WO2021187804A1

WO2021187804A1 - Photo-curable composition for tooth restoration

Info

Publication number: WO2021187804A1
Application number: PCT/KR2021/003020
Authority: WO
Inventors: 심운섭
Original assignee: 주식회사 그래피
Priority date: 2020-03-19
Filing date: 2021-03-11
Publication date: 2021-09-23
Also published as: KR102374377B1; KR20210117427A

Abstract

The present invention relates to a photo-curable composition for tooth restoration, wherein the composition can be provided as a patient-specific tooth restoration material through 3D printing, can be prepared to have various colors by using pigments, and can be used as a tooth restoration material having excellent aesthetic characteristics due to having the same colors as teeth. Furthermore, the present invention relates to a photo-curable composition for tooth restoration, which is excellent in moisture absorption resistance, strength, and elongation and thus can be permanently used and cause no cracks or breakage due to the occlusion pressure between teeth.

Description

Photocurable tooth restoration composition

The present invention relates to a photocurable dental restoration composition, and more particularly, to a photocurable dental restoration composition that can be used as a patient-customized dental restoration material through 3D printing.

In order to treat damaged and defective teeth, in general, amalgam, gold, dental restoration resin, etc. are filled in the defective portion to reinforce the defective portion so that it does not progress further. Each of the materials used to restore these tooth defects has advantages and disadvantages, and an appropriate material is used according to the purpose.

The amalgam is manufactured and used by mixing silver, tin, copper and mercury, has a strength similar to that of a tooth, withstands occlusal pressure well, and is mainly used because of its simple treatment and low price. , long-term use or cracks around the filled part may additionally generate and progress tooth damage and defects, which may result in re-treatment or the need to remove the tooth. In case of contact, electricity may cause discomfort due to galvanic phenomenon.

As a noble metal, gold is often used despite its high price due to its excellent properties. Since gold is a metal with a fairly low ionization tendency, it has excellent corrosion resistance to saliva and other foods, so it does not deteriorate or corrode. It is expensive and requires a long period of treatment because it has to be modeled and made of gold alloy, and the treatment process is more complicated than that of amalgam.

Lastly, resin has recently been in the spotlight due to the esthetic factor that it is most similar to the color of the tooth, and it can be treated by using a special adhesive to minimize damage to the tooth, has good adhesion, and has strong resistance to discoloration and corrosion. However, care must be taken as it is absolutely vulnerable to moisture during the treatment process, its strength is relatively low, so it can easily be abraded, and its high coefficient of thermal expansion can cause tooth damage due to the occurrence of gaps at the interface with the teeth. It is also quite complicated.

In addition, the development of a resin that expresses the color most similar to the color of teeth, which is subtly different for each individual, is one of the most important factors.

Amalgam, which has been widely used so far, has been widely used due to its excellent physical properties and low price despite the color difference and low bonding properties. In the same case, resin is the trend due to a significant price increase.

In general, a material used for a dental restoration resin consists of a resin-based oligomeric matrix and inorganic fillers such as bisphenol A-glycidylmethacrylate (BISMA) or urethane dimethacrylate (UDMA) and silica. In addition, improved dental restoration resins such as silver nano-added products or Bis-GMA have been developed.

It is possible to maintain uniformity and reproducibility by manufacturing pigments that are more subdivided and match different tooth colors for each individual and can distinguish tooth colors in stages.

However, in the case of the currently used resin composition for dental restoration, when manufactured using a polymer, it is deteriorated due to the property of absorbing water, so that it cannot be used as a permanent dental restoration material.

Also, unlike amalgam, cracks or cracks occur due to occlusal pressure between teeth.

Therefore, it is necessary to develop a material for restoration of teeth that can be customized to the patient, has excellent hygroscopicity, has excellent strength and elongation, can be used permanently, and does not crack or break due to occlusal pressure between teeth. do.

[Prior art literature]

[Patent Literature]

(Patent Document 1) KR 10-2017-0055320 A1

It is an object of the present invention to provide a photocurable composition for dental restoration.

Another object of the present invention is to provide a patient-customized dental restoration material through 3D printing, and it is possible to manufacture in various colors using pigments. It is to provide a composition for restoration of a photocurable tooth that can be used.

Another object of the present invention is to provide a photocurable composition for restoration that has excellent hygroscopicity, excellent strength and elongation, so that it can be used permanently, and cracks or cracks do not occur due to occlusal pressure between teeth.

