Photo-curing material, preparation method and application thereof and orthopedic external fixation support

Abstract

The invention belongs to the technical field of medical instruments, and particularly relates to a photocuring material, a preparation method and application thereof and an orthopedic external fixation support. The photocuring material disclosed by the invention is prepared by carrying out photocuring on raw materials comprising the following components: 40 to 50 parts of polyurethane acrylic acid, 20 to 30 parts of epoxy acrylate, 5 to 10 parts of isobornyl methacrylate, 8 to 16 parts of acrylate monomer and 0.5 to 2 parts of photoinitiator. The invention further provides an orthopedic external fixation support made of the photocuring material. The photo-curing material disclosed by the invention is good in mechanical property and flexibility, capable of meeting the application requirements of external fixing braces for orthopedics, free of pungent smell, low in heat productivity during curing and very good in safety. Therefore, the photo-curing material and the orthopedic external fixation brace prepared from the photo-curing material have good application prospects.

Description

Technical Field

[0001] The present invention belongs to the technical field of medical devices, and in particular relates to a photocurable material, a preparation method and application thereof, and an orthopedic external fixation bracket. Background Art

[0002] In the emergency department, patients with fractures are common. For the treatment of fractures, the fracture site needs to be fixed to avoid dislocation. Common fracture external fixation and reduction braces include splints, plaster, gauze bands, etc. Splint fixation is a traditional fixation method. Choose a suitable splint to ensure that the splint can cover the upper and lower joints of the fracture. Multiple splints are evenly distributed around the limb for binding and fixation to provide greater stability. However, splint fixation also has certain shortcomings. For example, the splints are arranged at intervals. In order to provide sufficient stability, the binding force may be slightly greater, which will cause pressure ulcers at the splint position, and the soft tissue in the splint interval area will be squeezed and deformed, restricting blood circulation, leading to local tissue ischemia and necrosis, and will also affect the nerve function of the limbs, leading to decreased sensory and motor function. Plaster fixation is one of the external fixation methods in orthopedics. The plaster bandage made of gypsum powder and absorbent gauze is soaked in warm water and wrapped around the limb. After drying, it becomes a hard solid, achieving the purpose of shaping and fixation. Plaster fixation has great plasticity and can be shaped according to the length, thickness and body shape of the fixed part. However, the production and shaping of plaster is time-consuming, usually requiring 20-30 minutes, and the air permeability of plaster is poor, making it uncomfortable to wear for a long time.

[0003] In order to solve the defects of the above-mentioned existing splints or plaster fixation, the Chinese patent application "CN 116459057A Visible light-cured orthopedic splint and its preparation method, and adjustable tightness splint device" develops a new orthopedic external fixator, whose structure is to fill the outer shell of the splint with photocurable resin, and provide the mechanical properties required by the splint through the photocurable resin. The splint device has the advantages of adjustable tightness, easy manufacture and use. However, in an orthopedic external fixator of this structure, how to select the type of photocurable resin, balance the mechanical strength and flexibility required for orthopedic external fixation, and how to reduce the heat generated during the photocuring process to ensure safety is an important issue. At least one aspect of the above-mentioned properties of existing photocurable materials is difficult to meet the application requirements of orthopedic external fixators. Therefore, the development of photocurable materials suitable for orthopedic external fixators remains an important topic in this field. Summary of the invention

[0004] In view of the problems of the prior art, the present invention provides a photocurable material, a preparation method and use thereof, and an orthopedic external fixation bracket.

[0005] A photocurable material is prepared by photocuring raw materials including the following components:

[0006] Polyurethane acrylic acid 40-50 parts,

[0007] Epoxy acrylate 20-30 parts,

[0008] 5-10 parts of isobornyl methacrylate,

[0009] 8-16 parts of acrylate monomer,

[0010] Photoinitiator 0.5-2 parts.

