KR101937887B1 - Dental filling material composition cmoprising isosorbide derivatives - Google Patents

Abstract

[구조식 2]

이에 의하여, 본 발명의 아이소소바이드 유도체 화합물을 포함하는 조성물은 히드록시기(hydroxyl group) 및 메타크릴레이트기를 포함하는 아이소소바이드(isosorbide) 유도체 화합물과 우레탄계 화합물, 두 개의 메타크릴레이트기를 포함하는 글리콜계 화합물을 적절한 조성비로 배합하여 방향족 코어를 갖는 BisGMA 기반 치과용 충전재 대비 동등 또는 그 이상의 기계적 강도를 가지며, 인체 무해, 수축률 및 수분흡수율이 개선시키는 효과가 있다.The present invention relates to a composition comprising a compound represented by the following Structural Formula (1) and Structural Formula (2).
[Structural formula 1]

[Structural formula 2]

Accordingly, the composition containing the isosorbide derivative compound of the present invention can be produced by reacting an isosorbide derivative compound having a hydroxyl group and a methacrylate group with a urethane compound, a glycol-based compound having two methacrylate groups Compounds having a mechanical strength equal to or higher than that of BisGMA-based dental fillers having an aromatic core are compounded at an appropriate composition ratio and have the effect of improving the harmlessness of human body, shrinkage rate and water absorption rate.

Description

[0001] DENTAL FILLING MATERIAL COMPOSITION CMOPRISING ISOSORBIDE DERIVATIVES [0002]

The present invention relates to a composition comprising an isosorbide derivative compound, and more particularly to a composition comprising an isosorbide derivative compound containing a hydroxy group and a methacryl group and a urethane compound, The present invention relates to a dental filler composition comprising a glycol compound.

Curable materials such as adhesives, adhesives, sealants, coatings and paints are currently being used in various industrial fields such as packaging, bookbinding, automotive, electronics, precision, optical products, woodworking, plywood, It is widely used for home use, and its use has become widespread, and recently it has also been applied to concrete. Such adhesives and the like are manufactured in the form of a mixture of chemical materials based on a synthetic resin. Since the volatile organic compounds (VOC) are added due to the organic solvent (solvent) used in the manufacturing process and various volatile additives added to improve the physical properties, , Dioxins, and environmental hormones. In recent years, environmental regulations under international agreements have strictly restricted the production and use of these harmful substances. Furthermore, the EU has used such regulations as a means of new trade sanctions. In keeping with this trend, conventional solvent type adhesives have been replaced by water-soluble, solvent-free, hot-melt type and the like. Furthermore, not only these adhesive materials, but most of the fine chemical materials we currently use are petrochemical products derived from the Oil Refinery Process. However, international oil prices are steadily rising due to a decrease in reserves and a surge in demand centering on BRICs. As international conventions that strictly regulate greenhouse gas emissions become effective, future use of irreversible fossil resources such as oil will lead to enormous environmental costs . Therefore, many efforts have been made to obtain existing petroleum-derived fine chemical products from new resources, and the most representative example is to use carbohydrate-based biomass as a supply source. The natural world produces about 170 billion tons of carbohydrates every year through photosynthesis. Human beings use only about 3% of them as food, paper, furniture, and building materials. Thus, fine chemicals manufactured from renewable and sustainable carbohydrate biomass are expected to replace petrochemicals. Accordingly, in order to replace conventional light source curing adhesive materials derived from petroleum resources, development of a technology for synthesizing compounds having predetermined adhesion or adhesion properties using such environmentally friendly carbohydrate-based biomass is required. As a representative example of the carbohydrate-based biomass, there is an isosorbide derivative.

