KR20190058327A - Polyarylketone composites with high strength for medical application and implants comprising the same - Google Patents

Abstract

The present invention relates to a medical high strength resin composite, in which a graphene compound containing a hydroxyl group or an organic acid group is contained in a polyarylketone resin. The medical high strength resin composite has excellent rigidity suitable for use in an implant, thereby being able to be usefully used in various forms of products such as a block, a pin, a screw, a cage, a rod and the like, which are widely used in medical fields such as orthopedics, plastic surgery, dentistry, maxillofacial surgery and the like.

Description

TECHNICAL FIELD [0001] The present invention relates to a medical polyarylketone-based high-strength resin composite and an implant including the same,

TECHNICAL FIELD The present invention relates to a medical polyarylketone-based high-strength resin composite and an implant including the same, and more particularly to a polyarylketone resin composite having excellent strength suitable for use in an implant and excellent in molding processability and biocompatibility, A tissue fixing component, a fusion splinting member, and the like.

BACKGROUND ART Conventionally, in medical fields such as orthopedics, plastic surgery, dentistry, and maxillofacial surgery, there have been used implants such as tissue fixing parts and fusion splinting materials for various types of treatment such as blocks, pins, screws, plates, cages and rods . These implants are mainly made of metal because they have excellent rigidity and high shapability. However, metal implants have been suffering from major disadvantages such as low biocompatibility, stress shielding, image distortion, and implant movement.

Recently, a porous metal implant has been developed which accelerates the formation of bone tissue during implantation and reduces the Young's modulus to prevent stress shielding. However, it has a low stiffness and is very vulnerable to external impact.

Ceramic implants have been developed to solve the problems of the metal implant. However, these ceramic implants are superior to metal implants in terms of biocompatibility, but they are easily broken by external impact and have a disadvantage in that they are very poor in molding processability.

Implants made of polyaryl ketone resin, such as polyether ether ketone, which has improved biocompatibility and molding processability, have been spotlighted by improving the disadvantages of metal and ceramic implants and the market is growing rapidly. However, such a polyarylate-based resin has drawbacks in that it lacks strength compared to conventional materials. Therefore, a lot of efforts have been made to improve it. For example, a resin composite reinforced by adding an excess amount of carbon fiber has been developed, but the extrusion or injection molding processability is very poor there was.

As a new improvement method capable of remarkably increasing the strength at the same time as the molding processability is excellent, a resin composite in which a very small amount of graphene is added to a polyarylketone resin has been proposed, but the compatibility of graphene to a polyarylketone resin is very high The resin composite of the desired level of high strength could not be obtained. As a result, a resin composite excellent in molding processability and excellent in biocompatibility capable of dramatically increasing the strength at the same time, and an implant made therefrom are urgently needed.

The present invention is to overcome the limitations of the prior art and to provide a resin composite capable of exhibiting high strength and the medical molded article or the bioactive implant containing the same.

One aspect of the present invention relates to a high strength resin composite for medical use in which a polyaryl ketone resin contains a graphene compound containing a hydroxyl group or an organic acid group.

Another aspect of the present invention relates to a medical molded article obtained by extrusion or injection of a medical high-strength resin composite.

According to various embodiments of the present invention, high strength can be expressed by the hydrogen bonding of the polyarylketone-based ketone group and the hydroxyl or organic acid period contained in the graphene compound.

Hereinafter, various aspects and various embodiments of the present invention will be described in more detail.

One aspect of the present invention relates to a high strength resin composite for medical use in which a polyaryl ketone resin contains a graphene compound containing a hydroxyl group or an organic acid group.

According to one embodiment, the polyaryl ketone resin is selected from the group consisting of polyether ketone, polyetheretherketone, polyetheretheretherketone, polyetheretheretheretherketone, polyetherketoneketone, polyetheretherketoneketone, polyetherketoneether Ketone, and polyether ketone ether ketone ketone.

According to another embodiment, the polyarylketone resin is a polyether ether ketone.

According to another embodiment, the organic acid group is any one or two or more selected from the group consisting of a carboxylic acid group, a sulfonic acid group and a phosphoric acid group.

According to another embodiment, the graphene compound is at least one selected from the group consisting of graphene, graphene oxide and reduced graphene oxide.

