Slumping-resistant dental composite resin composition

Abstract

One embodiment of the present specification provides a dental composite resin composition comprising 0.1 wt% to 1.4 wt% of glycerol di(meth)acrylate and 60-90 wt% of a filler, wherein the loss modulus at 23 °C, a frequency of 1 Hz, and an amplitude of 0.05% is 10,000 Pa or more.

Description

Slumping-resistant dental composite resin composition

[0001] This specification relates to a slumping-resistant dental composite resin composition.

[0002] Dental photocurable composite resin, also known as Light-Curing Composite Resin or Universal Composite Resin, is used to fill cavities formed in teeth after removing carious parts of the tooth. These dental photocurable composite resins are mainly composed of dimethacrylate-based monomers, photoinitiators, photosensitizers, pigments, other additives, and inorganic fillers, and are cured by a blue light source (blue LED).

[0003] Dental photocurable composite resins are divided into two types: flowable composite resins, which are of a flowing type, and packable composite resins, which are in paste form. The biggest difference between flowable composite resins and packable composite resins lies in their form, and the form of the composite resin is determined by the ratio of polymers and inorganic fillers in the composition. Low-viscosity flowable composite resins have an inorganic filler content of 70 weight% or less and are in a flowing form, whereas packable composite resins have an inorganic filler content of 80 weight% or more and the proportion of polymers and other additives is 20 weight% or less.

[0004] Composite resins with a very high content of inorganic fillers, such as condensed composite resins, have high viscosity, exist in a solid form, and exhibit rheologically viscoelastic properties. The viscoelasticity of dental photocurable composite resins can vary depending on the type and content of monomers or inorganic fillers included in the composition, and whether the composite resin is soft or hard during manipulation can be determined by the absolute and relative values ​​of the storage modulus and loss modulus. The storage modulus G' represents the solid properties of the composite resin, i.e., elasticity, while the loss modulus G'' represents the liquid properties of the composite resin, i.e., viscosity. The loss factor (tan δ), which represents the ratio of the storage modulus to the loss modulus, indicates that viscosity is dominant as its value increases.

[0005] The rheological properties of such composite resins are the most important factor determining ease of manipulation when the operator handles the resin in the oral cavity. If the flowability of the composite resin is excessively high, it may not maintain the shape formed by the operator after application to the cavity and may flow down until light-curing, which may require more time for adjustment and polishing after polymerization or lead to restoration failure.

[0006] Therefore, it is necessary to develop a high-viscosity dental composite resin composition that has high viscosity due to a high filler content, while simultaneously possessing slumping resistance by controlling the flowability of the composite resin.

[0007] The details described in this specification are intended to solve the problems of the aforementioned prior art, and one objective of this specification is to provide a high-viscosity dental composite resin composition having slumping resistance.

[0008] According to one aspect, a dental composite resin composition is provided comprising 0.1 wt% or more and less than 1.4 wt% of glycerol di(meth)acrylate and 60 to 90 wt% of filler, and having a loss modulus of elasticity of 10,000 Pa or more at a frequency of 1 Hz and an amplitude of 0.05% at 23°C.

[0009] In one embodiment, the glycerol di(meth)acrylate may be one selected from the group consisting of glycerol 1,3-dimethacrylate, glycerol 1,3-diacrylate, glycerol 1,2-dimethacrylate, and combinations of two or more of these.

[0010] In one embodiment, the dental composite resin composition may further include 0.1 to 5 weight percent of polyalkylene glycol-based di(meth)acrylate.

[0011] In one embodiment, the polyalkylene glycol-based di(meth)acrylate may be one selected from the group consisting of polyethylene glycol dimethacrylate, polyethylene glycol diacrylate, polypropylene glycol dimethacrylate, polypropylene glycol diacrylate, and combinations of two or more of these.

[0012] In one embodiment, the dental composite resin composition may further include 0.1 to 5 weight percent of alkanediol di(meth)acrylate.

[0013] In one embodiment, the alkanediol di(meth)acrylate may be one selected from the group consisting of 1,12-dodecanediol dimethacrylate, 1,12-dodecanediol diacrylate, 1,10-decanediol dimethacrylate, 1,10-decanediol diacrylate, 1,9-nonanediol dimethacrylate, 1,9-nonanediol diacrylate, 1,8-octanediol dimethacrylate, 1,8-octanediol diacrylate, 1,6-hexanediol dimethacrylate, 1,6-hexanediol diacrylate, and combinations of two or more of these.