In order to achieve the above object, a photocurable tooth restoration composition according to an embodiment of the present invention includes a photocurable polyurethane compound represented by the following Chemical Formula 1; photoinitiators; silane coupling agents; oligomers; and stabilizers:

[Formula 1]

[Formula 2]

[Formula 3]

[Formula 4]

here,

* means the part to be joined,

R _{1 To} R ₆ are the same as or different from each other, and each independently hydrogen, deuterium, cyano group, nitro group, halogen group, hydroxy group, substituted or unsubstituted C 1 to C 30 alkyl group, substituted or unsubstituted C 1 to C 20 A cycloalkyl group, a substituted or unsubstituted alkenyl group having 2 to 30 carbon atoms, a substituted or unsubstituted alkynyl group having 2 to 24 carbon atoms, a substituted or unsubstituted aralkyl group having 7 to 30 carbon atoms, or a substituted or unsubstituted aryl group having 6 to 30 carbon atoms , a substituted or unsubstituted heteroaryl group having 5 to 60 carbon atoms, a substituted or unsubstituted heteroarylalkyl group having 6 to 30 carbon atoms, a substituted or unsubstituted alkoxy group having 1 to 30 carbon atoms, a substituted or unsubstituted alkylamino group having 1 to 30 carbon atoms , substituted or unsubstituted arylamino group having 6 to 30 carbon atoms, substituted or unsubstituted aralkylamino group having 6 to 30 carbon atoms, substituted or unsubstituted heteroarylamino group having 2 to 24 carbon atoms, substituted or unsubstituted alkylsilyl having 1 to 30 carbon atoms It is selected from the group consisting of a group, a substituted or unsubstituted arylsilyl group having 6 to 30 carbon atoms and a substituted or unsubstituted aryloxy group having 6 to 30 carbon atoms,

L ₁ and L ₃ are the same as or different from each other, and each independently a substituted or unsubstituted C 1 to C 20 alkylene group, a substituted or unsubstituted C 6 to C 30 arylene group, a substituted or unsubstituted C 5 to C 30 of a heteroarylene group and a substituted or unsubstituted cycloalkylene group having 3 to 30 carbon atoms,

L ₂ is selected from the group consisting of compounds represented by Formulas 2 to 4,

n and m are the same as or different from each other, and are each independently an integer from 1 to 10,

R ₇ to R ₁₂ are the same as or different from each other, and each independently represents hydrogen, deuterium, a halogen group, a hydroxy group, a substituted or unsubstituted C 1 to C 30 alkyl group, a substituted or unsubstituted C 1 to C 20 cycloalkyl group, a substituted or unsubstituted A ring having 2 to 30 carbon atoms, a substituted or unsubstituted alkynyl group having 2 to 24 carbon atoms, a substituted or unsubstituted aralkyl group having 7 to 30 carbon atoms, a substituted or unsubstituted aryl group having 6 to 30 carbon atoms, and a substituted or unsubstituted carbon number It is selected from the group consisting of 5 to 60 heteroaryl groups,

The substituted alkylene group, substituted arylene group, substituted heteroarylene group, substituted cycloalkylene group, substituted alkyl group, substituted cycloalkyl group, substituted alkenyl group, substituted alkynyl group, substituted aralkyl group, substituted aryl Group, substituted heteroaryl group, substituted heteroarylalkyl group, substituted alkoxy group, substituted alkylamino group, substituted arylamino group, substituted aralkylamino group, substituted heteroarylamino group, substituted alkylsilyl group, substituted aryl A silyl group and a substituted aryloxy group include hydrogen, deuterium, a cyano group, a nitro group, a halogen group, a hydroxyl group, an alkyl group having 1 to 30 carbon atoms, a cycloalkyl group having 1 to 20 carbon atoms, an alkenyl group having 2 to 30 carbon atoms, 2 to 24 carbon atoms. of an alkynyl group, an aralkyl group having 7 to 30 carbon atoms, an aryl group having 6 to 30 carbon atoms, a heteroaryl group having 5 to 60 nuclear atoms, a heteroarylalkyl group having 6 to 30 carbon atoms, an alkoxy group having 1 to 30 carbon atoms, 1 carbon atoms A to 30 alkylamino group, an arylamino group having 6 to 30 carbon atoms, an aralkylamino group having 6 to 30 carbon atoms, a heteroarylamino group having 2 to 24 carbon atoms, an alkylsilyl group having 1 to 30 carbon atoms, an arylsilyl group having 6 to 30 carbon atoms, and It is substituted with one or more substituents selected from the group consisting of an aryloxy group having 6 to 30 carbon atoms, and when substituted with a plurality of substituents, they are the same or different from each other.

Wherein R ₁ and R ₆ may be a compound represented by the following formula (5):

[Formula 5]

here,

* means the part to be joined,

R ₁₃ is hydrogen, deuterium, a halogen group, a hydroxy group, a substituted or unsubstituted alkyl group having 1 to 30 carbon atoms, a substituted or unsubstituted cycloalkyl group having 1 to 20 carbon atoms, a substituted or unsubstituted alkenyl group having 2 to 30 carbon atoms, a substituted or unsubstituted It is selected from the group consisting of an alkynyl group having 2 to 24 carbon atoms in the ring, a substituted or unsubstituted aralkyl group having 7 to 30 carbon atoms, a substituted or unsubstituted aryl group having 6 to 30 carbon atoms and a substituted or unsubstituted heteroaryl group having 5 to 60 carbon atoms, ,

