Photocurable resin composition for surgical guide, surgical guide produced therefrom, and method for producing same

Abstract

One aspect of the present invention provides a photocurable resin composition for surgical guides, which comprises 20 to 50 parts by weight of a photocurable (meth)acrylate urethane copolymer, 40 to 70 parts by weight of a first (meth)acrylate monomer, 4 to 9 parts by weight of a second (meth)acrylate monomer, 1 to 4 parts by weight of a photoinitiator, and 0.005 to 1 part by weight of a UV absorber, a surgical guide produced from the composition, and a method for producing the same.

Description

[Technical field]

[0001] The present invention relates to a photocurable resin composition for a surgical guide, a surgical guide produced from the composition, and a method for producing the same. [Background technology]

[0002] Dental implant surgery is a medical procedure that restores the function of lost teeth by implanting artificial teeth into missing teeth. The medical device that fixes the artificial teeth to the jawbone is called a fixture, and the practitioner inserts the fixture through drilling and fixes it to the patient's jawbone. At this time, the planned fixture insertion position and angle may change depending on the practitioner's skill, and such errors will have a negative impact on the durability of the implant fixture and artificial teeth.

[0003] In order to solve these problems, attempts have been made to introduce surgical guides, which are devices that guide the surgeon in determining the insertion position and angle of the fixture according to the surgical plan.

[0004] A surgical guide is a device that has drill holes through which fixtures and drills can pass, and guides implantation surgery using the position and angle of the drill holes. By using such a surgical guide, surgeons can minimize implantation errors and increase the success rate of surgery.

[0005] However, conventional surgical guides are manufactured through milling, which takes a long time to manufacture and is difficult to realize complex shapes.

[0006] Therefore, we attempted to produce a resin composition for surgical guides that can be applied to 3D printing, but in the case of surgical guides for 3D printing produced by the light irradiation method, safety issues may arise.

[0007] In order to solve the above problems, there is a need to develop a resin composition for a surgical guide or a surgical guide that can reduce the manufacturing time of the surgical guide through lamination manufacturing and can realize safety and complex shapes. Summary of the Invention [Problem to be solved by the invention]

[0008] The present invention has been made to solve the above-mentioned problems of the conventional art, and an object of the present invention is to provide a photocurable resin composition for a surgical guide, which has excellent accuracy and photostability. [Means for solving the problem]

[0009] One aspect of the present invention provides a photocurable resin composition for surgical guides, comprising 20 to 50 parts by weight of a (meth)acrylate urethane copolymer, 40 to 70 parts by weight of a first (meth)acrylate monomer, 4 to 9 parts by weight of a second (meth)acrylate monomer, 1 to 4 parts by weight of a photoinitiator, and 0.005 to 1 part by weight of a UV absorber.

[0010] In one embodiment, the first and second (meth)acrylate-based monomers may be multifunctional and monofunctional (meth)acrylate-based monomers, respectively.

[0011] In an embodiment, the photoinitiator may be one selected from the group consisting of acetophenone-based compounds, benzophenone-based compounds, triazine-based compounds, non-imidazole-based compounds, thioxanthone-based compounds, oxime ester-based compounds, acylphosphine oxide-based compounds, and mixtures of two or more thereof.

[0012] In one embodiment, the UV absorber may be one selected from the group consisting of phenyl salicylates, benzophenones, and benzotriazoles.

[0013] In one embodiment, the composition may be a liquid composition for use in 3D printing using one of the following methods: stereolithography, digital light processing, and stereolithography surface curing.

[0014] Another aspect of the present invention provides a surgical guide manufactured by irradiating the above-mentioned photocurable resin composition for a surgical guide with light by 3D printing.

[0015] In one embodiment, the surgical guide may be manufactured by irradiating it with light from a light source of 360 to 405 nm.

[0016] Yet another aspect of the present invention provides a method for manufacturing a surgical guide, comprising: (a) preparing the above-mentioned photocurable resin composition for a surgical guide; (b) stacking the photocurable resin composition by 3D printing; (c) washing the product of step (b) with a cleaning solution; and (d) curing the product of step (c) for 10 to 30 minutes with a light source of 360 to 405 nm.

