US-12624178-B2 - Manufacturing method of a modified polymer layer modified by hydroxyapatite

US12624178B2US 12624178 B2US12624178 B2US 12624178B2US-12624178-B2

Abstract

A manufacturing method of a modified polymer layer modified by hydroxyapatite is provided in the present disclosure, including following steps: (a) providing a polymer layer; (b) plasma-activating acrylic acid using an atmospheric cold plasma device to modify a surface of the polymer layer to obtain an acrylic-modified polymer layer; (c) immersing the acrylic-modified polymer layer in a first solution containing a calcium ion to obtain a calcium-containing modified layer; and (d) immersing the calcium-containing modified layer in a second solution containing phosphate salt to obtain a modified polymer layer modified by hydroxyapatite.

Inventors

Wei-Yu Chen
Jui-Sheng Lee
Hui-Ju Hsu

Assignees

TAIWAN TEXTILE RESEARCH INSTITUTE

Dates

Publication Date: 20260512
Application Date: 20230609
Priority Date: 20221027

Claims (10)

1 . A manufacturing method of a modified polymer layer modified by hydroxyapatite, comprising following steps: (a) providing a polymer layer; (b) plasma-activating acrylic acid using an atmospheric cold plasma device comprising a plasma treatment zone to modify a surface of the polymer layer to obtain an acrylic-modified polymer layer, wherein the plasma treatment zone includes a V-shaped hollow tube and a hollow metal electrode accommodated in the V-shaped hollow tube; (c) immersing the acrylic-modified polymer layer in a first solution containing calcium ions to obtain a calcium-containing modified layer; and (d) immersing the calcium-containing modified layer in a second solution containing phosphate salt to obtain a modified polymer layer modified by the hydroxyapatite.
2 . The manufacturing method of the modified polymer layer modified by the hydroxyapatite of claim 1 , wherein the step (b) comprises introducing the acrylic acid and argon gas into the hollow metal electrode accommodated in a first hollow element of the V-shaped hollow tube, thereby generating an acrylic acid plasma from a bottom opening of the V-shaped hollow tube to modify the surface of the polymer layer.
3 . The manufacturing method of the modified polymer layer modified by the hydroxyapatite of claim 2 , wherein the step (b) further comprises modifying the surface of the polymer layer by using a needle-shaped metal electrode accommodated in a second hollow element of the V-shaped hollow tube, wherein the first hollow element intersects with the second hollow element to form the bottom opening.
4 . The manufacturing method of the modified polymer layer modified by the hydroxyapatite of claim 1 , wherein the step (b) comprises plasma-activating the acrylic acid at a temperature of from 25° C. to 70° C.
5 . The manufacturing method of the modified polymer layer modified by the hydroxyapatite of claim 1 , wherein the step (b) comprises plasma-activating the acrylic acid with a current of from 10-5 A to 1 A.
6 . The manufacturing method of the modified polymer layer modified by the hydroxyapatite of claim 1 , wherein the step (b) comprises modifying the surface of the polymer layer for 0.5 s to 20 s.
7 . The manufacturing method of the modified polymer layer modified by the hydroxyapatite of claim 1 , wherein in the step (c), a concentration of the calcium ions in the first solution is from 0.1 M to 0.5 M, and in the step (d), a concentration of the phosphate salt in the second solution is from 0.05 M to 0.3 M.
8 . The manufacturing method of the modified polymer layer modified by the hydroxyapatite of claim 1 , wherein the first solution in the step (c) is calcium nitrate tetrahydrate solution, and the second solution in step (d) is diammonium hydrogen phosphate solution.
9 . The manufacturing method of the modified polymer layer modified by the hydroxyapatite of claim 1 , wherein an immersion time of the step (c) or the step (d) is from 0.25 hr to 1 hr.
10 . The manufacturing method of the modified polymer layer modified by the hydroxyapatite of claim 1 , further comprising repeating the step (c) and the step (d), wherein the modified polymer layer is alternately immersed in the first solution and the second solution for 1 cycle to 5 cycles.