The substituted alkyl group, substituted cycloalkyl group, substituted alkenyl group, substituted alkynyl group, substituted aralkyl group, substituted aryl group and substituted heteroaryl group include hydrogen, deuterium, cyano group, nitro group, halogen group, hydroxy group, An alkyl group having 1 to 30 carbon atoms, a cycloalkyl group having 1 to 20 carbon atoms, an alkenyl group having 2 to 30 carbon atoms, an alkynyl group having 2 to 24 carbon atoms, an aralkyl group having 7 to 30 carbon atoms, an aryl group having 6 to 30 carbon atoms, the number of nuclear atoms A heteroaryl group having 5 to 60 carbon atoms, a heteroarylalkyl group having 6 to 30 carbon atoms, an alkoxy group having 1 to 30 carbon atoms, an alkylamino group having 1 to 30 carbon atoms, an arylamino group having 6 to 30 carbon atoms, an aralkylamino group having 6 to 30 carbon atoms, It is substituted with one or more substituents selected from the group consisting of a heteroarylamino group having 2 to 24 carbon atoms, an alkylsilyl group having 1 to 30 carbon atoms, an arylsilyl group having 6 to 30 carbon atoms and an aryloxy group having 6 to 30 carbon atoms, and a plurality of substituents When substituted with, they are the same as or different from each other.

The L ₁ and L ₃ are the same as or different from each other and each independently may be selected from the group consisting of compounds represented by the following Chemical Formulas 6 to 10:

[Formula 6]

[Formula 7]

[Formula 8]

[Formula 9]

[Formula 10]

here,

* means the part to be joined,

p and r are the same as or different from each other, and are each independently an integer of 0 to 4,

q is an integer from 1 to 10,

L ₄ and L ₅ are the same or different from each other, and each independently a substituted or unsubstituted C 1 to C 20 alkylene group, a substituted or unsubstituted C 6 to C 30 arylene group, a substituted or unsubstituted C 5 to a heteroarylene group of 30 and a substituted or unsubstituted cycloalkylene group having 3 to 30 carbon atoms,

R ₁₄ to R ₁₇ are the same as or different from each other, and each independently represents hydrogen, deuterium, a halogen group, a hydroxy group, a substituted or unsubstituted C 1 to C 30 alkyl group, a substituted or unsubstituted C 1 to C 20 cycloalkyl group, a substituted or unsubstituted A ring having 2 to 30 carbon atoms, a substituted or unsubstituted alkynyl group having 2 to 24 carbon atoms, a substituted or unsubstituted aralkyl group having 7 to 30 carbon atoms, a substituted or unsubstituted aryl group having 6 to 30 carbon atoms, and a substituted or unsubstituted carbon number It is selected from the group consisting of 5 to 60 heteroaryl groups,

The photoinitiator may be a compound represented by the following formula (11):

[Formula 11]

here,

X ₁ is S, O or N(R ₂₀ ),

R ₁₉ to R ₂₀ are the same as or different from each other, and each independently represents hydrogen, deuterium, a cyano group, a nitro group, a halogen group, a hydroxy group, a substituted or unsubstituted alkyl group having 1 to 30 carbon atoms, and a substituted or unsubstituted C 3 to 30 carbon group a cycloalkyl group,

The substituted alkyl group and the substituted cycloalkyl group are hydrogen, deuterium, cyano group, nitro group, halogen group, hydroxy group, alkyl group having 1 to 30 carbon atoms, cycloalkyl group having 1 to 20 carbon atoms, alkenyl group having 2 to 30 carbon atoms, and 2 carbon atoms. to 24 alkynyl group, C7 to C30 aralkyl group, C6 to C30 aryl group, nuclear atom 5 to 60 heteroaryl group, C6 to C30 heteroarylalkyl group, C1 to C30 alkoxy group, C1-C30 alkylamino group, C6-C30 arylamino group, C6-C30 aralkylamino group, C2-C24 hetero arylamino group, C1-C30 alkylsilyl group, C6-C30 arylsilyl It is substituted with one or more substituents selected from the group consisting of a group and an aryloxy group having 6 to 30 carbon atoms, and when substituted with a plurality of substituents, they are the same or different from each other.

The oligomer may be selected from the group consisting of epoxy acrylate oligomer, H12 dianthane-bis-glycidyl ether (4,4'-(1-Methylethylidene)biscyclohexanol, polymer with (chloromethyl)oxirane), and mixtures thereof.

The stabilizer may be selected from the group consisting of 2,6-di-tert-butyl-p-cresol, diethylethanolamine, trihexylamine, hindered amine, organic phosphate, hindered phenol and mixtures thereof.

The patient-customized dental restoration material according to another embodiment of the present invention may include the photocurable dental restoration composition.

The photocurable dental restoration composition of the present invention can be provided as a patient-customized dental restoration material through 3D printing, and can be manufactured in various colors using pigments. It can be used as a dental restoration material.

In addition, it is possible to provide a photocurable composition for dental restoration that has excellent hygroscopic resistance, excellent strength and elongation, so that it can be used permanently, and cracks or cracks do not occur due to occlusal pressure between teeth.

The present invention is a photocurable polyurethane compound represented by the following formula (1); photoinitiators; silane coupling agents; oligomers; And it relates to a photocurable dental restoration composition comprising a stabilizer:

[Formula 1]

[Formula 2]

[Formula 3]

[Formula 4]

here,

* means the part to be joined,

Hereinafter, embodiments of the present invention will be described in detail so that those of ordinary skill in the art can easily carry out the present invention. However, the present invention may be embodied in many different forms and is not limited to the embodiments described herein.