[0017] In one embodiment, the 3D printing in step (b) may be performed with a light source of 360 to 405 nm.

[0018] In one embodiment, the 3D printing may be performed by one selected from the group consisting of a stereolithography device, a digital light source processing, and a stereolithography surface hardening method.

[0019] In one embodiment, the z-axis precision of the 3D printing may be 50-100 μm. Effect of the Invention

[0020] The photocurable resin composition for a surgical guide according to one embodiment of the present invention has excellent precision and photostability by controlling the contents of a UV absorbent and a photoinitiator.

[0021] The effects of the present invention are not limited to the effects described above, but should be understood to include all effects that can be inferred from the configuration of the invention described in the detailed description of the present invention or the claims. [Brief description of the drawings]

[0022] [Figure 1] FIG. 1 is a graph showing working curves according to the content of light absorbent in compositions of an embodiment and a comparative example of the present invention. [Diagram 2] FIG. 2 is an image of a scaffold cube produced using a 3D printer from the compositions of an embodiment of the present invention and a comparative example. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0023] The present invention will now be described in detail with reference to the accompanying drawings. However, the present invention may be embodied in various different forms and is not limited to the embodiments described herein. In addition, in the drawings, parts that are not related to the description are omitted in order to clearly explain the present invention, and similar parts are designated by similar reference numerals throughout the specification.

[0024] Throughout the specification, when a part is described as being "connected" to another part, this includes not only when it is "directly connected" to another part, but also when it is "indirectly connected" to another part via another member in between. Furthermore, when a part is described as "including" a certain component, this does not mean that it excludes other components, but that it can further include other components, unless otherwise specified.

[0025] When a range of numerical values ​​is given herein, unless a specific range is specifically stated, the values ​​have the precision of the significant figures provided in accordance with standard rules in chemistry for significant figures, for example, the number 10 includes a range of 5.0 to 14.9, and the number 10.0 includes a range of 9.50 to 10.49.

[0026] As used herein, "(meth)acryl-" means "methacryl-", "acryl-", or both.

[0027] Hereinafter, embodiments of the present invention will be described in detail with reference to the accompanying drawings.

[0028] Photocurable resin composition for surgical guide One aspect of the present invention provides a photocurable resin composition for surgical guides, comprising 20 to 50 parts by weight of a (meth)acrylate urethane copolymer, 40 to 70 parts by weight of a first (meth)acrylate monomer, 4 to 9 parts by weight of a second (meth)acrylate monomer, 1 to 4 parts by weight of a photoinitiator, and 0.005 to 1 part by weight of a UV absorber.

[0029] If the composition ratio of the composition is outside the above range, the curing speed may be too slow or the physical properties of the manufactured surgical guide may be defective.

[0030] In addition, when the content of the photoinitiator and UV absorber is within the above range, the photocurable resin composition has excellent z-axis precision when applied to a 3D printer, and can prevent deterioration of photostability due to continuous light source treatment. For example, when the content ratio of the (meth)acrylate-based urethane copolymer to the photoinitiator and UV absorber is outside the above range, photocuring may not occur sufficiently, physical properties may deteriorate, and the precision of the manufactured surgical guide may decrease, resulting in a decrease in the precision of surgery using the surgical guide.

[0031] The first and second (meth)acrylate monomers may be polyfunctional and monofunctional (meth)acrylate monomers, respectively.

[0032] The monofunctional (meth)acrylate monomer may be a (meth)acrylic acid ester monomer, a (meth)acrylate silane monomer, or a nitrogen-containing compound monomer. Specific examples thereof include, but are not limited to, one selected from the group consisting of methyl (meth)acrylate, ethyl (meth)acrylate, butyl (meth)acrylate, hexyl (meth)acrylate, glycidyl (meth)acrylate, lauryl (meth)acrylate, cyclohexyl (meth)acrylate, benzyl (meth)acrylate, allyl (meth)acrylate, 2-ethoxyethyl (meth)acrylate, glycerol (meth)acrylate, isobornyl (meth)acrylate, γ-(meth)acryloyloxypropyltrimethoxysilane, γ-(meth)acryloyloxypropyltriethoxysilane, tetrahydroperfuryl (meth)acrylate, 2-(N,N-dimethylamino)ethyl (meth)acrylate, and N-methylol (meth)acrylamide.

