Dental composite resin composition having good long-term stability

Abstract

Provided is a dental composite resin composition according to one embodiment of the present specification comprising: 60-80 wt% micro-filler of 0.1-100 μm average particle size; and 4-5 wt% nano-filler of 1-100 nm average particle size.

Description

Dental composite resin composition with excellent long-term stability

[0001] This specification relates to a dental composite resin composition having excellent long-term stability.

[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 ratio of storage modulus to loss modulus is too low at high vibration frequencies of 1 Hz or higher, the shape of the resin may become elongated, making restoration difficult and potentially leading to restoration failure. Furthermore, conventional dental photocurable composite resins have poor long-term stability at room temperature, resulting in a failure to maintain a stable shape and the occurrence of syneresis.

[0006] Therefore, there is a need to develop a high-viscosity dental composite resin composition that has a high viscosity due to its high filler content, does not sag during manipulation in the oral cavity, and exhibits excellent long-term stability at room temperature.

[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 with excellent long-term stability at room temperature.

[0008] According to one aspect, a dental composite resin composition is provided comprising 60 to 80 weight% of microfillers having an average particle size greater than 0.1 μm and less than or equal to 100 μm, and 4 to 5 weight% of nanofillers having an average particle size greater than 1 nm and less than or equal to 100 nm.

[0009] In one embodiment, the microfiller and the nanofiller may each independently 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.

[0010] In one embodiment, the dental composite resin composition may further include a di(meth)acrylate-based monomer.

[0011] In one embodiment, the content of the di(meth)acrylate-based monomer may be 12 to 35 weight percent based on the total weight of the dental composite resin composition.

[0012] In one embodiment, the di(meth)acrylate-based monomer may be one selected from the group consisting of polyalkylene glycol-based di(meth)acrylate, alkanediol di(meth)acrylate, glycerol di(meth)acrylate, bisphenol-A-based di(meth)acrylate, alkylene glycol-based di(meth)acrylate, and combinations of two or more of these.

[0013] In one embodiment, the dental composite resin composition may further comprise 0.1 to 5 weight% of polyalkylene glycol-based di(meth)acrylate and 0.1 to 5 weight% of alkanediol di(meth)acrylate.

[0014] 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.

[0015] 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.

[0016] 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.

[0017] 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.

[0018] 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.

[0019] 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.

[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 loss factor (tan δ) of 0.15 to 0.25 at 23°C, 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, does not sag when manipulated in the oral cavity, and has excellent long-term stability at room temperature, allowing it to maintain a stable shape even during long-term storage.

[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] Dental composite resin composition

[0028] A dental composite resin composition according to one aspect of the present specification comprises 60 to 80 weight% of microfillers having an average particle size greater than 0.1 μm and less than or equal to 100 μm, and 4 to 5 weight% of nanofillers having an average particle size greater than 1 nm and less than or equal to 100 nm.

[0029] The above dental composite resin composition has a high viscosity due to the high filler content, and by controlling the nano-filler content, it does not stretch when manipulated in the oral cavity, exhibits excellent long-term stability at room temperature, maintains a stable shape even during long-term storage, and can demonstrate the effect of preventing liquid separation.

[0030] The average particle size of the above microfiller may be greater than 0.1 μm and less than or equal to 100 μm. For example, it may be 0.11 μm, 0.5 μm, 1 μm, 5 μm, 10 μm, 15 μm, 20 μm, 25 μm, 30 μm, 35 μm, 40 μm, 45 μm, 50 μm, 55 μm, 60 μm, 65 μm, 70 μm, 75 μm, 80 μm, 85 μm, 90 μm, 59 μm, 100 μm, or a range between two of these values.