[0011] Preferably, it is made by light curing raw materials including the following components:

[0012] 45 parts of polyurethane acrylic acid,

[0013] Epoxy acrylate 30 parts,

[0014] Isobornyl methacrylate 10 parts,

[0015] Acrylate monomer 14 parts,

[0016] 1 part of photoinitiator.

[0017] Preferably, the polyurethane acrylic is selected from at least one of the following products of Sartomer Sartomer (Guangzhou) Chemical Co., Ltd.: CN8888 NS, CN8881 NS, CN8010 NS, CN9302 NS, CN965 NS, CN989 NS, CN9010NS;

[0018] The epoxy acrylate is selected from at least one of the following products of Sartomer (Guangzhou) Chemical Co., Ltd.: CN131 NS, CN104 NS, CN110 NS, CN120 NS, or selected from at least one of the following products of Changxing Materials Industry Co., Ltd.: 621-100, 6219-100, 623-100, 6270, 6278;

[0019] The acrylate monomer is selected from at least one of isobornyl methacrylate, hydroxyethyl methacrylate, 2-phenoxyethyl methacrylate, glycidyl methacrylate, 3,3,5-trimethylcyclohexyl methacrylate, tetrahydrofurfuryl methacrylate, lauryl methacrylate, isobornyl acrylate, 2-phenoxyethyl acrylate, 3,3,5-trimethylcyclohexyl methacrylate, tetrahydrofurfuryl acrylate, and lauryl acrylate;

[0020] The photoinitiator is selected from at least one of 2-hydroxy-2-methyl-1-phenylpropanone, 1-hydroxycyclohexyl-phenyl ketone, 2,4,6-trimethylbenzoylbenzene-diphenylphosphine oxide, ethyl 2,4,6-trimethylbenzoylphenylphosphonate, and di(2,4,6-trimethylbenzoyl)phenylphosphine oxide.

[0021] Preferably, the Shore hardness of the photocurable material is greater than or equal to 85±5D;

[0022] And / or, the breaking strength of the photocurable material is greater than or equal to 20 MPa;

[0023] and / or, the temperature of the photocurable material during the photocuring process is less than or equal to 52° C.;

[0024] And / or, the photocurable material is prepared by photocuring under blue light with a wavelength of 420-450 nm.

[0025] The present invention also provides a method for preparing the above-mentioned photocurable material, comprising the following steps: mixing the raw materials and then photocuring them under blue light with a wavelength of 420-450nm to obtain the photocurable material.

[0026] The present invention also provides use of the above-mentioned photocurable material in preparing a medical device for orthopedic external fixation.

[0027] The present invention also provides an orthopedic external fixation brace made of the above-mentioned photocurable material, comprising a photocurable shell, a photocurable cavity is arranged in the photocurable shell, and the photocurable cavity is filled with the above-mentioned photocurable material.

[0028] Preferably, the photocuring shell is made of a transparent silicone rubber material; and / or, the photocuring shell is provided with a plurality of grid-shaped ventilation windows.

[0029] Preferably, a protruding structure is provided on one side of the light-curing shell; and / or a buffer layer is provided on one side of the light-curing shell, and the buffer layer is made of elastic silicone, rubber or foam material.

[0030] Preferably, a fixing structure is provided on the light-curing shell, and the fixing structure is selected from one or more of buttons, zippers, Velcro, and straps.

[0031] The present invention provides a new photocurable material. By optimizing the formulation of the photocurable solution and the photocuring reaction conditions, a photocurable material with excellent mechanical strength and good flexibility is prepared. Its mechanical strength and flexibility can meet the application requirements of orthopedic external fixation brackets. Specifically, the hardness of the photocurable material of the present invention can be guaranteed to be 85±5D Shore hardness, which meets good support; the breaking strength is 20Mpa.

[0032] In addition, the photocurable material of the present invention needs to be photocured after the orthopedic external fixator is installed on the patient's body, so the safety of the photocuring process is of great importance. The photocurable material of the present invention has a lower photocuring reaction temperature, which can ensure that the patient's skin is not burned, and there is no odor during the curing process; in addition, the photocuring process only requires blue light irradiation, without ultraviolet light irradiation, which reduces the impact of irradiation on human skin.