[0014] In one embodiment, the dental composite resin composition may further comprise 6 to 15 weight% of bisphenol-A-based di(meth)acrylate and 0.1 to 5 weight% of alkylene glycol-based di(meth)acrylate.

[0015] In one embodiment, the bisphenol-A di(meth)acrylate may be one selected from the group consisting of bisphenol-A glycidyl dimethacrylate, bisphenol-A ethoxylate dimethacrylate, bisphenol-A dimethacrylate, bisphenol-A diacrylate, bisphenol-A ethoxylate diacrylate, bisphenol-A diglycidyl ether diacrylate, bisphenol-A epoxy diacrylate, and combinations of two or more of these.

[0016] In one embodiment, the alkylene glycol-based di(meth)acrylate may be one selected from the group consisting of ethylene glycol dimethacrylate, diethylene glycol dimethacrylate, triethylene glycol dimethacrylate, tetraethylene glycol dimethacrylate, diethylene glycol diacrylate, triethylene glycol diacrylate, tetraethylene glycol diacrylate, and combinations of two or more of these.

[0017] In one embodiment, the bisphenol-A-based di(meth)acrylate may comprise 1 to 5 weight% of bisphenol-A glycidyl dimethacrylate and 5 to 10 weight% of bisphenol-A ethoxylate dimethacrylate.

[0018] In one embodiment, the filler may be one selected from the group consisting of fumed silica, barium silicate, barium aluminum silicate, aluminum silicate, lithium aluminum silicate, strontium aluminum silicate, zirconium silicate, glass, barium silicate glass, strontium silicate glass, and combinations of two or more of these.

[0019] In one embodiment, the filler may comprise 50 to 80 weight percent of microfillers having an average particle size greater than 0.1 μm and less than or equal to 100 μm, and 1 to 10 weight percent of nanofillers having an average particle size greater than 1 nm and less than or equal to 100 nm.

[0020] In one embodiment, the dental composite resin composition may further include one or more selected from the group consisting of a photosensitizer, a photoinitiator, a curing inhibitor, a UV absorber, and a pigment.

[0021] In one embodiment, the dental composite resin composition may have a storage modulus of 30,000 Pa or more at a frequency of 1 Hz and an amplitude of 0.05%.

[0022] A dental composite resin composition according to one aspect of the present specification has a high viscosity due to a high filler content, and at the same time, by controlling the flowability of the composition, it has slumping resistance during tooth restoration, making tooth restoration easier.

[0023] The effects of one aspect of this specification are not limited to the effects described above, and should be understood to include all effects that can be inferred from the configurations described in the detailed description or claims of this specification.

[0024] Hereinafter, one aspect of this specification will be described based on specific examples. However, the details described in this specification may be implemented in various different forms and are therefore not limited to the embodiments described herein.

[0025] Throughout the specification, when a part is described as "including" a certain component, this means that, unless specifically stated otherwise, it does not exclude other components but rather allows for the inclusion of additional components.

[0026] When a range of numerical values ​​is described in this specification, unless a specific range is otherwise described, the value has the precision of significant figures provided according to the standard rules in chemistry for significant figures. For example, 10 includes a range of 5.0 to 14.9, and the number 10.0 includes a range of 9.50 to 10.49.

[0027] The term “slumping resistance” as used in this specification refers to the property of a dental composite resin composition not flowing after being applied to a cavity.

[0028] Dental composite resin composition

[0029] A dental composite resin composition according to one aspect of the present specification comprises 0.1% by weight or more and less than 1.4% by weight of glycerol di(meth)acrylate, and 60 to 90% by weight of filler, and has a loss modulus of elasticity of 10,000 Pa or more at 23°C, a frequency of 1 Hz, and an amplitude of 0.05%.

[0030] The above dental composite resin composition has a high viscosity due to the high filler content, and at the same time, by controlling the flowability of the composition through the control of the glycerol di(meth)acrylate monomer content, it has slumping resistance during tooth restoration, making tooth restoration easier.