Isosorbide is a heterocyclic compound derived from glucose, which can be obtained by hydrogenating glucose to form sorbitol, which can be double dehydrated. Isosorbide is a V-shaped material with two tetrahydrofuran rings joined at an angle of 120 ° and has a hydroxyl group at carbon positions 2 and 5. Isosorbide is a compound of a solid structure having optical asymmetry, and derivatives thereof are useful as raw materials for pharmaceutical raw materials and high-functional industrial materials in that they exhibit specific functions. In addition, isosorbide is excellent in optical properties and thermal properties and is used in optical electronic components such as optical disk substrates, optical fibers, and lenses. In addition, the composition of the present invention can be utilized as a composition of a dental filler by applying an isosorbide derivative. Bisphenol-based 2,2-bis- (4- (2-hydroxy-3-methacryloyloxypropoxy) phenyl) propane (BisGMA) is most commonly used as a prepolymer of a dental material composition. This has a drawback in that when it is used as a dental material, it penetrates into fine parts of the teeth and the dispersion efficiency is lowered when the dental composite resin is manufactured, since it has a very high viscosity and a high molecular weight as compared with other acrylic monomers. In order to overcome such disadvantages, dimethacrylate monomer having lower molecular weight and lower viscosity than BisGMA is used as a diluent, and triethylene glycol dimethacrylate (TEGDMA) is a typical diluent. However, the addition of the diluent results in decreasing the average molecular weight of the whole molecule, thus increasing the polymerization shrinkage rate. Also, the bisphenol-based compound has a small degree of polymerization shrinkage and has advantages such as excellent strength of a polymerized product using it. However, the bisphenol-based compound is useful to be applied to a matrix resin and the like, but has a problem that it can act as estrogen in the human body and cause endocrine disruption there was. In order to solve such a problem, there has been an effort to replace it with an isosorbide-based compound derived from biomass which is harmless to human body.

However, such isobide-based compounds are harmless to the human body, unlike bisphene-based BisGMA, but have poor mechanical strength such as flexural strength and compressive strength because of less toughness of the main chain than BisGMA having an aromatic core. Since the compound has a property of absorbing water when it contains a hydroxy group, there is a problem that when the compound is used as a dental filler or the like, the mechanical strength is decreased and the aesthetic property is lowered.

Korean Patent No. 10-0739935

The object of the present invention is to solve the above-mentioned problems, and an object of the present invention is to provide a process for producing an isosorbide derivative compound containing a hydroxyl group and a methacrylate group, a urethane compound and a glycol compound containing two methacrylate groups, Wherein the dental filler composition comprises an isosorbide derivative compound having a mechanical strength equal to or higher than that of a bisGMA based dental filler having an aromatic core and having improved harmlessness, shrinkage and water absorption.

According to an aspect of the present invention, there is provided a compound represented by the following structural formula 1; And a compound represented by the following structural formula 2; ≪ / RTI >

[Structural formula 1]

In formula 1,

R ¹ and R ² may be the same or different from each other and are each independently selected from a hydrogen atom, a C 1 to C 6 alkyl group, a C 2 to C 6 alkenyl group, a C 2 to C 6 alkynyl group, a C 5 to C 6 cycloalkyl group, and a C 6 to C 10 aryl group It is either.

[Structural formula 2]

In formula 2,

n is an integer of 2 to 5,

R ³ and R ² may be the same or different and are each independently selected from a hydrogen atom, a C 1 to C 6 alkyl group, a C 2 to C 6 alkenyl group, a C 2 to C 6 alkynyl group, a C 5 to C 6 cycloalkyl group, and a C 6 to C 10 aryl group It is either.

Wherein the composition is a compound represented by the following structural formula 3; May be further included.

[Structural Formula 3]

In Structure 3,

R ⁵ and R ^{6, which} may be the same or different, are each independently selected from a hydrogen atom, a C 1 to C 6 alkyl group, a C 2 to C 6 alkenyl group, a C 2 to C 6 alkynyl group, a C 5 to C 6 cycloalkyl group, and a C 6 to C 10 aryl group Any one,

R ⁷ and R ⁸ may be the same or different from each other and are each independently selected from a hydrogen atom, a C 1 to C 6 alkyl group, a C 2 to C 6 alkenyl group, a C 2 to C 6 alkynyl group, a C 5 to C 6 cycloalkyl group, and a C 6 to C 10 aryl group Any one,

and q is an integer of 1 to 10.

And n may be 3.

R ¹ to R ⁴ may be the same or different from each other and each independently may be a hydrogen atom or a methyl group.

R ⁵ to R ⁶ may be the same or different from each other, and each independently may be a hydrogen atom or a methyl group.

The composition may further comprise a filler.

Wherein the filler is selected from the group consisting of barium aluminosilicate, synthetic amorphous silica, crystalline silica, barium silicate, barium borosilicate, barium fluoroaluminoborosilicate fluoroaluminoborosilicate, barium aluminoborosilicate, strontium silicate, strontium borosilicate, strontium aluminoborosilicate, calcium silicate, aluminosilicate at least one selected from alumino silicate, silicon nitride, titanium dioxide, calcium hydroxyapatite, zirconia, and bioactive glass.