BACKGROUND ART A dental restoration (dental filling) is a treatment for restoring the function and state of a tooth structure that has been lost due to cavities or an external shock.

An esthetic restoration of a tooth is a restoration that satisfies both function and esthetics by restoring teeth using esthetic materials that harmonize with the color of natural teeth.

As interest in the esthetics of dental prostheses increases, many types of esthetic prosthetic make materials are being introduced to the clinic. The scope of application is expanding, and non-metallic prosthetic restoration materials include ceramic reinforced polymer & fiber reinforced composite, all ceramics, and metal free post & core.

As for the all-ceramic, more specifically, glass infiltration systems and press able ceramic systems are mainly used, and zirconia ceramics with high flexural strength. (ceramics) was developed.

Glass-impregnated ceramics systems include In-Ceram Alumina, Spinelle and Celay systems, followed by In-Ceram Splint (Vita, Vita, Vita, Inc. Germany) was recently released and used, and the Wol-Ceram system technique using CNC-Workcenter has the advantage of omitting the replica model manufacturing process because it is directly manufactured on individual die during In-Ceram manufacturing. .

Looking at ceramic restoration materials, unlike metal, it is a very esthetic material because it can be treated similarly to the color of teeth. Ceramics, laminating, inlay, and onlay It can be used as a substitute for composite resin restoration or composite resin inlays and onlays in areas where aesthetics is emphasized.

However, in the case of ceramic restorations, the vicinity of the tooth and adhesion may be lifted, or cracking may occur due to the occlusal pressure between the teeth. Due to the above problems, after dental restoration treatment, contamination of the tooth area, bacterial infection of materials, insecure sterilization of instruments, etc. has occurred frequently.

The structure of the tooth is composed of enamel, dentin, pulp, and tooth root. It acts as a shock absorber when stimulated.

On the other hand, dental caries, the main culprit of dental disease, is a disease that occurs when host factors, pathogenic factors, and environmental factors act in a complex way at the same time. It acts as a pathogenic factor in the occurrence of dental caries).

No matter what food is eaten, tooth decay does not occur in the teeth of animals without mutans bacteria in the oral cavity, and thus, tooth decay can be considered a bacterial disease.

In the teeth of children raised by mothers who have a lot of S. mu tans in their mouths, relatively many cavities occur.

In addition, the probability of tooth decay varies depending on the degree of stickiness of food, the shape, position, and arrangement of teeth. Although there are various theories about the cause of tooth decay and pain, the theory that the acid produced by the decomposition of food by microorganisms in the oral cavity destroys the tooth tissue and causes tooth decay is universally accepted. Eating habits act as one of several important factors affecting the occurrence of tooth decay (dental caries).

In particular, sugar contained in food is a component that causes tooth decay. Sugar contained in food is easily fermented inside the bacterial membrane to produce acid, as well as a very sticky glycoprotein, so that the bacterial membrane is on the back side. It helps to adhere firmly and limits the acid from being washed out by saliva.

In addition to sugar, carbohydrates such as starch, fructose, and glucose contained in cooked food are also easily fermented to produce acid, which is a major cause of tooth decay.

As such, the frequency and timing of intake of foods containing fermentable carbohydrates have a great influence on the occurrence of tooth decay.

In addition to ceramic materials, conventional dental restoration materials may have a problem that cracks or cracks may easily occur due to occlusal pressure between teeth.

In the present invention, as a photocurable composition for dental restoration, unlike conventional dental restoration materials, it can be manufactured in various colors using pigments, and due to the same color as the tooth color, it can be used as a dental restoration material with excellent esthetics. In addition, it has excellent moisture absorption resistance, excellent strength and elongation, so that it can be used permanently, and cracks or cracks do not occur due to occlusal pressure between teeth.

More specifically, the photocurable dental restoration material of the present invention can be customized to the patient by using a 3D printer, so that it can be used as an optimal customized dental restoration material for the patient.

In addition, it is possible to prevent cracks and cracks caused by occlusal pressure between teeth through chemical bonding with commonly used dental adhesives.

That is, not only can the bonding strength be increased through chemical bonding with the dental adhesive, but also, as the following photocurable polyurethane compound is included, a buffering effect is exhibited, and cracks and cracks caused by occlusal pressure between teeth are prevented.

In addition, by including the photocurable polyurethane compound, it can exhibit excellent physical properties as well as excellent moisture absorption resistance.

When a conventional high molecular compound is used as a resin material, due to the property of absorbing moisture in the oral cavity, it is deteriorated and a problem of easily cracking or breaking occurs due to an external impact.

That is, although the dental restoration material should be able to be used permanently, there is a problem in that it cannot be used permanently due to the property that the polymer compound easily absorbs water.

The photocurable polyurethane compound of the present invention enables permanent use due to excellent moisture absorption resistance and excellent physical properties, unlike such a high molecular compound.