[0031] The content of the glycerol di(meth)acrylate may be 0.1 wt% or more and less than 1.4 wt% based on the total weight of the dental composite resin composition. For example, it may be 0.1 wt%, 0.2 wt%, 0.3 wt%, 0.4 wt%, 0.5 wt%, 0.6 wt%, 0.7 wt%, 0.8 wt%, 0.9 wt%, 1 wt%, 1.1 wt%, 1.2 wt%, 1.3 wt%, 1.39 wt%, or a range between two of these values. If the content of the glycerol di(meth)acrylate is less than the above range, the bonding strength between the polymer matrix and the filler is reduced, and the resin may crack or tear. If the content of glycerol di(meth)acrylate exceeds the above range, the resin composition may exhibit an excessively flowing formulation, and after applying the composite resin to the cavity, it may not maintain the shape formed by the operator until light polymerization, causing it to flow down and resulting in slumping. Consequently, more time may be required for adjustment and polishing after polymerization, or it may lead to restoration failure.

[0032] The above glycerol di(meth)acrylate may be one selected from the group consisting of glycerol 1,3-dimethacrylate, glycerol 1,3-diacrylate, glycerol 1,2-dimethacrylate, and combinations of two or more of these, but is not limited thereto.

[0033] In one embodiment, the glycerol di(meth)acrylate may be glycerol 1,3-dimethacrylate (GDMA). Glycerol 1,3-dimethacrylate contains a hydrophilic hydroxyl group (-OH) and can bond well with a hydrophilic filler, thereby imparting properties to the composite resin that prevent it from cracking or tearing. In addition, it may have excellent stability due to lower water absorption compared to 2-hydroxyethyl methacrylate (HEMA) of a similar class.

[0034] In one embodiment, the dental composite resin composition may further include polyalkylene glycol-based di(meth)acrylate, alkanediol di(meth)acrylate, bisphenol-A-based di(meth)acrylate, alkylene glycol-based di(meth)acrylate, or a combination of two or more of these.

[0035] The above dental composite resin composition may further include 0.1 to 5 weight percent of polyalkylene glycol-based di(meth)acrylate.

[0036] The content of the polyalkylene glycol-based di(meth)acrylate may be 0.1 to 5 wt% based on the total weight of the dental composite resin composition. For example, it may be 0.1 wt%, 0.5 wt%, 1 wt%, 1.5 wt%, 2 wt%, 2.5 wt%, 3 wt%, 3.5 wt%, 4 wt%, 4.5 wt%, 5 wt%, or a range between two of these values. If the content of the polyalkylene glycol-based di(meth)acrylate is below the above range, the flexibility of the polymer matrix is ​​reduced, which may reduce the softness when handling the resin composition; if it exceeds the above range, the resin composition may exhibit an excessively flowing formulation, which may cause slumping when applied to a cavity.

[0037] The above polyalkylene glycol-based di(meth)acrylate may be one selected from the group consisting of polyethylene glycol dimethacrylate, polyethylene glycol diacrylate, polypropylene glycol dimethacrylate, polypropylene glycol diacrylate, and combinations of two or more of these, but is not limited thereto.

[0038] In one embodiment, the polyalkylene glycol-based di(meth)acrylate may be polyethylene glycol dimethacrylate (PEGDMA). Polyethylene glycol dimethacrylate contains a bulky methyl group within the molecule and has a relatively long ethylene oxide chain compared to triethylene glycol dimethacrylate, resulting in excellent chain flexibility. Accordingly, the polymer matrix has excellent flexibility, allowing for soft characteristics when manipulating the resin composition.

[0039] The above dental composite resin composition may further include 0.1 to 5 weight percent of alkanediol di(meth)acrylate.

[0040] The content of the alkanediol di(meth)acrylate may be 0.1 to 5 wt% based on the total weight of the dental composite resin composition. For example, it may be 0.1 wt%, 0.5 wt%, 1 wt%, 1.5 wt%, 2 wt%, 2.5 wt%, 3 wt%, 3.5 wt%, 4 wt%, 4.5 wt%, 5 wt%, or a range between two of these values. If the content of the alkanediol di(meth)acrylate is below the above range, the flexibility of the polymer matrix is ​​reduced, which may result in reduced softness when handling the resin composition and a decrease in the curing speed of the resin composition. If the content of the alkanediol di(meth)acrylate exceeds the above range, the resin composition may exhibit an excessively flowing formulation, which may cause slumping when applied to a cavity.

[0041] The above alkanediol di(meth)acrylate may be one selected from the group consisting of 1,12-dodecanediol dimethacrylate, 1,12-dodecanediol diacrylate, 1,10-decanediol dimethacrylate, 1,10-decanediol diacrylate, 1,9-nonanediol dimethacrylate, 1,9-nonanediol diacrylate, 1,8-octanediol dimethacrylate, 1,8-octanediol diacrylate, 1,6-hexanediol dimethacrylate, 1,6-hexanediol diacrylate, and combinations of two or more of these, but is not limited thereto.