[0031] The content of the microfiller is 60 to 80 wt% based on the total weight of the dental composite resin composition. For example, it may be 60 wt%, 61 wt%, 62 wt%, 63 wt%, 64 wt%, 65 wt%, 66 wt%, 67 wt%, 68 wt%, 69 wt%, 70 wt%, 71 wt%, 72 wt%, 73 wt%, 74 wt%, 75 wt%, 76 wt%, 77 wt%, 78 wt%, 79 wt%, 80 wt%, or a range between two of these values. If the content of the microfiller is less than the above range, the viscosity of the resin composition may decrease and take on a liquid form, and flowability may increase, making it difficult to restore the cavity. If the microfiller content exceeds the above range, the long-term stability of the composite resin may be reduced, or polymer formation through the curing of the composite resin may become difficult.

[0032] The average particle size of the above nanofiller may be 1 nm or more and 100 nm or less. For example, it may be 1 nm, 5 nm, 10 nm, 15 nm, 20 nm, 25 nm, 30 nm, 35 nm, 40 nm, 45 nm, 50 nm, 55 nm, 60 nm, 65 nm, 70 nm, 75 nm, 80 nm, 85 nm, 90 nm, 95 nm, 100 nm, or a range between two of these values.

[0033] The content of the nano-filler is 4 to 5 weight percent based on the total weight of the dental composite resin composition. For example, it may be 4 weight percent, 4.1 weight percent, 4.2 weight percent, 4.3 weight percent, 4.4 weight percent, 4.5 weight percent, 4.6 weight percent, 4.7 weight percent, 4.8 weight percent, 4.9 weight percent, 5 weight percent, or a range between two of these values. If the content of the nano-filler is less than the above range, the long-term stability of the composite resin at room temperature may be reduced, the resin may stretch when manipulated in the oral cavity, and a dilution phenomenon may occur. If the content of the nano-filler exceeds the above range, the resin may be too hard, making it difficult to manipulate in the oral cavity, and consequently, it may be difficult to form a restoration.

[0034] The content of the nano-filler may be 5 to 7 wt% based on the total content of the micro-filler and the nano-filler. For example, it may be 5 wt%, 5.1 wt%, 5.2 wt%, 5.3 wt%, 5.4 wt%, 5.5 wt%, 5.6 wt%, 5.7 wt%, 5.8 wt%, 5.9 wt%, 6 wt%, 6.1 wt%, 6.2 wt%, 6.3 wt%, 6.4 wt%, 6.5 wt%, 6.6 wt%, 6.7 wt%, 6.8 wt%, 6.9 wt%, 7 wt%, or a range between two of these values. If the content of the nano-filler is less than the above range, the long-term stability of the composite resin at room temperature may be reduced, the resin may stretch when manipulated in the oral cavity, and a slurry phenomenon may occur. If the nano-filler content exceeds the above range, the resin may become too hard, making it difficult to manipulate within the oral cavity, and consequently, it may be difficult to form a restoration.

[0035] The above microfillers and the above nanofillers may each independently be inorganic fillers, organic fillers, or a combination thereof.

[0036] The above microfiller and the above nanofiller may each be independently 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 are not limited thereto, and known inorganic fillers generally used in dental composite resin compositions may be used.

[0037] In one embodiment, the microfiller may be a barium silicate filler, and the nanofiller may be a fumed silica filler. In another 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.

[0038] The above dental composite resin composition may further include a di(meth)acrylate-based monomer.

[0039] The content of the above di(meth)acrylate-based monomer may be 12 to 35 weight percent based on the total weight of the dental composite resin composition.

[0040] The above di(meth)acrylate-based monomer may be one selected from the group consisting of polyalkylene glycol-based di(meth)acrylate, alkanediol di(meth)acrylate, glycerol di(meth)acrylate, bisphenol-A-based di(meth)acrylate, alkylene glycol-based di(meth)acrylate, and combinations of two or more of these, but is not limited thereto.

[0041] The above dental composite resin composition may further include 0.1 to 5 weight percent of polyalkylene glycol-based di(meth)acrylate.