The photocurable tooth restoration composition of the present invention includes a photocurable polyurethane compound represented by the following Chemical Formula 1; photoinitiators; silane coupling agents; oligomers; and stabilizers:

[Formula 1]

[Formula 2]

[Formula 3]

[Formula 4]

here,

* means the part to be joined,

[Formula 5]

here,

* means the part to be joined,

[Formula 6]

[Formula 7]

[Formula 8]

[Formula 9]

[Formula 10]

here,

* means the part to be joined,

q is an integer from 1 to 10,

The photoinitiator may be a compound represented by the following formula (11):

[Formula 11]

here,

X ₁ is S, O or N(R ₂₀ ),

More preferably, it is a compound represented by the following formula (12):

[Formula 12]

The oligomer may be selected from the group consisting of epoxy acrylate oligomer, H ₁₂ dianthane-bis-glycidyl ether (4,4'-(1-Methylethylidene)biscyclohexanol, polymer with (chloromethyl)oxirane), and mixtures thereof. .

More specifically, the epoxy acrylate oligomer is more specifically a phenyl epoxy (meth) acrylate oligomer, a bisphenol A epoxy di (meth) acrylate oligomer, an aliphatic alkyl epoxy di (meth) acrylate oligomer, and an aliphatic alkyl epoxy tri (meth) One or more compounds selected from the group consisting of acrylate oligomers may be used. The oligomer may not only reduce swelling caused by the organic solvent, but also improve surface hardness, abrasion resistance, heat resistance, and the like.

The silane coupling agent is more specifically 3-methacryloxypropyltrimethoxysilane, but is not limited thereto.

The stabilizer is selected from the group consisting of 2,6-di-tert-butyl-p-cresol, diethylethanolamine, trihexylamine, hindered amine, organic phosphate, hindered phenol and mixtures thereof, more specifically as 2,6-di-tert-butyl-p-cresol.

In order to improve thermal and oxidative stability, storage stability, surface properties, flow properties and process properties, for example, conventional additives such as leveling agents, slip agents or stabilizers may be included.

In addition, it may further include a pigment for making the color the same as or similar to the tooth color.

The color can be manufactured in various ways according to the patient's choice in addition to the tooth color.

The photocurable composition for a 3D printer for manufacturing the dental restoration material includes a photocurable polyurethane compound, and based on 100 parts by weight of the photocurable polyurethane compound, 1.5 to 15 parts by weight of a photoinitiator; 0.1 to 1.5 parts by weight of a silane coupling agent; 15 to 45 parts by weight of an oligomer; and 0.1 to 2 parts by weight of a stabilizer. When the silane coupling agent is used within the above range, compatibility with resin and adhesion strength can be improved when used for surface treatment of pigments and fillers. When the oligomer exceeds the range of use, the surface energy is increased to deteriorate the mold and resin releasability, and the surface hardness is increased to reduce the surface properties such as restoring force after stamping of the mold. In the case of the stabilizer, when used within the range of use, it is possible to reduce peripheral curing and increase strength.

The manufacturing of the dental restoration material of the present invention includes a 3D input step of receiving 3D information on a tooth structure, and a plurality of regions with the central axis of the tooth structure as the x-axis by setting a range of interest using the 3D information. It includes a 3D model generation step of generating a plurality of 3D models, and a 3D output step of outputting the plurality of 3D models using a digital light processing (DLP) method.

The 3D output unit outputs a plurality of 3D models in a digital light processing (DLP) method. The 3D output unit can generate the entire orthodontic device in a short time by outputting each 3D model at the same time or at the same time. The 3D output unit may output a dental restoration material using the photocurable composition for a 3D printer of the present invention according to a user's setting.

As the dental restoration material is manufactured by outputting it in a DLP method using a 3D model, the orthodontic effect may be increased by adjusting the thickness of a specific region.

The dental restoration material generates a 3D model so that the attachment 400 can be positioned in a portion corresponding to the inside of the tooth, and the 3D model can be output in a SLA (Stereolithography Apparatus) or DLP (Digital Light Processing) method.

In addition, the 3D output unit may surface-treat each boundary surface to enhance coupling between the plurality of 3D outputs corresponding to the plurality of 3D models. For example, UV treatment or heat treatment may be performed on the interface of each 3D output, but the present invention is not limited thereto. This is to facilitate bonding between neighboring 3D outputs by roughening the interface between the 3D outputs. A plurality of divided 3D printed products can be bonded through heat treatment after applying a resin to the interface.

제조예manufacturing example

치아 수복용 조성물의 제조Preparation of compositions for dental restoration

UV curing polyurethane compound represented by the following formula (13); A photoinitiator represented by the following formula (5); 3-methacryloxypropyltrimethoxysilane; epoxy acrylate oligomers; And 2,6-di-tert-butyl-p-cresol was mixed to prepare a photocurable polymer composition for a 3D printer. The oligomers used in the preparation of the polymer composition were purchased and used, and the contents of the constituents are shown in Table 1 below.

[Formula 13]

[Formula 12]

[Formula 14]

[Formula 15]

here,

* means the part to be joined,

L ₁ and L ₃ may be selected from Formula 14 or Formula 15.

When L ₁ and L ₃ are of Formula 14, it is referred to as GRP1, and when L1 and L3 are of Formula 15, it is referred to as GRP2.