[0042] In one embodiment, the alkanediol di(meth)acrylate may be 1,12-dodecanediol dimethacrylate (1,12-DDDMA). 1,12-dodecanediol dimethacrylate has a hydrophobic backbone structure, which can increase the fluidity of the molecular structure and, accordingly, impart rapid curing characteristics and flexibility to the polymer matrix.

[0043] The above dental composite resin composition may further include 6 to 15 weight percent of bisphenol-A-based di(meth)acrylate.

[0044] The content of the bisphenol-A-based di(meth)acrylate may be 6 to 15 wt% based on the total weight of the dental composite resin composition. For example, it may be 6 wt%, 6.5 wt%, 7 wt%, 7.5 wt%, 8 wt%, 8.5 wt%, 9 wt%, 9.5 wt%, 10 wt%, 10.5 wt%, 11 wt%, 11.5 wt%, 12 wt%, 12.5 wt%, 13 wt%, 13.5 wt%, 14 wt%, 14.5 wt%, 15 wt%, or a range between two of these values.

[0045] The above dental composite resin composition may further include 0.1 to 5 weight percent of alkylene glycol-based di(meth)acrylate.

[0046] The content of the above alkylene glycol-based di(meth)acrylate may be 0.1 to 5 wt% based on the total weight of the dental composite resin composition. For example, it may be 0.1 wt%, 0.5 wt%, 1 wt%, 1.5 wt%, 2 wt%, 2.5 wt%, 3 wt%, 3.5 wt%, 4 wt%, 4.5 wt%, 5 wt%, or a range between two of these values.

[0047] The above dental composite resin composition may further include 6 to 15 weight% of bisphenol-A-based di(meth)acrylate and 0.1 to 5 weight% of alkylene glycol-based di(meth)acrylate.

[0048] The above bisphenol-A di(meth)acrylate may be one selected from the group consisting of bisphenol-A glycidyl dimethacrylate, bisphenol-A ethoxylate dimethacrylate, bisphenol-A dimethacrylate, bisphenol-A diacrylate, bisphenol-A ethoxylate diacrylate, bisphenol-A diglycidyl ether diacrylate, bisphenol-A epoxy diacrylate, and combinations of two or more of these, but is not limited thereto.

[0049] The above alkylene glycol-based di(meth)acrylate may be one selected from the group consisting of ethylene glycol dimethacrylate, diethylene glycol dimethacrylate, triethylene glycol dimethacrylate, tetraethylene glycol dimethacrylate, diethylene glycol diacrylate, triethylene glycol diacrylate, tetraethylene glycol diacrylate, and combinations of two or more of these, but is not limited thereto. However, the above alkylene glycol-based di(meth)acrylate does not include polyalkylene glycol-based di(meth)acrylate.

[0050] The above bisphenol-A-based di(meth)acrylate may comprise 1 to 5 weight% of bisphenol-A glycidyl dimethacrylate and 5 to 10 weight% of bisphenol-A ethoxylate dimethacrylate.

[0051] The content of the bisphenol-A glycidyl dimethacrylate may be 1 to 5 weight% based on the total weight of the dental composite resin composition. For example, it may be 1 weight%, 1.5 weight%, 2 weight%, 2.5 weight%, 3 weight%, 3.5 weight%, 4 weight%, 4.5 weight%, 5 weight%, or a range between two of these values.

[0052] The content of the bisphenol-A ethoxylate dimethacrylate may be 5 to 10 weight% based on the total weight of the dental composite resin composition. For example, it may be 5 weight%, 5.5 weight%, 6 weight%, 6.5 weight%, 7 weight%, 7.5 weight%, 8 weight%, 8.5 weight%, 9 weight%, 9.5 weight%, 10 weight%, or a range between two of these values.

[0053] The content of the filler may be 60 to 90 weight% based on the total weight of the dental composite resin composition. For example, it may be 60 weight%, 61 weight%, 62 weight%, 63 weight%, 64 weight%, 65 weight%, 66 weight%, 67 weight%, 68 weight%, 69 weight%, 70 weight%, 71 weight%, 72 weight%, 73 weight%, 74 weight%, 75 weight%, 76 weight%, 77 weight%, 78 weight%, 79 weight%, 80 weight%, 81 weight%, 82 weight%, 83 weight%, 84 weight%, 85 weight%, 86 weight%, 87 weight%, 88 weight%, 89 weight%, 90 weight%, or a range between two of these values. If the filler content is below the above range, the viscosity of the resin composition may decrease and take on a liquid form, and the flowability may increase, making it difficult to restore the cavity. If the filler content exceeds the above range, it may be difficult to form a polymer through the curing of the composite resin.