[0033] Therefore, the photocurable material of the present invention and the orthopedic external fixator made thereof have excellent mechanical properties and flexibility, meet the requirements of orthopedic external fixators, have good fixation effect and little pressure on the patient's body, and have the advantages of high safety, and have good application prospects.

[0034] Obviously, according to the above contents of the present invention, in accordance with common technical knowledge and customary means in the art, without departing from the above basic technical ideas of the present invention, other various forms of modification, replacement or change may be made.

[0035] The above contents of the present invention are further described in detail below through specific implementation methods in the form of embodiments. However, this should not be understood as the scope of the above subject matter of the present invention being limited to the following examples. All technologies realized based on the above contents of the present invention belong to the scope of the present invention. BRIEF DESCRIPTION OF THE DRAWINGS

[0036] Figure 1 A schematic top view of a preferred structure of an orthopedic external fixator according to Example 2 of the present invention;

[0037] Figure 2 A schematic top view of a preferred structure of an orthopedic external fixator according to Example 2 of the present invention;

[0038] Figure 3 A schematic diagram of a longitudinal cross-section structure of a preferred structure of an orthopedic external fixator according to Example 2 of the present invention;

[0039] Figure 4 A bottom-up structural schematic diagram of a preferred structure of an orthopedic external fixator according to Example 2 of the present invention;

[0040] Figure 5 This is a physical diagram of a preferred structure of an orthopedic external fixator according to Example 2 of the present invention.

[0041] Among them, 1-light-curing shell, 2-light-curing material, 3-air permeable window, 4-buffer layer, 5-fixing structure. DETAILED DESCRIPTION

[0042] In the following examples and experimental examples, reagents and raw materials not specifically described are all commercially available products.

[0043] Example 1 Photocurable Material

[0044] The photocurable material of this embodiment is made by photocuring raw materials including the following components:

[0045] 45wt.% polyurethane acrylic acid,

[0046] 30wt.%Epoxy acrylate,

[0047] 10wt.% isobornyl methacrylate,

[0048] 14wt.% acrylate monomer,

[0049] 1wt.% photoinitiator.

[0050] The components are selected as follows:

[0051] The polyurethane acrylic can be selected from:

[0052] CN8888 NS, CN8881 NS, CN8010NS, CN9302NS, CN965 NS, CN989 NS, CN9010 NS, etc. from Sartomer Sartomer (Guangzhou) Chemical Co., Ltd.

[0053] The epoxy acrylate may be selected from:

[0054] CN131 NS, CN104 NS, CN110 NS, CN120 NS, etc. from Sartomer Sartomer (Guangzhou) Chemical Co., Ltd.

[0055] 621-100, 6219-100, 623-100, 6270, 6278, etc. of Changxing Materials Industry Co., Ltd.

[0056] The acrylate monomer may be selected from:

[0057] Methacrylate monomers such as isobornyl methacrylate (SR423 NS from Sartomer (Guangzhou) Chemical Co., Ltd.), hydroxyethyl methacrylate (Wanhua Chemical), 2-phenoxyethyl methacrylate (SR340 NS from Sartomer (Guangzhou) Chemical Co., Ltd.), glycidyl methacrylate (Sigma Aldrich), 3,3,5-trimethylcyclohexyl methacrylate (SR421ANS from Sartomer (Guangzhou) Chemical Co., Ltd.), tetrahydrofurfuryl methacrylate (SR 203NS from Sartomer (Guangzhou) Chemical Co., Ltd.), and lauryl methacrylate (SR313 NS from Sartomer (Guangzhou) Chemical Co., Ltd.);

[0058] Acrylate monomers such as isobornyl acrylate (SR506 NS, Sartomer (Guangzhou) Chemical Co., Ltd.), 2-phenoxyethyl acrylate (SR339 NS, Sartomer (Guangzhou) Chemical Co., Ltd.), 3,3,5-trimethylcyclohexyl acrylate (SR420 NS, Sartomer (Guangzhou) Chemical Co., Ltd.), tetrahydrofurfuryl acrylate (SR285 NS, Sartomer (Guangzhou) Chemical Co., Ltd.), and lauryl acrylate (EM215, Changxing Materials Industry Co., Ltd.).