[0033] The polyfunctional (meth)acrylate monomer may be one selected from the group consisting of di- to hexafunctional (meth)acrylate monomers.

[0034] Specific examples of the bifunctional (meth)acrylate monomer include 1,2-ethylene glycol diacrylate, 1,12-dodecanediol acrylate, 1,4-butanediol di(meth)acrylate, 1,6-hexanediol di(meth)acrylate, neopentyl glycol di(meth)acrylate, polyethylene glycol di(meth)acrylate, neopentyl glycol adipate di(meth)acrylate, hydroxypivalic acid neopentyl glycol di(meth)acrylate, dicyclopentanyl pentanyl) di(meth)acrylate, caprolactone-modified dicyclopentenyl di(meth)acrylate, ethylene oxide-modified di(meth)acrylate, allyl-modified cyclohexyl di(meth)acrylate, tricyclodecane dimethanol (meth)acrylate, dimethylol dicyclopentane di(meth)acrylate, ethylene oxide-modified hexahydrophthalic acid di(meth)acrylate, tricyclodecane dimethanol (meth)acrylate, neopentyl glycol-modified trimethylpropane di(meth)acrylate, adamantane di(meth)acrylate, 9,9-bis[4-(2-acryloyloxyethoxy)phenyl]fluorine, or bisphenol A ethoxylate di(meth)acrylate.

[0035] The trifunctional (meth)acrylate monomer may be trimethylolpropane tri(meth)acrylate, dipentaerythritol tri(meth)acrylate, propionic acid modified dipentaerythritol tri(meth)acrylate, pentaerythritol tri(meth)acrylate, or propylene oxide modified trimethylolpropane tri(meth)acrylate.

[0036] The tetrafunctional (meth)acrylate monomer may be diglycerol tetra(meth)acrylate or pentaerythritol tetra(meth)acrylate, the pentafunctional (meth)acrylate monomer may be propionic acid modified dipentaerythritol penta(meth)acrylate, and the hexafunctional (meth)acrylate monomer may be dipentaerythritol hexa(meth)acrylate or caprolactone modified dipentaerythritol hexa(meth)acrylate, but are not limited thereto.

[0037] The (meth)acrylate-based urethane copolymer may be a copolymer in which one or more selected from the group consisting of monofunctional (meth)acrylate-based or polyfunctional (meth)acrylate-based monomers are copolymerized with a urethane-based monomer, for example, a urethane-di(meth)acrylate copolymer, but is not limited thereto.

[0038] The photoinitiator may be one selected from the group consisting of acetophenone-based compounds, benzophenone-based compounds, triazine-based compounds, non-imidazole-based compounds, thioxanthone-based compounds, oxime ester-based compounds, acylphosphine oxide-based compounds, and mixtures of two or more thereof, for example, phenylbis(2,4,6-trimethylbenzoyl)-phosphine oxide, but is not limited thereto.

[0039] The UV absorber may be one selected from the group consisting of phenyl salicylates, benzophenones, and benzotriazoles, for example, benzophenones or benzotriazoles.Specific examples include 2,5-bis(5-tert-butylbenzoxazol-2-yl)thiophene, 2-hydroxy-4-methoxybenzophenone, 2-hydroxy-4-octoxybenzophenone, 2,2'-di-hydroxy-4-methoxybenzophenone, 2-(2'-hydroxy-5'-methylphenyl)benzotriazole, 2-(2'-hydroxy-3',5'-t-butylphenyl)benzotriazole, 2-(2'-hydroxy-5'-t-octylphenyl)benzotriazole, or 2,4-di-t-butylphenyl-3',5'-di-t-butyl-4'-hydroxybenzotriazole.

[0040] The content of the UV absorber may be 0.005 to 1 part by weight, for example, 0.005 parts by weight, 0.05 parts by weight, 0.5 parts by weight, 1.0 parts by weight, or a value between any two of these values.