	G1G1	G2G2	G3G3	G4G4	G5G5	G6G6	G7G7	G8G8
GRP1GRP1	100100	100100	100100	100100	100100	100100	--	--
GRP2GRP2	--	--	--	--	--	--	100100	100100
광개시제photoinitiator	1One	1.51.5	55	1010	1515	2020	1010	1515
실란커플링제Silane coupling agent	0.050.05	0.10.1	0.50.5	1One	1.51.5	22	1One	1.51.5
올리고머oligomer	1010	1515	2525	3030	4545	5050	3030	4545
안정제stabilizator	0.050.05	0.10.1	0.50.5	1One	22	33	1One	22

(unit weight parts)

In addition to the components of Table 1, a pigment capable of exhibiting the same color as the tooth color may be further included.

As a comparative example, a composition was prepared using the compounds represented by the following Chemical Formulas 16 to 19 in place of the polyurethane oligomer.

[Formula 16]

[Formula 17]

[Formula 18]

[Formula 19]

here,

s is an integer from 1 to 10;

The composition comprising Chemical Formula 16 is shown in Comparative Example 1, the composition comprising Chemical Formula 17 is shown in Comparative Example 2, the composition comprising Chemical Formula 18 is shown in Comparative Example 3, and the composition comprising Chemical Formula 19 is shown in Comparative Example 4.

실험예Experimental example

기계적 강도 측정Mechanical strength measurement

1. Test conditions

Shore hardness

Test Method: ASTM D2240

Test equipment: Shore hardness gauge

bend test

Test method: ISO 10477

Testing equipment: Universal testing machine (Qmesys QM100TM)

Test speed: 1mm/min

Distance between spans: 20mm

Elasticity section: (0.05 ~ 0.25)%

Test environment: (23±2)℃, (50±2)% R. H.

IZOD Impact Test (Notch)

Test method: ASTM D256

Test Equipment: Digital impact tester (Qmesys QM700A)

Weight: 60Kgf

Specimen Shape: V-notch

Test environment: (23±2)℃, (50±2)% R. H.

2. Test environment

In order to check whether the excellent mechanical properties can be exhibited even in the oral humidity conditions, the compositions of G1 to G8 and Comparative Examples 1 to 4 were printed as specimens using a 3D printer, and then the composition was printed at a temperature of 37° C. with a humidity of 80 % was maintained for 1 week, and then the mechanical strength was measured.

	G1G1	G2G2	G3G3	G4G4	G5G5	G6G6	G7G7	G8G8	비교예1Comparative Example 1	비교예2Comparative Example 2	비교예3Comparative Example 3	비교예4Comparative Example 4
Shore Hardness (D)Shore Hardness (D)	8585	8787	9090	9191	8888	8686	8989	9393	7070	6666	6969	7171
굴곡 강도 (MPa)curve burglar (MPa)	178178	180180	199199	200200	185185	187187	198198	204204	141141	132132	138138	146146
탄성 계수 (MPa)Shout Coefficient (MPa)	35703570	35603560	34503450	35003500	36103610	35903590	33803380	34003400	24502450	23002300	24802480	25102510
Impact Strength(J/㎡)Impact Strength(J/㎡)	41204120	42904290	43004300	42004200	40504050	41504150	42504250	40004000	30003000	31003100	28002800	27502750

According to Table 2, the composition of the present invention and the composition of Comparative Example are the results of a comparative experiment.

Considering that the dental restoration material should be a material that can be used permanently, an experiment for mechanical properties was conducted under a humidity condition higher than that of the oral environment.

As a result of the experiment, in Comparative Examples 1 to 4, it can be confirmed that the compound absorbs moisture in an environment with high humidity, and thus the mechanical properties are relatively low.

In addition, it was confirmed that excellent mechanical properties can be exhibited when carried out within the scope of the present invention.

Although the preferred embodiment of the present invention has been described in detail above, the scope of the present invention is not limited thereto, and various modifications and improvements by those skilled in the art using the basic concept of the present invention as defined in the following claims are also provided. is within the scope of the

Claims

A photocurable polyurethane compound represented by the following formula (1);

photoinitiators;

silane coupling agents;

oligomers; and

containing stabilizers

Compositions for photocurable dental restoration:

[Formula 1]

[Formula 2]

[Formula 3]

[Formula 4]

here,

* means the part to be joined,

R 1 To R 6 are the same as or different from each other, and each independently hydrogen, deuterium, cyano group, nitro group, halogen group, hydroxy group, substituted or unsubstituted C 1 to C 30 alkyl group, substituted or unsubstituted C 1 to C 20 A cycloalkyl group, a substituted or unsubstituted alkenyl group having 2 to 30 carbon atoms, a substituted or unsubstituted alkynyl group having 2 to 24 carbon atoms, a substituted or unsubstituted aralkyl group having 7 to 30 carbon atoms, or a substituted or unsubstituted aryl group having 6 to 30 carbon atoms , a substituted or unsubstituted heteroaryl group having 5 to 60 carbon atoms, a substituted or unsubstituted heteroarylalkyl group having 6 to 30 carbon atoms, a substituted or unsubstituted alkoxy group having 1 to 30 carbon atoms, a substituted or unsubstituted alkylamino group having 1 to 30 carbon atoms , substituted or unsubstituted arylamino group having 6 to 30 carbon atoms, substituted or unsubstituted aralkylamino group having 6 to 30 carbon atoms, substituted or unsubstituted heteroarylamino group having 2 to 24 carbon atoms, substituted or unsubstituted alkylsilyl having 1 to 30 carbon atoms It is selected from the group consisting of a group, a substituted or unsubstituted arylsilyl group having 6 to 30 carbon atoms and a substituted or unsubstituted aryloxy group having 6 to 30 carbon atoms,