[0054] The above filler may be an inorganic filler, an organic filler, or a combination thereof.

[0055] The above filler may be one selected from the group consisting of fumed silica, barium silicate, barium aluminum silicate, aluminum silicate, lithium aluminum silicate, strontium aluminum silicate, zirconium silicate, glass, barium silicate glass, strontium silicate glass, and combinations of two or more of these, but is not limited thereto, and known inorganic fillers generally used in dental composite resin compositions may be used.

[0056] The above filler may comprise 50 to 80 weight percent of microfillers having an average particle size greater than 0.1 μm and less than or equal to 100 μm, and 1 to 10 weight percent of nanofillers having an average particle size greater than 1 nm and less than or equal to 100 nm.

[0057] In one embodiment, the microfiller may be a barium silicate filler surface-treated with a coupling agent, and the nanofiller may be a fumed silica filler surface-treated with a coupling agent.

[0058] The above dental composite resin composition may further include one or more additives selected from the group consisting of photosensitizers, photoinitiators, curing inhibitors, UV absorbers, and pigments.

[0059] The above photosensitizer is a substance that reacts by absorbing light of a wavelength of 400 to 500 nm, and may use quinone-based or phosphine oxide-based substances, but is not limited thereto. The content of the above photosensitizer may be 0.01 to 2 weight% based on the total weight of the dental composite resin composition.

[0060] The above photoinitiator may be a tertiary amine-based photoinitiator, but is not limited thereto. The content of the above photoinitiator may be 0.01 to 4 weight% based on the total weight of the dental composite resin composition.

[0061] The above-mentioned curing inhibitor serves to stabilize the composition so that the di(meth)acrylate-based monomer does not cure at room temperature, and may use an aromatic monomer containing a hydroxyl group, but is not limited thereto. The content of the above-mentioned curing inhibitor may be 0.01 to 1 weight% based on the total weight of the dental composite resin composition. If the content of the curing inhibitor exceeds the above range, curing may not occur even when sufficient blue LED is applied.

[0062] The above UV absorber is a substance that absorbs light with a wavelength of 400 nm or less to prevent the resin from being easily cured by an external light source such as a fluorescent lamp, and may use light absorbers of the benzotriazole, benzophenone, oxalanilide, or triazine series, but is not limited thereto. The content of the above UV absorber may be 0.01 to 1 weight% based on the total weight of the dental composite resin composition.

[0063] Iron oxide-based pigments may be used as the above pigments, but are not limited thereto. The content of the above pigment may be 0.01 to 0.1 weight% based on the total weight of the dental composite resin composition.

[0064] The above dental composite resin composition may be in the form of a paste.

[0065] The above dental composite resin composition may have a loss modulus of 10,000 Pa or more at 23°C, a frequency of 1 Hz, and an amplitude of 0.05%. For example, it may be 10,000 Pa or more, 10,100 Pa or more, 10,200 Pa or more, 10,300 Pa or more, 10,400 Pa or more, 10,500 Pa or more, 10,600 Pa or more, 10,700 Pa or more, 10,800 Pa or more, 10,900 Pa or more, 11,000 Pa or more, 11,100 Pa or more, 11,200 Pa or more, 11,300 Pa or more, 11,400 Pa or more, 11,500 Pa or more, 11,600 Pa or more, 11,700 Pa or more, 11,800 Pa or more, 11,900 Pa or more, 12,000 Pa or more, 12,100 Pa or more, or 12,200 Pa or more. If the loss modulus is below the above range, the resin composition exhibits an excessively flowing formulation, and after applying the composite resin to the cavity, it may not maintain the shape formed by the operator until light polymerization, causing it to flow down and resulting in slumping. Consequently, more time may be required for adjustment and polishing after polymerization, or it may lead to restoration failure.

[0066] The above dental composite resin composition may have a loss modulus of elasticity of 20,000 Pa or less at 23°C, a frequency of 1 Hz, and an amplitude of 0.05%. For example, it may be 20,000 Pa or less, 19,000 Pa or less, 18,000 Pa or less, 17,000 Pa or less, 16,000 Pa or less, 15,000 Pa or less, or 14,000 Pa or less. If the loss modulus of elasticity exceeds the above range, the shape of the resin composition may become elongated, making restoration difficult, which may lead to restoration failure.