[0041] When the UV absorbent is a benzophenone-based agent, it can be combined with a photoinitiator to improve the photostability of the surgical guide. Specifically, the UV absorbent can be included to improve photostability, but if the content of the UV absorbent exceeds 1 part by weight, the UV absorbent does not dissolve in the composition and precipitates, exceeding its solubility, and the lamination thickness to be laminated, i.e., Z-axis precision, may be too far outside the range of 50 to 100 μm. Also, if the UV absorbent is less than 0.005 parts by weight, the lamination thickness to be laminated, i.e., Z-axis precision, may be too far outside the range of 100 μm, resulting in insufficient improvement of photostability.

[0042] The term "light stability" as used herein refers to the property of indicating how constant the degree of cure of a laminate remains as a function of the amount of light applied.

[0043] The composition may be a liquid composition used for one 3D printing selected from the group consisting of a stereolithography device, a digital light source processing, and a photolithography surface hardening method. Therefore, the 3D printing may be performed using a printer that uses a liquid resin. A photohardening 3D printer is a printer that hardens a material by irradiating light to a desired area, and has excellent surface roughness compared to other printing methods, which is advantageous for manufacturing structures with complex shapes.

[0044] The stereolithography method can produce a molded product by projecting an ultraviolet laser onto a water tank containing a photocurable resin composition, curing the composition, and laminating the composition. In such SLA 3D printing, the wavelength of the irradiated laser can be changed depending on the type of composition, and the curing speed, strength, surface roughness, etc. of the cured molded product can be changed.

[0045] The digital light source processing method is a mask projection image curing method, which can selectively project light onto a photocurable resin and harden it to produce a molded product of a desired shape. Unlike a general method in which a modeling plate moves down to produce a product, the modeling plate moves up to produce a product in a downward direction. In this case, a molded product can be produced by projecting light provided by a beam projector onto a curable resin composition for 3D printing. That is, the modeling plate can be cured in slice cross-sectional layer units in sequence to produce a 3D molded product.

[0046] The stereolithography surface hardening method uses an LCD, a liquid crystal display device developed with high resolution, as an imaging source, and is a method that is inexpensive and capable of large-area, high-resolution output. The stereolithography surface hardening method has the advantage of being capable of large-area output compared to laser and projection type printers, and is highly productive as it can produce large quantities at once. When the output time is divided by the number of unit outputs, the output time per output can be shortened.

[0047] Surgical Guide Another aspect of the present invention provides a surgical guide manufactured by irradiating the above-mentioned photocurable resin composition for a surgical guide with light by 3D printing.

[0048] The surgical guide may be manufactured by irradiating light with a light source of 360 to 405 nm, for example, 380 to 400 nm. If the light source for irradiating light is out of the above range, appropriate curing may not be performed during the lamination manufacturing, and it may be difficult to maintain an appropriate shape throughout the entire process of lamination manufacturing, cleaning, and post-curing.

[0049] In addition, the surgical guide may have a complete surgical guide shape through the processes of cleaning and post-curing after the lamination manufacturing, and the light source during the post-curing may be the same as the light source used in the lamination manufacturing.

[0050] Manufacturing method of surgical guide Yet another aspect of the present invention provides a method for producing a surgical guide, comprising: (a) preparing the above-mentioned photocurable resin composition for a surgical guide; (b) stacking the photocurable resin composition by 3D printing; (c) washing the product of step (b) with a cleaning solution; and (d) curing the product of step (c) for 10 to 30 minutes with a light source of 360 to 405 nm.

[0051] In the step (a), the photocurable resin composition for a surgical guide is prepared. The composition and effects of the photocurable resin composition for a surgical guide are the same as those described above.

[0052] In the step (b), the photocurable resin composition may be laminated by 3D printing, and in the step (c), the product of the step (b) may be washed with a cleaning solution. The 3D printing during lamination may be performed with a light source of 360 to 405 nm, for example, 380 to 400 nm. If the light source for irradiating light is outside the range, proper curing may not be performed during the lamination manufacturing, and it may be difficult to maintain a proper shape during the subsequent cleaning process.