According to another embodiment, 0.01 to 5 parts by weight of a graphene compound containing a hydroxyl group or a carboxylic acid group is contained in 100 parts by weight of the polyaryl ketone resin.

According to another embodiment, the high-strength medical resin composite is one or more selected from a calcium-phosphorus compound or a calcium-aluminate compound.

According to another embodiment, 5 to 100 parts by weight of any one or two or more calcium compound particles selected from a calcium-phosphorus compound or a calcium-aluminate compound is further included in 100 parts by weight of the high-strength medical resin composite.

According to another embodiment, the calcium compound is selected from the group consisting of hydroxyapatite, tricalcium phosphate, calcium metaphosphate, calcium phosphate,? -Tricalcium phosphate,? -Tricalcium phosphate, amorphous calcium phosphate, octacalcium phosphate, anhydrous dicalcium phosphate , Dicalcium phosphate dihydrate, anhydrous monocalcium phosphate, monocalcium phosphate monohydrate, and calcium sulfate.

According to another embodiment, the calcium compound is hydroxyapatite, tricalcium phosphate or a mixture thereof.

According to another embodiment, the calcium compound has an average particle diameter of 0.01 to 100 탆.

According to another embodiment, the medical high-strength resin composite further includes carbon fibers or carbon oxide fibers.

According to another embodiment, 1 to 80 parts by weight of carbon fiber or oxidized carbon fiber is further added to 100 parts by weight of the medical high strength resin composite.

According to another embodiment, the carbon fiber or the carbon oxide fiber has a diameter of 1 to 50 mu m and a length of 5 to 300 mu m.

Another aspect of the present invention relates to a medical molded article obtained by extrusion or injection of a medical high-strength resin composite.

Another aspect of the present invention relates to a bio-implantable implant comprising the medical molded article.

Hereinafter, preferred embodiments of the present invention will be described in detail.

A preferred aspect of the present invention relates to a high strength resin composite for medical use comprising a polyaryl ketone resin, a carbon filler, and a ceramic material.

More preferably, the polyaryl ketone resin is a polyether ether ketone.

According to one embodiment, the carbon filler is at least one selected from the group consisting of a graphene compound, a carbon fiber (CF), a carbon nanotube (CNT), and a graphene nanoplate (GnP).

According to another preferred embodiment, the carbon filler is a mixture of a graphene compound and carbon fibers.

More preferably, the graphene compound is graphene oxide in which at least a part of the surface terminal group is modified with an amine group (-NH ₂ ).

Even more preferably, the amine group modification is effected by treatment of a silane-based coupling agent, more preferably (3-aminopropyl) triethoxysilane.

According to another preferred embodiment, the carbon fiber has a hydroxyl group (-OH) and a carboxylic acid group (-COOH) introduced at the surface end.

At this time, introduction of a hydroxyl group and a carboxylic acid is carried out by nitric acid treatment.

According to another preferred embodiment, only the carboxylic acid group (-COOH) may be introduced at the surface of the carbon fiber.

More preferably, the carboxylic acid group introduction is carried out by treatment with sulfuric acid and nitric acid.

According to another preferred embodiment, the calcium compound is hydroxyapatite in which most of the surface hydroxyl groups (-OH) are modified with carboxylic acid groups (-COOH). In the present invention, a calcium compound is used as a bioactive substance that binds directly to bone in vivo. When calcium compounds such as tricalcium phosphate (TCP) other than hydroxyapatite are complexed with a polyether ether ketone resin, It was confirmed that the bioactivity of the polyether ether ketone resin was lowered by interfering with cell proliferation. Particularly, hydroxyapatite has a weak affinity with polyetheretherketone resin and tends to coagulate itself. Therefore, it is possible to improve the affinity with the polyetheretherketone matrix through surface modification and improve the dispersibility of the calcium compound in the composite . However, when it is modified with an amine group, it poses a positive charge (NH4 +) in vivo, which may adversely affect the bioactivity by aggregating negative charge cells. On the other hand, in the case of modifying into a carboxylic acid group having a negative charge, Respectively.

More preferably, the carboxylic acid modification is accomplished by sequential treatment of (i) a silane-based coupling agent and (ii) an acid or acid anhydride.