L 1 and L 3 are the same as or different from each other, and each independently a substituted or unsubstituted C 1 to C 20 alkylene group, a substituted or unsubstituted C 6 to C 30 arylene group, a substituted or unsubstituted C 5 to C 30 of a heteroarylene group and a substituted or unsubstituted cycloalkylene group having 3 to 30 carbon atoms,

L 2 is selected from the group consisting of compounds represented by Formulas 2 to 4,

n and m are the same as or different from each other, and are each independently an integer from 1 to 10,

R 7 to R 12 are the same as or different from each other, and each independently represents hydrogen, deuterium, a halogen group, a hydroxy group, a substituted or unsubstituted C 1 to C 30 alkyl group, a substituted or unsubstituted C 1 to C 20 cycloalkyl group, a substituted or unsubstituted A ring having 2 to 30 carbon atoms, a substituted or unsubstituted alkynyl group having 2 to 24 carbon atoms, a substituted or unsubstituted aralkyl group having 7 to 30 carbon atoms, a substituted or unsubstituted aryl group having 6 to 30 carbon atoms, and a substituted or unsubstituted carbon number It is selected from the group consisting of 5 to 60 heteroaryl groups,

The substituted alkylene group, substituted arylene group, substituted heteroarylene group, substituted cycloalkylene group, substituted alkyl group, substituted cycloalkyl group, substituted alkenyl group, substituted alkynyl group, substituted aralkyl group, substituted aryl Group, substituted heteroaryl group, substituted heteroarylalkyl group, substituted alkoxy group, substituted alkylamino group, substituted arylamino group, substituted aralkylamino group, substituted heteroarylamino group, substituted alkylsilyl group, substituted aryl A silyl group and a substituted aryloxy group include hydrogen, deuterium, a cyano group, a nitro group, a halogen group, a hydroxyl group, an alkyl group having 1 to 30 carbon atoms, a cycloalkyl group having 1 to 20 carbon atoms, an alkenyl group having 2 to 30 carbon atoms, 2 to 24 carbon atoms. of an alkynyl group, an aralkyl group having 7 to 30 carbon atoms, an aryl group having 6 to 30 carbon atoms, a heteroaryl group having 5 to 60 nuclear atoms, a heteroarylalkyl group having 6 to 30 carbon atoms, an alkoxy group having 1 to 30 carbon atoms, 1 carbon atoms A to 30 alkylamino group, an arylamino group having 6 to 30 carbon atoms, an aralkylamino group having 6 to 30 carbon atoms, a heteroarylamino group having 2 to 24 carbon atoms, an alkylsilyl group having 1 to 30 carbon atoms, an arylsilyl group having 6 to 30 carbon atoms, and It is substituted with one or more substituents selected from the group consisting of an aryloxy group having 6 to 30 carbon atoms, and when substituted with a plurality of substituents, they are the same or different from each other.
According to claim 1,

Wherein R 1 and R 6 are a compound represented by the following formula (5)

Compositions for photocurable dental restoration:

[Formula 5]

here,

* means the part to be joined,

R 13 is hydrogen, deuterium, a halogen group, a hydroxy group, a substituted or unsubstituted alkyl group having 1 to 30 carbon atoms, a substituted or unsubstituted cycloalkyl group having 1 to 20 carbon atoms, a substituted or unsubstituted alkenyl group having 2 to 30 carbon atoms, a substituted or unsubstituted It is selected from the group consisting of an alkynyl group having 2 to 24 carbon atoms in the ring, a substituted or unsubstituted aralkyl group having 7 to 30 carbon atoms, a substituted or unsubstituted aryl group having 6 to 30 carbon atoms and a substituted or unsubstituted heteroaryl group having 5 to 60 carbon atoms, ,

The substituted alkyl group, substituted cycloalkyl group, substituted alkenyl group, substituted alkynyl group, substituted aralkyl group, substituted aryl group and substituted heteroaryl group include hydrogen, deuterium, cyano group, nitro group, halogen group, hydroxy group, An alkyl group having 1 to 30 carbon atoms, a cycloalkyl group having 1 to 20 carbon atoms, an alkenyl group having 2 to 30 carbon atoms, an alkynyl group having 2 to 24 carbon atoms, an aralkyl group having 7 to 30 carbon atoms, an aryl group having 6 to 30 carbon atoms, the number of nuclear atoms A heteroaryl group having 5 to 60 carbon atoms, a heteroarylalkyl group having 6 to 30 carbon atoms, an alkoxy group having 1 to 30 carbon atoms, an alkylamino group having 1 to 30 carbon atoms, an arylamino group having 6 to 30 carbon atoms, an aralkylamino group having 6 to 30 carbon atoms, It is substituted with one or more substituents selected from the group consisting of a heteroarylamino group having 2 to 24 carbon atoms, an alkylsilyl group having 1 to 30 carbon atoms, an arylsilyl group having 6 to 30 carbon atoms and an aryloxy group having 6 to 30 carbon atoms, and a plurality of substituents When substituted with, they are the same as or different from each other.
According to claim 1,

wherein L 1 and L 3 are the same as or different from each other and each independently selected from the group consisting of compounds represented by the following Chemical Formulas 6 to 10