[0067] The above dental composite resin composition may have a storage modulus of 30,000 Pa or more at 23°C, a frequency of 1 Hz, and an amplitude of 0.05%. For example, it may be 30,000 Pa or more, 31,000 Pa or more, 32,000 Pa or more, 33,000 Pa or more, 34,000 Pa or more, 35,000 Pa or more, or 36,000 Pa or more. If the storage modulus is below the above range, the resin composition may have an excessively flowing formulation, which may cause slumping when applied to a cavity.

[0068] The above dental composite resin composition may have a storage modulus of 50,000 Pa or less at 23°C, a frequency of 1 Hz, and an amplitude of 0.05%. For example, it may be 50,000 Pa or less, 49,000 Pa or less, 48,000 Pa or less, 47,000 Pa or less, 46,000 Pa or less, 45,000 Pa or less, 44,000 Pa or less, 43,000 Pa or less, 42,000 Pa or less, 41,000 Pa or less, or 40,000 Pa or less. If the storage modulus exceeds the above range, the resin may be too hard and difficult to manipulate in the oral cavity, and consequently, it may be difficult to form a restoration.

[0069] If the above dental composite resin composition has a loss modulus of less than 10,000 Pa and a storage modulus of less than 30,000 Pa at 23°C, a frequency of 1 Hz, and an amplitude of 0.05%, the resin composition exhibits an excessively flowing formulation. Consequently, after applying the composite resin to a cavity, it may not maintain the shape formed by the operator until it is light-cured, causing it to flow down and resulting in slumping. This may lead to more time being required for adjustment and polishing after polymerization, or result in restoration failure.

[0070] The above dental composite resin composition may have a loss factor (tan δ) of 0.3 to 0.4 at 23°C, a frequency of 1 Hz, and an amplitude of 0.05%. For example, it may be 0.3, 0.31, 0.32, 0.33, 0.34, 0.35, 0.36, 0.37, 0.38, 0.39, 0.4, or a range between two of these values. If the loss factor is below the above range, the resin may be too hard to manipulate in the oral cavity, and consequently, it may be difficult to form a restoration. If the loss factor exceeds the above range, the resin composition may have an excessively flowing formulation, which may cause slumping when applied to a cavity.

[0071] The embodiments of this specification will be described in more detail below. However, the following experimental results represent only representative results among the above embodiments, and the scope and content of this specification should not be interpreted as being narrowed or limited by the embodiments. The respective effects of various embodiments of this specification not explicitly presented below will be described in detail in the relevant sections.

[0072] Examples and Comparative Examples

[0073] Polyethylene glycol dimethacrylate (PEGDMA), 1,12-dodecanediol dimethacrylate (1,12-DDDMA), glycerol 1,3-dimethacrylate (GDMA), a mixture of bisphenol-A glycidyl dimethacrylate (BisGMA) and triethylene glycol dimethacrylate (TEGDMA) (weight ratio of BisGMA to TEGDMA is 8:2), bisphenol-A ethoxylate dimethacrylate (BisEMA), and additives were placed in a mixing vessel according to the composition of Table 1 below, and in an environment of 50 ℃ The mixture was mixed at 50 rpm for 10 minutes. As additives, a mixture of the photosensitizer camphorquinone, the photoinitiator ethyl-4-dimethylaminobenzoate (EDAB), the curing inhibitor butyl-hydroxytoluene, the UV absorber 2-(2'-hydroxy-5'-methylphenyl)benzotriazole, and an iron oxide-based dye was used.

[0074] After adding the microfiller according to the composition of Table 1 below, the mixture was mixed at 20 rpm for 2 hours in a 50 ℃ environment. As the microfiller, barium silicate filler surface-treated with a coupling agent having an average particle size greater than 0.1 μm (average particle size range 0.7–2.0 μm, 6.0% silane treatment, Schott 8235 series) was used.

[0075] After adding the nano filler according to the composition of Table 1 below, the mixture was mixed at 5 rpm for at least 4 hours in a 50 ℃ environment. As the nano filler, fumed silica filler surface-treated with a coupling agent having an average particle size of 100 nm or less (2-Propenoic acid, 2-methyl-, 3-(trimethoxysilyl)propylester or diemthyldichlorosilane surface treatment, Evonik R972, R7200) was used.