Even more preferably, the silane-based coupling agent is (3-aminopropyl) triethoxysilane and the acid anhydride is succinic anhydride.

According to a most preferred embodiment, the polyaryl ketone resin is a polyether ether ketone, the carbon filler is at least one selected from a mixture of a graphene compound and a carbon fiber, and the graphene compound has a surface terminal group Wherein at least a part of the carbon fibers are graphene oxide modified with an amine group (-NH ₂ ), (4) the carbon fiber has only a carboxylic acid group (-COOH) or a hydroxyl group and a carboxylic acid group introduced at the surface end, The material is a hydroxyapatite in which at least a part of the surface hydroxyl group (-OH) is modified with a carboxylic acid group (-COOH), and (6) 0.4 to 0.6 part by weight of the modified graphene oxide based on 100 parts by weight of the polyetheretherketone 25 to 35 parts by weight of the modified carbon fiber, and 8 to 10 parts by weight of the modified hydroxyapatite. (7) Amine group modification of the graphene oxide can be carried out by treatment of (3-aminopropyl) triethoxysilane. (8) Carboxylic acid introduction of the carbon fiber is carried out by nitric acid or sulfuric acid treatment for 1 to 2 hours (I) the carboxylic acid modification of the hydroxyapatite can be carried out by sequential treatment of (i) (3-aminopropyl) triethoxysilane and (ii) succinic anhydride.

When both of the above conditions (1) to (6) are satisfied, the interaction between the carbonyl group of the polyetheretherketone and the surface functional group of the additive is increased to maximize the interfacial adhesion, thereby improving the compressive strength, flexural strength and bioactivity And the brittle failure phenomenon of the composite is greatly reduced. On the other hand, when any one of the conditions (1) to (6) is not satisfied, the compressive strength and flexural strength of the composite, It was found that not only these properties but also the brittleness of the composite were increased.

In addition to this, it has been confirmed that when the conditions of ⑦ and ⑨ are satisfied, the compatibility of the composite for commercialization is improved along with the properties mentioned above.

Another preferred aspect of the present invention relates to a medical molded article obtained by extrusion or injection of the medical high-strength resin composite according to the present invention.

Another preferred aspect of the present invention relates to a bioactive implant comprising the preferred medical molded article of the present invention.

Hereinafter, the present invention will be described in more detail with reference to Examples and the like, but the scope and content of the present invention can not be construed to be limited or limited by the following Examples. It will be apparent to those skilled in the art that various modifications and variations can be made in the present invention without departing from the spirit and scope of the present invention as set forth in the following claims. It is natural that it belongs to the claims.

In addition, the experimental results presented below only show representative experimental results of the embodiments and the comparative examples, and the respective effects of various embodiments of the present invention which are not explicitly described below will be specifically described in the corresponding part.

Example

Assessment Methods

Flexural strength, compressive strength, biocompatibility and molding processability of the resin composite samples prepared according to the following examples and comparative examples were evaluated as follows.

1. Flexural strength

Flexural strength (MPa) was determined according to ISO 178 using rectangular parallelepiped bar specimens of 80 mm length, 10 mm width and 4 mm thickness.

2. Compressive strength

The compressive strength (MPa) was determined according to ISO 604 using a rectangular parallelepiped specimen of 10 mm in length, 10 mm in width and 4 mm in thickness.

3. Biocompatibility

Biocompatibility was assessed according to ISO 10993 (conformity or nonconformance).

4. Moldability

The molding processability of the rectangular parallelepiped specimen was evaluated in four steps using a resin composite sample in a 2.3-ton injection machine (Bautec, Mini-molder) (⊚ Excellent, Good △ Good, X defective).

Example 1

First, a powdery polyether ether ketone resin (Victrex Corp. 450PF, PEEK) was prepared as a polyarylketone resin. Further, Grade GE-3550 (G (-OH)) having a carbon content of 50 to 55% by weight and a thickness of 5 nm or less was obtained from PROMICO Corp. as a graft compound containing a hydroxyl group.

100 parts by weight of PEEK and 0.3 parts by weight of G (-OH) were injected to prepare rectangular parallelepiped-shaped specimens. The flexural strength, compressive strength and biocompatibility of the specimens were evaluated, and the results are shown in Table 1.