Wherein the composition comprises 100 parts by weight of the compound represented by Formula 1; And 100 to 100 parts by weight of the compound represented by Formula 2; . ≪ / RTI >

The composition may further comprise 20 to 100 parts by weight of a compound represented by the following structural formula (3).

[Structural Formula 3]

In Structure 3,

R ⁵ and R ^{6, which} may be the same or different, are each independently selected from a hydrogen atom, a C 1 to C 6 alkyl group, a C 2 to C 6 alkenyl group, a C 2 to C 6 alkynyl group, a C 5 to C 6 cycloalkyl group, and a C 6 to C 10 aryl group Any one,

R ⁷ and R ⁸ may be the same or different from each other and are each independently selected from a hydrogen atom, a C 1 to C 6 alkyl group, a C 2 to C 6 alkenyl group, a C 2 to C 6 alkynyl group, a C 5 to C 6 cycloalkyl group, and a C 6 to C 10 aryl group Any one,

and q is an integer of 1 to 10.

The composition may further comprise a filler, wherein the filler content may be 20 to 80 wt% based on the composition comprising the filler.

The compound represented by Formula 1 may be a compound represented by Formula 1 below.

[Chemical Formula 1]

The compound represented by Formula 2 may be a compound represented by Formula 2 below.

(2)

The compound represented by Formula 3 may be a compound represented by Formula 3 below.

(3)

According to another aspect of the present invention, there is provided a dental filler comprising the composition.

The composition comprising the isosorbide derivative compound of the present invention can be prepared by reacting an isosorbide derivative compound containing a hydroxyl group and a methacrylate group with a urethane compound and a glycol compound containing two methacrylate groups Composition ratio, which is equivalent to or higher than that of a bisGMA-based dental filling material having an aromatic core, is harmless to the human body and has an effect of improving shrinkage and water absorption rate.

1 is a graph showing the result of analysis of compressive strength according to the composition ratio of the composition according to Test Example 1. Fig.
FIG. 2 is a graph showing the results of analysis of the compressive strength and flexural strength according to Test Example 2. FIG.
3 is a graph showing the results of analysis of resin shrinkage ratios according to Test Example 3. Fig.
4 is a graph showing the results of analysis of water absorption according to Test Example 4. Fig.
5 is a graph showing the results of thermal property change analysis of the composition of Example 1 according to Test Example 5. Fig.

The invention is capable of various modifications and may have various embodiments, and particular embodiments are exemplified and will be described in detail in the detailed description. It is to be understood, however, that the invention is not to be limited to the specific embodiments, but includes all modifications, equivalents, and alternatives falling within the spirit and scope of the invention. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS Hereinafter, the present invention will be described in detail with reference to the accompanying drawings.

Furthermore, terms including an ordinal number such as first, second, etc. to be used below can be used to describe various elements, but the constituent elements are not limited by the terms. The terms are used only for the purpose of distinguishing one component from another. For example, without departing from the scope of the present invention, the first component may be referred to as a second component, and similarly, the second component may also be referred to as a first component.

Also, when an element is referred to as being "formed" or "laminated" on another element, it may be directly attached or laminated to the front surface or one surface of the other element, It will be appreciated that other components may be present in the < / RTI >

The singular expressions include plural expressions unless the context clearly dictates otherwise. In the present application, the terms "comprises" or "having" and the like are used to specify that there is a feature, a number, a step, an operation, an element, a component or a combination thereof described in the specification, But do not preclude the presence or addition of one or more other features, integers, steps, operations, elements, components, or combinations thereof.

Hereinafter, the dental filler composition comprising the isosorbide derivative of the present invention will be described.

A compound represented by the following structural formula 1; And a compound represented by the following structural formula 2; ≪ / RTI >

 [Structural formula 1]

In formula 1,

R ¹ and R ² may be the same or different from each other and are each independently selected from a hydrogen atom, a C 1 to C 6 alkyl group, a C 2 to C 6 alkenyl group, a C 2 to C 6 alkynyl group, a C 5 to C 6 cycloalkyl group, and a C 6 to C 10 aryl group It is either.