[0053] In step (d), the product of step (c) may be cured for 10 to 30 minutes with a light source of 360 to 405 nm, for example, for 15 to 25 minutes with a light source of 380 to 400 nm. Step (d) may be cured using a post-curing machine, and a precise surgical guide may be manufactured through detailed post-processing including step (d).

[0054] The 3D printing may be performed by one selected from the group consisting of a stereolithography device, a digital light source processing, and a photolithography surface hardening method, and the characteristics of the methods are as described above.

[0055] The z-axis precision of the 3D printing is 50-100 μm, which is a thickness commonly used in dental 3D printing. If the z-axis precision of the 3D printing is less than 50 μm, the total amount and frequency of light energy applied to the composition may increase, resulting in a slow output speed.

[0056] Hereinafter, examples of the present invention will be described in detail.

[0057] Example 1 A photocurable resin composition was prepared by mixing 35 parts by weight of urethane dimethacrylate copolymer, 55 parts by weight of bisphenol A ethoxylate dimethacrylate, 6 parts by weight of tetrahydrofurfuryl methacrylate, 2 parts by weight of phenylbis(2,4,6-trimethylbenzoyl)-phosphine oxide, and 0.005 parts by weight of 2,5-bis(5-tert-butyl-2-benzoxazolyl)thiophene.

[0058] Example 2 A photocurable resin composition was prepared by mixing 35 parts by weight of urethane-dimethacrylate copolymer, 55 parts by weight of bisphenol A ethoxylate dimethacrylate, 6 parts by weight of tetrahydrofurfuryl methacrylate, 2 parts by weight of phenylbis(2,4,6-trimethylbenzoyl)-phosphine oxide, and 0.05 parts by weight of 2,5-bis(5-tert-butylbenzoxazol-2-yl)thiophene.

[0059] Example 3 A photocurable resin composition was prepared by mixing 35 parts by weight of urethane-dimethacrylate copolymer, 55 parts by weight of bisphenol A ethoxylate dimethacrylate, 6 parts by weight of tetrahydrofurfuryl methacrylate, 2 parts by weight of phenylbis(2,4,6-trimethylbenzoyl)-phosphine oxide, and 0.5 parts by weight of 2,5-bis(5-tert-butylbenzoxazol-2-yl)thiophene.

[0060] Example 4 A photocurable resin composition was prepared by mixing 35 parts by weight of urethane-dimethacrylate copolymer, 55 parts by weight of bisphenol A ethoxylate dimethacrylate, 6 parts by weight of tetrahydrofurfuryl methacrylate, 2 parts by weight of phenylbis(2,4,6-trimethylbenzoyl)-phosphine oxide, and 1.0 part by weight of 2,5-bis(5-tert-butylbenzoxazol-2-yl)thiophene.

[0061] Comparative Example 1 A photocurable resin composition was prepared by mixing 35 parts by weight of urethane-dimethacrylate copolymer, 55 parts by weight of bisphenol A ethoxylate dimethacrylate, 6 parts by weight of tetrahydrofurfuryl methacrylate, and 2 parts by weight of phenylbis(2,4,6-trimethylbenzoyl)-phosphine oxide.

[0062] Experimental example 1: Light stability and Z-axis accuracy confirmation The compositions of the examples and comparative examples were tested to plot a working curve using a 3D printer disclosed in Korean Patent No. 1,772,999, and the results are shown in FIG.

[0063] In FIG. 1, it can be seen that each embodiment realizes the targeted Z-axis accuracy of the lamination thickness of 50 to 100 μm.

[0064] In the cases of Examples 2 to 4, the amount of light input to realize the target laminate thickness was large, but the slope was low and the range of light input to reach the target thickness was wide, so the photostability was excellent. In the cases of Example 1, which contains a low amount of light absorbent, and Comparative Example 1, which does not contain a light absorbent, the range of laminate thickness was wide, but the photostability was lower than the other candidates.

[0065] In the case of Examples 3 and 4, an excessively long time was required for lamination to a thickness of 100 μm, which resulted in a side reaction causing over-hardening, resulting in undesirable shapes such as sludge being output.