Example 2

Except that a mixture of 100 parts by weight of PEEK and 0.5 part by weight of G (-OH) was used. The flexural strength, compressive strength and biocompatibility of the obtained specimens were evaluated, Respectively.

Example 3

100 parts by weight of PEEK and 1.0 part by weight of G (-OH) were used in the same manner as in Example 1. The flexural strength, compressive strength and biocompatibility of the obtained specimens were evaluated, Respectively.

Example 4

Grade GO-4401 (G (-COOH)) having a carbon content of 45 to 50% by weight and a thickness of 5 nm or less was prepared from PROMICO SA as a carboxylic acid group-containing graphene compound. Except that a mixture of 100 parts by weight of PEEK and 0.5 part by weight of G (-COOH) was used. The flexural strength, compressive strength and biocompatibility of the obtained specimens were evaluated, Respectively.

Example 5

Hydroxyapatite (HAIHANG Industry Co., HAP04) particles having an average particle diameter of 80 mu m were prepared as calcium compound particles. Except that a mixture of 100 parts by weight of PEEK, 0.5 part by weight of G (-OH) and 20 parts by weight of HAP was used. The flexural strength, compressive strength and biocompatibility of the obtained specimens were evaluated, The results are shown in Table 1.

Example 6

A carbon fiber (Zoltek, Grade PX35, CF) having a diameter of 7.2 μm and a length of 100 to 200 μm was prepared. Except that a mixture of 100 parts by weight of PEEK, 1.0 part by weight of G (-OH) and 10 parts by weight of CF was used, and the flexural strength, compressive strength and biocompatibility of the obtained specimens were evaluated, The results are shown in Table 1.

Example 7

Except that a mixture of 100 parts by weight of PEEK, 1.0 part by weight of G (-OH) and 20 parts by weight of CF was used. The flexural strength, compressive strength and biocompatibility of the obtained specimens were evaluated, The results are shown in Table 1.

Example  8

In the reflux apparatus, 1 kg of CF was subjected to an acid treatment at 80 DEG C for 90 minutes using 10 L HNO3, and the resultant was washed several times with distilled water until it became neutral and dried to obtain carbon oxide fibers (oxi-CF). Except that a mixture of 100 parts by weight of PEEK, 0.5 parts by weight of G (-OH) and 30 parts by weight of oxi-CF was used. Evaluation of bending strength, compressive strength and biocompatibility The results are shown in Table 1.

Example 9

Except that a mixture of 100 parts by weight of PEEK, 0.5 part by weight of G (-OH), 10 parts by weight of HAP, and 30 parts by weight of oxi-CF was used and the flexural strength, compressive strength And biocompatibility were evaluated. The results are shown in Table 1.

Comparative Example 1

The flexural strength, compressive strength and biocompatibility of the obtained specimens were evaluated in the same manner as in Example 1 except that only 100 parts by weight of PEEK was used. The results are shown in Table 1.

 According to the embodiment of the present invention, even when only a very small amount of a graphene compound containing a hydroxyl group or an organic acid group is added to a polyaryl ketone resin, it has excellent strength due to excellent compatibility and excellent biocompatibility and molding processability. Further, it is understood that addition of further calcium compound particles or carbon fibers results in superior strength and excellent biocompatibility.

As described above, the polyaryl ketone resin according to the present invention contains graphene containing a hydroxyl group or an organic acid group. The high strength resin composite for medical use has excellent biocompatibility and molding processability, and has excellent rigidity suitable for an implant, Such as a block, a pin, a screw, a plate, a cage, a rod, and the like, which are widely used in the medical field such as plastic surgery, dentistry, and maxillofacial surgery.

