component is less than 150 μm. When the average particle size of the powder component is less than 150 μm, the 3D printing composition can be smoothly introduced into a 3D printing machine for the 3D printing process, and the 3D printing composition is prepared The size deviation of the bone implant is not large and can be formed smoothly.

The type of the calcium sulfate is not particularly limited, in order to make the powder component easy to recycle and reuse, preferably, the calcium sulfate is selected from the group consisting of calcium sulfate anhydrous, calcium sulfate hemihydrate and calcium sulfate dihydrate. at least one of the groups. Wherein, in order to further adjust the porosity and compressive strength of the bone implant, preferably, the calcium sulfate hemihydrate is selected from the group consisting of α-calcium sulfate hemihydrate and β-calcium sulfate hemihydrate at least one of the group.

The content of the calcium sulfate ranges from 81 to 99 wt % and the content of the tricalcium phosphate ranges from 1 to 19 wt %, based on the total amount of the powder components being 100 wt %. It should be noted that, in some embodiments of the present invention, a single type of calcium sulfate or a mixture of two or more different types of calcium sulfate can be used, and when two or more different types of calcium sulfate are mixed and used, different There is no particular limitation on the dosage ratio among the types of calcium sulfate, as long as the total content of calcium sulfate is controlled within the above range, the bone implant can have good compressive strength.

The type of the adhesive is not particularly limited, and can be any adhesive used in the 3D printing process in the prior art. In order to make the bone implant have good biocompatibility, preferably, the adhesive is selected from the group consisting of pregelatinized starch, maltodextrin, gum arabic, gelatin, shellac, guanhua bean gum, At least one from the group consisting of Sanxian gum and powdered cellulose. Wherein, the powdered cellulose is selected from the group consisting of methyl cellulose, sodium hydroxymethyl cellulose, ethyl cellulose, hydroxyethyl cellulose, hydroxypropyl cellulose and highly substituted hydroxypropyl cellulose at least one of the groups of . In some embodiments of the present invention, based on the total amount of the powder components as 100 parts by weight, the content of the adhesive ranges from 1 to 70 parts by weight. In order to make the bone implant have better ductility and structural strength, preferably, the content of the adhesive is in the range of 1 to 54 parts by weight.

In order to make the 3D printing composition more uniformly dispersed and not easy to agglomerate, preferably, the 3D printing composition further comprises a dispersant. The type of the dispersing agent is not particularly limited, in order to make the bone implant have good biocompatibility, preferably, the dispersing agent is selected from the group consisting of silica and aluminum magnesium silicate at least one. In some embodiments of the present invention, based on the total amount of the powder components as 100 parts by weight, the content of the dispersant ranges from more than 0 to less than 30 parts by weight.

The present invention will be further described with respect to the following examples, but it should be understood that the examples are only used for illustration and should not be construed as a limitation of the implementation of the present invention.

Example 1

[3D printing composition]

Calcium sulfate (the type is calcium sulfate hemihydrate) and tricalcium phosphate are respectively sieved through a sieve with a pore size of 150 μm to obtain calcium sulfate and tricalcium phosphate with an average particle size of less than 150 μm. Next, the sieved calcium sulfate with a total content of 99 wt% and the sieved tricalcium phosphate with a total content of 1 wt% were put into an electric three-dimensional mixer and stirred for 30 minutes. Powder components with a particle size of less than 150 μm. Finally, take 100 parts by weight of the powder component, 6.4 parts by weight of an adhesive (type of gum arabic) and 1 part by weight of a dispersant (type of silicon dioxide) into the electric three-dimensional mixer for stirring for 30 After mixing evenly, take it out to obtain a 3D printing composition.

[Bone Implant]

First, use SOLIDWORKS to draw the sample types with porous structures, and use 3D printing slice software to confirm whether the overall structure is damaged or broken. Next, put the 3D printing composition and the powder molding agent into a 3D printing machine (manufactured by Yanneng Technology Co., Ltd., model M10), and use the machine to spread powder to confirm that the 3D printing composition has no agglomeration or agglomeration. After scraping the powder, the 3D printing machine is used to directly print the sample according to the above-mentioned sample type. After confirming the shape, the bone implant is obtained by sintering at 800°C or more.

Examples 2 to 5 and Comparative Example 1

Examples 2 to 5 and Comparative Example 1 obtained 3D printed compositions and bone implants in a similar manner to Example 1, except that, as shown in Table 1, the 3D printed compositions of Examples 2 to 5 and Comparative Example 1 were changed. Print the proportion of each component in the composition.