[0076] When the mixture formulation became a paste, it was removed from the container, kneaded by hand, and returned to the container. The mixture was then mixed at 5 rpm while lowering the container temperature to 25 ℃. After the container temperature was lowered to 25 ℃, a vacuum was applied, and the mixture was degassed at 1 rpm for 30 minutes to 1 hour to obtain a dental composite resin composition in paste form.

[0077] Classification (Weight%) Preliminary Example 1 Comparative Example 2 Comparative Example 3 Comparative Example 4 Comparative Example 5 Comparative Example 6 PEGDMA 2.3 2.3 2.3 2.3 2.3 2.3 1,12-DDDMA 2.8 2.8 3.5 4.2 0 2.8 2.3 GDMA 0.7 0 0 4.2 1.4 1.4 BisGMA, TEGDMA Mixture 2.5 2.5 2.5 2.5 2.5 2.5 2.5 BisEMA 9.3 9.3 9.3 9.3 9.3 9.3 Additive 2.4 2.6 2.4 2.2 2.2 2.2 3.3 Microfiller 76.2 76.7 76.2 75.7 75.7 75.7 75.1 Nanofiller 3.8 3.8 3.8 3.8 3.8 3.8 3.8

[0078] Experimental Example

[0079] The storage modulus (G') and loss modulus (G'') of the dental composite resin compositions prepared by the methods of the above Examples and Comparative Examples 1 to 6 were measured using a rheometer, and the loss factor (tan δ) was calculated therefrom.

[0080] A plate with a diameter of 25 mm was used as an accessory for measuring storage modulus and loss modulus. Measurements were taken at a temperature of 23 ℃, and the frequency sweep measurement frequency range was set to 0.1–10 Hz, with an amplitude of 0.05%.

[0081] The results measured at 23 ℃, a frequency of 1 Hz, and an amplitude of 0.05% are shown in Table 2 below.

[0082] Classification Preliminary Comparative Example 1 Comparative Example 2 Comparative Example 3 Comparative Example 4 Comparative Example 5 Comparative Example 6 Storage Modulus G' (Pa) 36,167 39,151 23,150 15,096 15,279 24,434 27,438 Loss Modulus G'' (Pa) 12,281 13,820 7,883 4,425 6,577 8,735 9,289 Loss Factor tan δ (G'' / G') 0.34 0.35 0.34 0.29 0.43 0.36 0.34

[0083] Referring to Table 2 above, when comparing Comparative Examples 1 to 3, it was confirmed that as the content of 1,12-DDDMA in the composition increases, both the storage modulus and the loss modulus decrease, the composition becomes softer, and the flowability increases.

[0084] When comparing Comparative Example 3 and Comparative Example 4, Comparative Example 3 using 1,12-DDDMA and Comparative Example 4 using GDMA of the same content showed similar values ​​for storage modulus, but in the case of loss modulus, Comparative Example 4 using GDMA showed a higher value compared to Comparative Example 3 using 1,12-DDDMA, and it was confirmed that the composition is relatively soft and has high flowability.

[0085] When comparing the Examples, Comparative Examples 1, 5, and 6, it was confirmed that as the content of GDMA in the composition increased, both the storage modulus and the loss modulus decreased, resulting in a smoother composition and increased flowability. However, in the case of Comparative Examples 5 and 6, where the GDMA content was 1.4 wt%, the loss modulus decreased to less than 10,000 Pa, exhibiting an excessively flowing formulation, and it was confirmed that a slumping phenomenon occurred when applied to a cavity.

[0086] It was confirmed that the dental composite resin composition of the example, having a loss modulus of 10,000 Pa or more and a storage modulus of 30,000 Pa or more, facilitates tooth restoration without slumping when applied to a cavity. On the other hand, the resin compositions of Comparative Examples 2 to 6, having a loss modulus of less than 10,000 Pa and a storage modulus of less than 30,000 Pa, had an excessively flowing formulation, which caused slumping when applied to a cavity. The resin composition of Comparative Example 1, which does not contain GDMA, did not cause slumping, but had a problem where the resin cracked or tore due to low bonding strength with the filler.

[0087] The foregoing description of this specification is for illustrative purposes only, and those skilled in the art to which one aspect of this specification pertains will understand that other specific forms can be easily modified without altering the technical concept or essential features described in this specification. Therefore, the embodiments described above should be understood as illustrative in all respects and not restrictive. For example, each component described as a single unit may be implemented in a distributed manner, and components described as distributed may likewise be implemented in a combined form.