[0059] The photoinitiator may be selected from:

[0060] iGM photoinitiator Omnirad 1173 (2-hydroxy-2-methyl-1-phenylpropanone), Omnirad 184 (1-hydroxycyclohexyl-phenyl ketone), Omnirad TPO (2,4,6-trimethylbenzoylphenyl-diphenylphosphine oxide), Omnirad TPO-L (2,4,6-trimethylbenzoylphenylphosphonic acid ethyl ester), Omnirad 819 (bis (2,4,6-trimethylbenzoyl) phenylphosphine oxide), etc.

[0061] Specifically, as a preferred embodiment, the polyurethane acrylic in this embodiment is selected from Sartomer Sartomer (Guangzhou) Chemical Co., Ltd.: CN8888 NS, the epoxy acrylate is selected from Sartomer Sartomer (Guangzhou) Chemical Co., Ltd.: CN131 NS, the acrylate monomer is selected from isobornyl methacrylate, and the photoinitiator is selected from 2-hydroxy-2-methyl-1-phenylpropanone.

[0062] The synthesis method of the photocurable material is to cure the photocurable solution prepared by mixing the above raw materials under a blue light with a wavelength of 420-450nm, preferably 420nm in this embodiment. The intensity of the blue light can be 550-900mW / cm 2 , in this embodiment, the preferred value is 550mW / cm 2 The light curing time is 5-10 seconds, and 5 seconds is preferred in this embodiment.

[0063] The light-curable material provided in this embodiment has good mechanical properties and flexibility, can meet the support requirements of orthopedic external fixation medical devices, and will not cause excessive pressure on the patient's body.

[0064] Example 2 Orthopedic external fixation brace

[0065] This embodiment provides an orthopedic external fixation brace, the structure of which is as follows Figure 1-4 As shown, the actual picture is as Figure 5 shown.

[0066] The orthopedic external fixation brace comprises a light-curing shell 1, wherein a light-curing cavity is provided in the light-curing shell 1, and the light-curing cavity is filled with a light-curing material 2. The specific selection and preparation method of the light-curing material 2 are performed according to the description of the first embodiment.

[0067] The light-curing shell 1 is made of a transparent material to realize the process of curing the light-curing material 2 by light, and the transparent material is preferably made of a transparent silicone rubber material. The light-curing shell 1 is provided with a plurality of grid-shaped ventilation windows 3. The ventilation windows 3 can improve the air permeability of the brace and avoid some complications caused by airtightness.

[0068] As a preferred embodiment, a buffer layer 4 is provided on one side of the light-curing shell 1, and the buffer layer 4 is made of elastic silicone, rubber or foam material. The buffer layer 4 can further reduce the pressure on the patient's body. In addition, as another preferred form, the buffer layer 4 can also be replaced by some convex structures (such as Figure 4 As shown in the figure, the material of these protruding structures is the same as that of the light-cured shell 1, and they can be manufactured in an integrated manner, thereby simplifying the structure of the orthopedic external fixation brace.

[0069] The light curing chamber is a closed cavity, and its cross-sectional shape can be an O-shaped closed structure or an inverted U-shaped open structure, and the open structure and the buffer layer 4 together form a closed space.

[0070] The light-curing shell 1 is also provided with a fixing structure 5, which is selected from one or more of buttons, zippers, Velcro, and straps (such as Figure 1 or Figure 2 shown).