Description

CROSS-REFERENCE TO RELATED APPLICATION This application claims priority to Taiwan Application Serial Number 111140963, filed Oct. 27, 2022, which is herein incorporated by reference. BACKGROUND Field of Invention The present disclosure relates to a manufacturing method of a modified polymer layer. In particular, the present disclosure is related to a manufacturing method of a modified polymer layer modified by hydroxyapatite. Description of Related Art Along with the aggravation of aging trend, the number of the patients with joint injury or bone injury constantly increases. Therefore, the performance requirements for medical implant materials (usually including polymers, such as artificial ligaments prepared from polyethylene terephthalate) have also increased. However, the current artificial ligament materials usually have a hydrophobic surface, which has poor biocompatibility and is unfavorable for cell attachment. Therefore, how to improve the hydrophilicity and biocompatibility of the artificial ligament materials is a problem to be solved. SUMMARY A manufacturing method of a modified polymer layer modified by hydroxyapatite is provided in the present disclosure, including following steps: providing a polymer layer; plasma-activating acrylic acid using an atmospheric cold plasma device to modify a surface of the polymer layer to obtain an acrylic-modified polymer layer; immersing the acrylic-modified polymer layer in a first solution containing calcium ions to obtain a calcium-containing modified layer; and immersing the calcium-containing modified layer in a second solution containing phosphate salt to obtain a modified polymer layer modified by the hydroxyapatite. Functionalization of the polymer layer via the atmospheric cold plasma device decreases manufacturing time, reduces damage to the polymer layer and improves modification efficiency of the hydroxyapatite deposition. According to an embodiment of the present disclosure, the step (b) includes introducing the acrylic acid and argon gas into a hollow metal electrode accommodated in a first hollow element of a V-shaped hollow tube, thereby generating an acrylic acid plasma from a bottom opening of the V-shaped hollow tube to modify the surface of the polymer layer. According to an embodiment of the present disclosure, the step (b) further includes modifying the surface of the polymer layer by using a needle-shaped metal electrode accommodated in a second hollow element of the V-shaped hollow tube, in which the first hollow element intersects with the second hollow element to form the bottom opening. According to an embodiment of the present disclosure, the step (b) includes plasma-activating the acrylic acid at a temperature of from 25° C. to 70° C. According to an embodiment of the present disclosure, the step (b) includes plasma-activating the acrylic acid with a current of from 10−5 A to 1 A. According to an embodiment of the present disclosure, the step (b) includes modifying the surface of the polymer layer for 0.5 s to 20 s. According to an embodiment of the present disclosure, in the step (c), a concentration of the calcium ion in the first solution is from 0.1 M to 0.5 M, and a concentration of the phosphate salt in the second solution is from 0.05 M to 0.3 M. According to an embodiment of the present disclosure, the first solution in the step (c) is calcium nitrate tetrahydrate solution, and the second solution in the step (d) is diammonium hydrogen phosphate solution. According to an embodiment of the present disclosure, an immersion time of the step (c) or the step (d) is from 0.25 hr to 1 hr. According to an embodiment of the present disclosure, the manufacturing method further includes repeating the step (c) and the step (d), in which the modified polymer layer is alternately immersed in the first solution and the second solution for 1 cycle to 5 cycles. BRIEF DESCRIPTION OF THE DRAWINGS Aspects of the present disclosure are best understood from the following detailed description when read with the accompanying figures. It is emphasized that, in accordance with the standard practice in the industry, various features are not drawn to scale. In fact, the dimensions of the various features may be arbitrarily increased or reduced for clarity of discussion. FIG. 1 depicts a flowchart of a method of manufacturing a modified polymer layer modified by hydroxyapatite. FIG. 2 depicts a cross-sectional view of a plasma treatment zone of an atmospheric cold plasma device. FIG. 3A depicts a comparison figure of contact angles between a modified polymer layer and modified polymer layers obtained by different manufacturing conditions. FIG. 3B depicts a comparison figure of contact angles between the modified polymer layer and the modified polymer layers obtained by the different manufacturing conditions when left for different days. FIG. 3C depicts a tendency figure of cell viability of the polymer layer or the modified polymer layers obtained by t