Compositions for photocurable dental restoration:

[Formula 6]

[Formula 7]

[Formula 8]

[Formula 9]

[Formula 10]

here,

* means the part to be joined,

p and r are the same as or different from each other, and are each independently an integer of 0 to 4,

q is an integer from 1 to 10,

L 4 and L 5 are the same or different from each other, and each independently a substituted or unsubstituted C 1 to C 20 alkylene group, a substituted or unsubstituted C 6 to C 30 arylene group, a substituted or unsubstituted C 5 to a heteroarylene group of 30 and a substituted or unsubstituted cycloalkylene group having 3 to 30 carbon atoms,

R 14 to R 17 are the same as or different from each other, and each independently represents hydrogen, deuterium, a halogen group, a hydroxy group, a substituted or unsubstituted C 1 to C 30 alkyl group, a substituted or unsubstituted C 1 to C 20 cycloalkyl group, a substituted or unsubstituted A ring having 2 to 30 carbon atoms, a substituted or unsubstituted alkynyl group having 2 to 24 carbon atoms, a substituted or unsubstituted aralkyl group having 7 to 30 carbon atoms, a substituted or unsubstituted aryl group having 6 to 30 carbon atoms, and a substituted or unsubstituted carbon number It is selected from the group consisting of 5 to 60 heteroaryl groups,

The substituted alkyl group, substituted cycloalkyl group, substituted alkenyl group, substituted alkynyl group, substituted aralkyl group, substituted aryl group and substituted heteroaryl group include hydrogen, deuterium, cyano group, nitro group, halogen group, hydroxy group, An alkyl group having 1 to 30 carbon atoms, a cycloalkyl group having 1 to 20 carbon atoms, an alkenyl group having 2 to 30 carbon atoms, an alkynyl group having 2 to 24 carbon atoms, an aralkyl group having 7 to 30 carbon atoms, an aryl group having 6 to 30 carbon atoms, the number of nuclear atoms A heteroaryl group having 5 to 60 carbon atoms, a heteroarylalkyl group having 6 to 30 carbon atoms, an alkoxy group having 1 to 30 carbon atoms, an alkylamino group having 1 to 30 carbon atoms, an arylamino group having 6 to 30 carbon atoms, an aralkylamino group having 6 to 30 carbon atoms, It is substituted with one or more substituents selected from the group consisting of a heteroarylamino group having 2 to 24 carbon atoms, an alkylsilyl group having 1 to 30 carbon atoms, an arylsilyl group having 6 to 30 carbon atoms and an aryloxy group having 6 to 30 carbon atoms, and a plurality of substituents When substituted with, they are the same as or different from each other.
According to claim 1,

The photoinitiator is a compound represented by the following formula (11)

Compositions for photocurable dental restoration:

[Formula 11]

here,

X 1 is S, O or N(R 20 ),

R 19 to R 20 are the same as or different from each other, and each independently represents hydrogen, deuterium, a cyano group, a nitro group, a halogen group, a hydroxy group, a substituted or unsubstituted alkyl group having 1 to 30 carbon atoms, and a substituted or unsubstituted C 3 to 30 carbon group a cycloalkyl group,

The substituted alkyl group and the substituted cycloalkyl group are hydrogen, deuterium, cyano group, nitro group, halogen group, hydroxy group, alkyl group having 1 to 30 carbon atoms, cycloalkyl group having 1 to 20 carbon atoms, alkenyl group having 2 to 30 carbon atoms, and 2 carbon atoms. to 24 alkynyl group, C7 to C30 aralkyl group, C6 to C30 aryl group, nuclear atom 5 to 60 heteroaryl group, C6 to C30 heteroarylalkyl group, C1 to C30 alkoxy group, C1-C30 alkylamino group, C6-C30 arylamino group, C6-C30 aralkylamino group, C2-C24 hetero arylamino group, C1-C30 alkylsilyl group, C6-C30 arylsilyl It is substituted with one or more substituents selected from the group consisting of a group and an aryloxy group having 6 to 30 carbon atoms, and when substituted with a plurality of substituents, they are the same or different from each other.
According to claim 1,

The oligomer is an epoxy acrylate oligomer, H 12 Diane -bis-glycidyl ether (4,4'- (1-Methylethylidene) biscyclohexanol, polymer with (chloromethyl) oxirane) and mixtures thereof selected from the group consisting of

A composition for photocurable tooth restoration.
According to claim 1,

The stabilizer is selected from the group consisting of 2,6-di-tert-butyl-p-cresol, diethylethanolamine, trihexylamine, hindered amine, organic phosphate, hindered phenol, and mixtures thereof.

A composition for photocurable tooth restoration.
Claims 1 to 6, comprising the photocurable tooth restoration composition according to any one of claims

Patient-specific dental restoration materials.