[0088] The scope of this specification is defined by the claims set forth below, and all modifications or variations derived from the meaning and scope of the claims and equivalent concepts thereof should be interpreted as being included within the scope of this specification.

Claims

1. Glycerol di(meth)acrylate 0.1 wt% or more and less than 1.4 wt%, and Contains 60 to 90 weight percent of filler, and A dental composite resin composition having a loss modulus of 10,000 Pa or more at 23 ℃, a frequency of 1 Hz, and an amplitude of 0.05% 2. In Paragraph 1, A dental composite resin composition in which the above polyalkylene glycol-based di(meth)acrylate is one selected from the group consisting of polyethylene glycol dimethacrylate, polyethylene glycol diacrylate, polypropylene glycol dimethacrylate, polypropylene glycol diacrylate, and combinations of two or more of these.

3. In Paragraph 1, A dental composite resin composition further comprising 0.1 to 5 weight% of polyalkylene glycol-based di(meth)acrylate.

4. In Paragraph 3, A dental composite resin composition in which the above polyalkylene glycol-based di(meth)acrylate is one selected from the group consisting of polyethylene glycol dimethacrylate, polyethylene glycol diacrylate, polypropylene glycol dimethacrylate, polypropylene glycol diacrylate, and combinations of two or more of these.

5. In Paragraph 1, A dental composite resin composition further comprising 0.1 to 5 weight percent of alkanediol di(meth)acrylate.

6. In Paragraph 5, A dental composite resin composition wherein the above alkanediol di(meth)acrylate is one selected from the group consisting of 1,12-dodecanediol dimethacrylate, 1,12-dodecanediol diacrylate, 1,10-decanediol dimethacrylate, 1,10-decanediol diacrylate, 1,9-nonanediol dimethacrylate, 1,9-nonanediol diacrylate, 1,8-octanediol dimethacrylate, 1,8-octanediol diacrylate, 1,6-hexanediol dimethacrylate, 1,6-hexanediol diacrylate, and combinations of two or more of these.

7. In Paragraph 1, A dental composite resin composition further comprising 6 to 15 weight% of bisphenol-A-based di(meth)acrylate and 0.1 to 5 weight% of alkylene glycol-based di(meth)acrylate.

8. In Paragraph 7, A dental composite resin composition wherein the above bisphenol-A di(meth)acrylate is one selected from the group consisting of bisphenol-A glycidyl dimethacrylate, bisphenol-A ethoxylate dimethacrylate, bisphenol-A dimethacrylate, bisphenol-A diacrylate, bisphenol-A ethoxylate diacrylate, bisphenol-A diglycidyl ether diacrylate, bisphenol-A epoxy diacrylate, and combinations of two or more of these.

9. In Paragraph 7, A dental composite resin composition in which the above-mentioned alkylene glycol-based di(meth)acrylate is one selected from the group consisting of ethylene glycol dimethacrylate, diethylene glycol dimethacrylate, triethylene glycol dimethacrylate, tetraethylene glycol dimethacrylate, diethylene glycol diacrylate, triethylene glycol diacrylate, tetraethylene glycol diacrylate, and combinations of two or more of these.

10. In Paragraph 7, The above bisphenol-A-based di(meth)acrylate comprises 1 to 5 weight% of bisphenol-A glycidyl dimethacrylate and 5 to 10 weight% of bisphenol-A ethoxylate dimethacrylate, forming a dental composite resin composition.

11. In Paragraph 1, A dental composite resin composition in which the above filler is one selected from the group consisting of fumed silica, barium silicate, barium aluminum silicate, aluminum silicate, lithium aluminum silicate, strontium aluminum silicate, zirconium silicate, glass, barium silicate glass, strontium silicate glass, and combinations of two or more of these.

12. In Paragraph 1, A dental composite resin composition comprising 50 to 80 weight% of microfillers having an average particle size greater than 0.1 μm and less than or equal to 100 μm, and 1 to 10 weight% of nanofillers having an average particle size greater than 1 nm and less than or equal to 100 nm.

13. In Paragraph 1, A dental composite resin composition comprising one or more selected from the group consisting of photosensitizers, photoinitiators, curing inhibitors, UV absorbers, and pigments.

14. In Paragraph 1, A dental composite resin composition having a storage modulus of 30,000 Pa or more at 23 ℃, a frequency of 1 Hz, and an amplitude of 0.05%.