[0042] 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, and if it exceeds the above range, the resin composition may exhibit a flowing formulation and fail to maintain a stable shape.

[0043] The above dental composite resin composition may further include 0.1 to 5 weight percent of alkanediol di(meth)acrylate.

[0044] 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 during handling of 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 a flowing formulation and fail to maintain a stable shape.

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

[0046] 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.

[0047] 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.

[0048] 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.

[0049] 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.

[0050] The above dental composite resin composition may further include 6 to 15 weight percent of bisphenol-A-based di(meth)acrylate.

[0051] 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.

[0052] The above dental composite resin composition may further include 0.1 to 5 weight percent of alkylene glycol-based di(meth)acrylate.

[0053] 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.

[0054] 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.

[0055] 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.

[0056] 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.

[0057] 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.

[0058] 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.

[0059] 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.

[0060] 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.

[0061] 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.

[0062] 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.

[0063] 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.

[0064] 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.

[0065] 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.

[0066] The above dental composite resin composition may be in the form of a paste.

[0067] The above dental composite resin composition may have a loss factor (tan δ) of 0.15 to 0.25 at 23°C, a frequency of 1 Hz, and an amplitude of 0.05%. For example, it may be 0.15, 0.16, 0.17, 0.18, 0.19, 0.2, 0.21, 0.22, 0.23, 0.24, 0.25, 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 long-term stability of the composite resin at room temperature may be reduced, the resin may stretch during manipulation in the oral cavity, and a synovial phenomenon may occur.

[0068] The above dental composite resin composition satisfies the above range for the loss factor (tan δ), which is the ratio of the loss modulus to the storage modulus at high vibration frequencies of 1 Hz or higher, so it does not stretch when manipulated in the oral cavity and has excellent long-term stability at room temperature, so it can maintain a stable shape even during long-term storage.

[0069] 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.

[0070] Examples and Comparative Examples

[0071] Polyethylene glycol dimethacrylate (PEGDMA), 1,12-dodecanediol dimethacrylate (1,12-DDDMA), a mixture of bisphenol-A glycidyl dimethacrylate (BisGMA) and triethylene glycol dimethacrylate (TEGDMA) (the weight ratio of BisGMA to TEGDMA is 8:2), bisphenol-A ethoxylate dimethacrylate (BisEMA), and additives were placed in a mixing vessel with the composition shown in Table 1 below and mixed at 50 rpm for 10 minutes in a 50 ℃ environment. As additives, a mixture of the photosensitizer camphorquinone, the photoinitiator ethyl-4-dimethylaminobenzoate (EDAB), the hardening inhibitor butyl-hydroxytoluene, the UV absorber 2-(2'-hydroxy-5'-methylphenyl)benzotriazole, and an iron oxide-based dye was used.

[0072] 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.

[0073] 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.

[0074] 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.

[0075] Classification (Weight%) Preliminary Comparative Example 1 Comparative Example 2 Comparative Example 3 Comparative Example 4 PEGDMA 2.3 2.3 2.3 2.3 2.3 1,12-DDDMA 2.3 2.3 2.3 2.3 2.3 BisGMA,TEGDMA Mixture 3 3 3 3 BisEMA 9.5 9.5 9.5 9.5 9.5 Additives 1.9 2 21.8 2 Micro-fillers 76.9 7.7 1 7.7 4 7.9 78 Nano-fillers 4.1 3.8 3.5 3.2 2.9

[0076] Experimental Example

[0077] Dental composite resin compositions prepared by the methods of the above Examples and Comparative Examples 1 to 4 were stored at room temperature, and their storage modulus (G') and loss modulus (G'') were measured at 2-week intervals for 8 weeks to check the change in values, and the loss coefficient (tan δ) was calculated therefrom.

[0078] The storage modulus and loss modulus of the dental composite resin composition were measured using a rheometer. A plate with a diameter of 25 mm was used as an accessory for measuring the 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%.