[0071] The orthopedic external fixation brace of this embodiment is prepared according to the following method:

[0072] Step 1: integrally injecting the light-curing shell 1 (and the fixing structure 5) in a mold to obtain a completely cured silicone light-curing shell 1; or injecting different parts of the light-curing shell 1 (and the fixing structure 5) in a mold separately, and then bonding the parts with silicone glue;

[0073] Step 2, injecting the solution of the photocurable material described in Example 1 into the prepared photocurable shell 1 to obtain an uncured orthopedic external fixation brace;

[0074] Step 3, after installing the orthopedic external fixation brace to the part of the patient's body to be fixed, it is illuminated and cured.

[0075] The orthopedic external fixation brace of this embodiment can be set to a variety of shapes to adapt to different limb parts, such as the palm part, the arm part, the lower limb part, etc., and multiple braces of different shapes can be freely combined and used according to needs, which can save product processing costs. In addition, through actual testing, the orthopedic external fixation brace made in this embodiment can meet the mechanical properties of the fractured limb fixation, and can be opened and deformed by a large amount of manpower, has good flexibility, and can ensure the convenience and safety of application.

[0076] The technical solution of the present invention is further described below through experiments. The photocurable material and the preparation method used in the following experiments are the same as those in Example 1.

[0077] Experimental Example 1 Mechanical properties of photocurable materials

[0078] 1. Experimental Methods

[0079] In this embodiment, the photocurable material is placed in a tube with an outer diameter of 6 mm and an inner diameter of 5 mm (a food-grade silicone tube produced by Suku manufacturer, with a temperature resistance of -50-200 degrees Celsius), and its radial breaking force and Shore hardness are tested.

[0080] The samples of the photocurable material of this embodiment include:

[0081] 1. Experimental group: the light-curable material of Example 1;

[0082] 2. Control group: FlexiOH @ Medical external fixation brace for upper / lower limbs.

[0083] Among them, the test method of radial breaking force is: fix the sample horizontally on the fixture of HZ-1004B tensile testing machine, press the upper tooling downward, test the breaking force, the gauge length is 10mm, and the speed is 200mm / min.

[0084] 2. Experimental Results

[0085] After testing, the Shore hardness of the light-curing material prepared in Example 1 is 85±5D, and the radial fracture force is 117.4 N. The radial fracture force of the competing product is 91.4 N. This mechanical strength meets the support requirements of orthopedic external fixation braces.

[0086] Experimental Example 2: Testing of elongation at break and curing temperature after light-curing material is loaded into a tube

[0087] 1. Experimental Methods

[0088] In this embodiment, the light-curing material is placed in a tube with an outer diameter of 6 mm and an inner diameter of 5 mm (a food-grade silicone tube produced by Suku, with a temperature resistance of -50-200 degrees Celsius), and a shear force tool is used to perform a pressure test. The toughness of the glue is determined by calculating the elongation at break. Then the temperature of the tube surface during curing is tested.

[0089] The samples of the photocurable material of this embodiment include:

[0090] 1. Experimental group: the light-curable material of Example 1;

[0091] 2. Control group: FlexiOH @ Medical external fixation brace for upper / lower limbs.

[0092] 2. Experimental Results

[0093] The elongation at break, odor, and surface temperature of the tube during curing of the light-curing materials in each experimental group after light curing in the tube are as follows:

[0094] Experimental Group Control group odor No odor Slight odor Elongation at break 260％ 150％ Heat generation during curing 52℃ 62℃

[0095] It can be seen that compared with the existing photocurable materials, the photocurable material provided by the present invention has no odor and a higher elongation at break, indicating higher toughness. At the same time, the temperature generated during the curing process is lower and the safety is higher.

[0096] In summary, the present invention provides a photocurable material whose mechanical properties and flexibility meet the application requirements of orthopedic external fixation braces, and the photocurable material has no irritating odor, generates low heat during curing, and has good safety. Therefore, the photocurable material of the present invention and the orthopedic external fixation brace made thereof have good application prospects.