[0066] Experimental example 2: Confirmation of Z-axis precision The compositions of the examples and comparative examples were used to prepare scaffold cubes having a size of 10 mm on one axis and a thickness of 1 mm on one axis using a 3D printer disclosed in Korean Patent No. 1,772,999, as shown in FIG. 2. After cleaning with isopropyl alcohol, specimens were prepared five times by curing for 20 minutes using a curing machine equipped with a 380-400 nm light source, and the average thicknesses of the first and second axes are shown in FIG. 2 and Table 1 below.

[0067] [Table 1]

[0068] 2 and Table 1, it can be seen that the thickness of the axis changes depending on whether or not a UV absorbent is included, and that there is a difference in z-axis precision. In the case of 1-axis measurements, the error of the z-axis thickness from the design dimension was 0.040 mm or less in the comparative example and all examples. However, in the case of 2-axis measurements, while the errors were all 0.040 mm or less in Examples 1 to 4 that contained a UV absorbent, Comparative Example 1 that did not contain any UV absorbent had an error of 0.100 mm or more, and the z-axis precision was insufficient. Therefore, it can be seen that the photostability can be improved by including a UV absorbent.

[0069] The above description of the present invention is for illustrative purposes only, and those skilled in the art will understand that the present invention can be easily modified in other specific forms without changing the technical idea or essential features of the present invention. Therefore, it should be understood that the above-described embodiments are illustrative in all respects and are not limiting. For example, each component described as a single type may be implemented in a distributed manner, and similarly, each component described as a distributed manner may be implemented in a combined form.

[0070] The scope of the present invention is defined by the claims set forth below, and all modifications and variations that fall within the meaning and scope of the claims and their equivalent concepts should be construed as being included within the scope of the present invention.

Claims

1. 20 to 35 parts by weight of a (meth)acrylate-based urethane copolymer; 40 to 70 parts by weight of a first (meth)acrylate monomer; 4 to 9 parts by weight of a second (meth)acrylate monomer; 1 to 4 parts by weight of a photoinitiator; 0.005 to 1 part by weight of a UV absorber; The photocurable resin composition for a surgical guide, wherein the first and second (meth)acrylate monomers are polyfunctional and monofunctional (meth)acrylate monomers, respectively.

2. 2. The photocurable resin composition for surgical guides according to claim 1, wherein the photoinitiator is one selected from the group consisting of acetophenone-based compounds, benzophenone-based compounds, triazine-based compounds, non-imidazole-based compounds, thioxanthone-based compounds, oxime ester-based compounds, acylphosphine oxide-based compounds, and mixtures of two or more thereof.

3. 2. The photocurable resin composition for a surgical guide according to claim 1, wherein the UV absorber is one selected from the group consisting of phenyl salicylates, benzophenones, and benzotriazoles.

4. The photocurable resin composition for surgical guides according to claim 1, wherein the composition is a liquid composition used for 3D printing using one method selected from the group consisting of a stereolithography device, a digital light source processing method, and a photolithography surface curing method.

5. A method for producing a surgical guide, comprising irradiating the photocurable resin composition for a surgical guide according to any one of claims 1 to 4 with light by 3D printing.

6. A method for manufacturing the surgical guide described in claim 5, comprising irradiating light with a light source of 360 to 405 nm.

7. (a) preparing a photocurable resin composition for a surgical guide according to any one of claims 1 to 4; (b) depositing the photocurable resin composition by 3D printing; (c) washing the product of step (b) with a washing solution; (d) curing the product of step (c) with a light source of 360-405 nm for 10-30 minutes.

8. The method of claim 7, wherein in step (b), the 3D printing is performed using a light source of 360 to 405 nm.

9. The method for manufacturing a surgical guide according to claim 7, wherein the 3D printing is performed by one selected from the group consisting of a stereolithography device, a digital light source processing, and a photolithography surface hardening method.

10. The method for manufacturing a surgical guide according to claim 7, wherein the z-axis accuracy of the 3D printing is 50 to 100 μm.

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