[0079] The results measured at 23 ℃, a frequency of 1 Hz, and an amplitude of 0.05% are shown in Table 2 below.

[0080] Classification 0 weeks (immediately after manufacturing) 2 weeks 4 weeks 6 weeks 8 weeks Example G' (Pa) 40 1,180 380,100 40 3,760 47 5,200 500,910 G'' (Pa) 78,370 75,392 74,810 87,467 102,880 tan δ (G'' / G') 0.20 0.20 0.19 0.18 0.21 Comparative Example 1 G' (Pa) 80,077 53,909 42,005 36,607 31,172 G'' (Pa) 23,387 15,807 10,753 10,24 49,014 tan δ (G'' / G') 0.29 0.29 0.26 0.28 0.29 Comparative Example 2 G' (Pa)36,007 30,042 28,760 24,946 23,166 G'' (Pa)10,244 9,275 8,529 7,479 6,374 tan δ (G'' / G')0.28 0.31 0.30 0.30 0.28 Comparative Example 3 G' (Pa)20,479 13,082 11,853 7,857 6,846 G'' (Pa)6,368 4,807 4,513 3,550 3,345 tan δ (G'' / G')0.31 0.37 0.38 0.45 0.49 Comparative Example 4 G' (Pa)19,470 15,641 12,917 10,536 8,650 G'' (Pa)7,6416,3595,3694,3313,750tan δ (G'' / G')0.390.410.420.410.43

[0081] Referring to Table 2 above, when comparing the measurement results immediately after preparation of Examples and Comparative Examples 1 to 4, it was confirmed that the higher the nano-filler content, the higher the storage modulus and loss modulus of the resin composition, and the lower the loss factor. In addition, changes in the fluidity of the composition were felt during handling of the resin composition depending on the change in nano-filler content, and it was confirmed that the higher the nano-filler content, the harder the formulation.

[0082] When comparing the results measured at 2-week intervals, it was confirmed that the dental composite resin composition prepared by the method of the example containing 4.1 wt% of nanofiller maintained a relatively constant storage modulus and loss modulus for 8 weeks, indicating excellent long-term stability at room temperature. On the other hand, it was confirmed that the dental composite resin composition prepared by the methods of Comparative Examples 1 to 4, in which the nanofiller content was less than 4 wt%, showed a decrease in storage modulus and loss modulus values ​​over time, indicating poor long-term stability at room temperature.

[0083] 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.

[0084] 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. 60 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 A dental composite resin composition comprising 4 to 5 weight percent of nanofillers having an average particle size of 1 nm or more and 100 nm or less.

2. In Paragraph 1, A dental composite resin composition in which the microfiller and the nanofiller are each independently 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.

3. In Paragraph 1, A dental composite resin composition further comprising a di(meth)acrylate-based monomer.

4. In Paragraph 3, A dental composite resin composition in which the content of the above di(meth)acrylate-based monomer is 12 to 35 weight percent based on the total weight of the dental composite resin composition.

5. In Paragraph 3, A dental composite resin composition in which the above di(meth)acrylate-based monomer is one selected from the group consisting of polyalkylene glycol-based di(meth)acrylate, alkanediol di(meth)acrylate, glycerol di(meth)acrylate, bisphenol-A-based di(meth)acrylate, alkylene glycol-based di(meth)acrylate, and combinations of two or more of these.

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

7. In Paragraph 6, 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.

8. In Paragraph 6, 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.

9. 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.

10. In Paragraph 9, 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.

11. In Paragraph 9, 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.

12. In Paragraph 9, A dental composite resin composition comprising the above bisphenol-A di(meth)acrylate, 1 to 5 weight% bisphenol-A glycidyl dimethacrylate and 5 to 10 weight% bisphenol-A ethoxylate dimethacrylate.

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 loss factor (tan δ) of 0.15 to 0.25 at 23 ℃, a frequency of 1 Hz, and an amplitude of 0.05%.