[Evaluation of nature]

Compressive Strength Test

The surface of the bone implant in Example 1 was sprayed with a solid formulation, and the sprayed bone implant was dried at room temperature to obtain a bone implant sample to be tested. Next, according to the standard method of ASTM D695, the compressive strength test of the bone implant sample to be tested is carried out at a loading rate of 0.48 mm/min using the MTS 8.10 universal oil pressure tester, and the bone implant sample to be tested is recorded. The pressure to which the implant sample is fractured to obtain the compressive strength of the bone implant. Examples 2 to 5 and Comparative Example 1 measured the compressive strength of the bone implant in the same manner. Table 1 shows the results of Examples 1 to 5 and Comparative Example 1.

Table 1 Example Comparative example 1 2 3 4 5 1 powder component Calcium sulfate type Anhydrous calcium sulfate (wt%) -- 14 10 -- -- -- Calcium sulfate hemihydrate (wt%) 99 80 74 90 81 80 Calcium sulfate dihydrate (wt%) -- -- 8 -- -- -- Total content (wt%) 99 94 92 90 81 80 Tricalcium Phosphate Content (wt%) 1 6 8 10 19 20 3D printing composition Powder component (parts by weight) 100 100 100 100 100 100 Adhesive (parts by weight) 6.4 20.5 38 52 70 6.4 Dispersant (parts by weight) 1 0 2 0.5 0 1 Bone Implant Compressive strength (MPa) 23.52 17.74 15.47 14.83 12.31 3.27 Formed into pieces after pressurization none none none none Have Have

Referring to Table 1, in Examples 1 to 5, by controlling the content of calcium sulfate in the powder component to be in the range of 81 to 99 wt %, and the content of tricalcium phosphate in the range of 1 to 19 wt %, the prepared bone Implants have high compressive strength. In addition, it is worth mentioning that in Examples 1 to 4, the content of the adhesive in the 3D printing composition is further controlled in the range of 1 to 54 parts by weight, so that the bone implant can be tested by the universal oil pressure tester. After being pressurized to fracture, ductile fracture occurs without the generation of fine fragments, indicating that the bone implants of Examples 1 to 4 also have better ductility and structural strength.

In Comparative Example 1, because the content of calcium sulfate was less than 81 wt% and the content of tricalcium phosphate was more than 19 wt%, the bone implant had low compressive strength and was easy to break, and after being pressed to break, there were small particles. Fragments are generated.

To sum up, the 3D printing composition of the present invention controls the content of calcium sulfate and tricalcium phosphate within a specific range, so that the bone implants prepared from the 3D printing composition have good resistance. It has compressive strength and is not easy to break, so it can indeed achieve the purpose of the present invention.

However, the above are only examples of the present invention, and should not limit the scope of implementation of the present invention. Any simple equivalent changes and modifications made according to the scope of the patent application of the present invention and the contents of the patent specification are still included in the scope of the present invention. within the scope of the invention patent.

Claims (9)

A 3D printing composition, comprising: an adhesive; and a powder component, including calcium sulfate and tricalcium phosphate, and the average particle size of the powder component is less than 150 μm, and the total amount of the powder component is 100wt %, the content range of this calcium sulfate is 81 to 99wt%, the content range of this tricalcium phosphate is 1 to 19wt%, wherein, this calcium sulfate is selected from anhydrous calcium sulfate, hemihydrate calcium sulfate and dihydrate. at least one of the group consisting of calcium sulfate. The 3D printing composition of claim 1, wherein the calcium sulfate hemihydrate is at least one selected from the group consisting of α-calcium sulfate hemihydrate and β-calcium sulfate hemihydrate. The 3D printing composition according to claim 1, wherein, based on the total amount of the powder components being 100 parts by weight, the content of the adhesive ranges from 1 to 70 parts by weight. The 3D printing composition according to claim 3, wherein, based on the total amount of the powder components being 100 parts by weight, the content of the adhesive ranges from 1 to 54 parts by weight. The 3D printing composition of claim 1, further comprising a dispersant. The 3D printing composition according to claim 5, wherein, based on the total amount of the powder components being 100 parts by weight, the content of the dispersant ranges from more than 0 to less than 30 parts by weight. The 3D printing composition of claim 5, wherein the dispersant is at least one selected from the group consisting of silicon dioxide and aluminum magnesium silicate. The 3D printing composition according to claim 1, wherein the adhesive is selected from the group consisting of pregelatinized starch, maltodextrin, gum arabic, gelatin, shellac, Guanhua bean gum, Sanxian gum and At least one of the group consisting of powdered cellulose. A bone implant is prepared by mixing the 3D printing composition described in any one of claims 1 to 8 with a powder molding agent and through a 3D printing process.