Claims

1. A photocurable material, characterized in that: It is made of raw materials including the following components after light curing: Polyurethane acrylic acid 40-50 parts, Epoxy acrylate 20-30 parts, 5-10 parts of isobornyl methacrylate, 8-16 parts of acrylate monomer, Photoinitiator 0.5-2 parts.

2. The photocurable material according to claim 1, characterized in that: It is made of raw materials including the following components after light curing: 45 parts of polyurethane acrylic acid, Epoxy acrylate 30 parts, Isobornyl methacrylate 10 parts, Acrylate monomer 14 parts, 1 part of photoinitiator.

3. The photocurable material according to claim 1 or 2, characterized in that: The polyurethane acrylic is selected from at least one of the following products of Sartomer Sartomer (Guangzhou) Chemical Co., Ltd.: CN8888 NS, CN8881 NS, CN8010 NS, CN9302 NS, CN965NS, CN989 NS, CN9010 NS; The epoxy acrylate is selected from at least one of the following products of Sartomer (Guangzhou) Chemical Co., Ltd.: CN131 NS, CN104 NS, CN110 NS, CN120 NS, or selected from at least one of the following products of Changxing Materials Industry Co., Ltd.: 621-100, 6219-100, 623-100, 6270, 6278; The acrylate monomer is selected from at least one of isobornyl methacrylate, hydroxyethyl methacrylate, 2-phenoxyethyl methacrylate, glycidyl methacrylate, 3,3,5-trimethylcyclohexyl methacrylate, tetrahydrofurfuryl methacrylate, lauryl methacrylate, isobornyl acrylate, 2-phenoxyethyl acrylate, 3,3,5-trimethylcyclohexyl methacrylate, tetrahydrofurfuryl acrylate, and lauryl acrylate; The photoinitiator is selected from at least one of 2-hydroxy-2-methyl-1-phenylpropanone, 1-hydroxycyclohexyl-phenyl ketone, 2,4,6-trimethylbenzoylbenzene-diphenylphosphine oxide, ethyl 2,4,6-trimethylbenzoylphenylphosphonate, and di(2,4,6-trimethylbenzoyl)phenylphosphine oxide.

4. The photocurable material according to claim 1 or 2, characterized in that: The Shore hardness of the photocurable material is greater than or equal to 85±5D; And / or, the breaking strength of the photocurable material is greater than or equal to 20 MPa; and / or, the temperature of the photocurable material during the photocuring process is less than or equal to 52° C.; And / or, the photocurable material is prepared by photocuring under blue light with a wavelength of 420-450 nm.

5. The method for preparing a photocurable material according to any one of claims 1 to 4, characterized in that: The method comprises the following steps: mixing the raw materials, and then performing light curing under blue light with a wavelength of 420-450nm to obtain the product.

6. Use of the photocurable material according to any one of claims 1 to 4 in the preparation of a medical device for orthopedic external fixation.

7. An orthopedic external fixation brace made of the light-curable material according to any one of claims 1 to 4, characterized in that: The light-curing shell (1) comprises a light-curing cavity provided in the light-curing shell (1), and the light-curing cavity is filled with the light-curing material (2) according to any one of claims 1 to 4.

8. The orthopedic external fixation brace according to claim 7, characterized in that: The photocuring shell (1) is made of a transparent silicone rubber material; and / or the photocuring shell (1) is provided with a plurality of grid-shaped ventilation windows (3).

9. The orthopedic external fixation brace according to claim 7, characterized in that: A protruding structure is provided on one side of the light-curing shell (1); and / or a buffer layer (4) is provided on one side of the light-curing shell (1), and the buffer layer (4) is made of elastic silicone, rubber or foam material.

10. The orthopedic external fixation brace according to claim 7, characterized in that: The light-curing shell (1) is provided with a fixing structure (5), and the fixing structure (5) is selected from one or more of buttons, zippers, Velcro, and straps.

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