Claims (20)

Polyaryl ketone resin, carbon filler, and ceramic material. The method according to claim 1, wherein the polyaryl ketone resin is selected from the group consisting of polyether ketone, polyetheretherketone, polyetheretheretherketone, polyetheretheretheretherketone, polyetherketoneketone, polyetheretherketoneketone, polyetherketoneether Ketone and polyether ketone ether ketone ketone. ≪ RTI ID = 0.0 > 21. < / RTI > The medical high strength resin composite according to claim 1, wherein the polyaryl ketone resin is a polyether ether ketone. The medical high-strength resin composite according to claim 1, wherein the carbon filler is at least one selected from the group consisting of a graphene compound, a carbon fiber (CF), a carbon nanotube (CNT), and a graphene nanoplate (GnP). The medical high-strength resin composite according to claim 4, wherein the carbon filler is a mixture of a graphene compound and a carbon fiber or a carbon fiber. The medical high-strength resin composite according to claim 5, wherein the graphene compound is graphene oxide in which at least a part of the surface terminal group is modified with an amine group (-NH ₂ ). The method of claim 6, wherein the amine group is a modified medical high-strength resin composite, characterized in that is made by a silane-based platform keopil agent treatment. The medical high-strength resin composite according to claim 5, wherein the silane-based coupling agent is (3-aminopropyl) triethoxysilane. 6. The high strength resin composite for medical use according to claim 5, wherein the carbon fiber has a hydroxyl group (-OH) and a carboxylic acid group (-COOH) at the same or a carboxylic acid group. The medical high-strength resin composite according to claim 9, wherein the hydroxyl group and carboxylic acid group introduction are carried out by treatment with nitric acid and sulfuric acid. The medical high-strength resin composite according to claim 1, wherein the ceramic material is at least one calcium compound selected from a calcium-phosphorus compound or a calcium-aluminate compound. 12. The method of claim 11, wherein the calcium compound is selected from the group consisting of hydroxyapatite, tricalcium phosphate, calcium metaphosphate, calcium phosphate,? -Tricalcium phosphate,? -Tricalcium phosphate, amorphous calcium phosphate, octacalcium phosphate, anhydrous dicalcium phosphate, A mixture of at least one member selected from the group consisting of dicalcium phosphate dihydrate, anhydrous monocalcium phosphate, monocalcium phosphate monohydrate, and calcium sulfate. 12. The medical high-strength resin composite according to claim 11, wherein the calcium compound is hydroxyapatite in which at least a part of hydroxyapatite surface hydroxyl group (-OH) is modified with a carboxylic acid group (-COOH). The medical high strength resin composite according to claim 11, wherein the carboxylic acid modification is performed by sequential treatment of (i) a silane coupling agent and (ii) an acid or an acid anhydride. 15. The method of claim 14, wherein the silane-based coupling agent is (3-aminopropyl) triethoxysilane,
Wherein said acid anhydride is succinic anhydride. The medical high-strength resin composite according to claim 1, wherein 0.01 to 5 parts by weight of a graphene compound containing a hydroxyl group or a carboxylic acid group is contained in 100 parts by weight of the polyaryl ketone resin. The method of claim 1, wherein the polyaryl ketone resin is a polyether ether ketone,
The carbon filler is a carbon fiber or a mixture of a graphene compound and a carbon fiber,
The graphene compound is graphene oxide in which at least a part of the surface terminal group is modified with an amine group (-NH ₂ ), and the carbon fiber has a hydroxyl group (-OH) and a carboxylic acid group (-COOH) Only the phenyl radical is introduced,
The ceramic material is a hydroxyapatite in which at least a part of the surface hydroxyl group (-OH) is modified with a carboxylic acid group (-COOH)
0.4 to 0.6 parts by weight of the modified graphene oxide, 25 to 35 parts by weight of the modified carbon fiber, and 8 to 10 parts by weight of the modified hydroxyapatite, based on 100 parts by weight of the polyetheretherketone. High strength resin composite for medical use. 18. The method of claim 17, wherein the amine group modification of the graphene oxide is accomplished by treatment of (3-aminopropyl) triethoxysilane,
The hydroxyl group and carboxylic acid group introduction of the carbon fiber are carried out by nitric acid treatment for 1 to 2 hours,
The carboxylic acid group introduction of the carbon fibers is carried out by sulfuric acid treatment for 0.5 to 2 hours,
Wherein the hydroxyapatite is modified by a sequential treatment of (i) (3-aminopropyl) triethoxysilane and (ii) succinic anhydride. A medical molded article obtained by extrusion or injection of the medical high-strength resin composite according to any one of claims 1 to 18. A biocompatible implant comprising a medical molded article according to claim 19.