[Structural formula 2]

In formula 2,

n is an integer of 2 to 5, R ³ and R ⁴ may be the same or different from each other and each independently represents a hydrogen atom, a C 1 to C 6 alkyl group, a C 2 to C 6 alkenyl group, a C 2 to C 6 alkynyl group, C6 cycloalkyl group, and a C6 to C10 aryl group.

Wherein the composition is a compound represented by the following structural formula 3; May be further included.

 [Structural Formula 3]

In Structure 3,

R ⁵ and R ^{6, which} may be the same or different, are each independently selected from a hydrogen atom, a C 1 to C 6 alkyl group, a C 2 to C 6 alkenyl group, a C 2 to C 6 alkynyl group, a C 5 to C 6 cycloalkyl group, and a C 6 to C 10 aryl group Any one,

R ⁷ and R ⁸ may be the same or different from each other and are each independently selected from a hydrogen atom, a C 1 to C 6 alkyl group, a C 2 to C 6 alkenyl group, a C 2 to C 6 alkynyl group, a C 5 to C 6 cycloalkyl group, and a C 6 to C 10 aryl group Any one,

and q is an integer of 1 to 10.

Preferably n can be 3.

R ¹ to R ⁴ may be the same or different from each other and each independently may be a hydrogen atom or a methyl group, more preferably a methyl group.

R ⁵ to R ⁸ may be the same or different, and each independently may be a hydrogen atom or a methyl group.

The composition may further comprise a filler.

The filler may be selected from the group consisting of barium aluminosilicate, synthetic amorphous silica, crystalline silica, barium silicate, barium borosilicate, barium fluoroaluminoborosilicate fluoroaluminoborosilicate, barium aluminoborosilicate, strontium silicate, strontium borosilicate, strontium aluminoborosilicate, calcium silicate, aluminosilicate alumino silicate, silicon nitrides, titanium dioxide, calcium hydroxyapatite, zirconia, and bioactive glass, and preferably barium Aluminosilicates can be used.

100 parts by weight of the compound represented by the structural formula 1; And 10 to 100 parts by weight of the compound represented by Formula 2; . ≪ / RTI >

Wherein the composition comprises 20 to 100 parts by weight of a compound represented by the following structural formula 3; . ≪ / RTI >

[Structural Formula 3]

In Structure 3,

R ⁵ and R ^{6, which} may be the same or different, are each independently selected from a hydrogen atom, a C 1 to C 6 alkyl group, a C 2 to C 6 alkenyl group, a C 2 to C 6 alkynyl group, a C 5 to C 6 cycloalkyl group, and a C 6 to C 10 aryl group Any one,

R ⁷ and R ⁸ may be the same or different from each other and are each independently selected from a hydrogen atom, a C 1 to C 6 alkyl group, a C 2 to C 6 alkenyl group, a C 2 to C 6 alkynyl group, a C 5 to C 6 cycloalkyl group, and a C 6 to C 10 aryl group Any one,

and q is an integer of 1 to 10.

The composition may further comprise a filler and the filler content may be 20 to 80 wt%, preferably 25 to 75 wt%, based on the composition comprising the filler.

The compound represented by Formula 1 may be a compound represented by Formula 1 below.

[Chemical Formula 1]

The compound represented by Formula 2 may be a compound represented by Formula 2 below.

(2)

The compound represented by Formula 3 may be a compound represented by Formula 3 below.

(3)

The composition may be used as a dental filler.

[Example]

Manufacturing example  One: IsoGMA  Preparation of compounds

(Step 1)

Eye 50mL round bottom flask into the Sound carbide (isosorbide) (1-1) (1.0g , 6.8mmol), KOH (2.8g, 42mmol) and then covered with a rubber septum under N ₂ gas atmosphere in dry DMSO (dimethyl sulfoxide) ( 5 mL) was added. A round bottom flask containing the reaction solution was immersed in a bath of 40 and thermally equilibrated. When the inside of the flask was thermally equilibrated, epibromohydrin (3.84 g, 28 mmol) was slowly added via the syringe. At this time, as the suspension was slowly added, the color of the suspension inside the flask was gradually changed to dark brown. After the dropwise addition, the mixture was reacted by stirring at 40 for 2 hours. Thereafter, the reaction solution was filtered through a syringe filter to remove salts from the residue, the filtrate was diluted with an appropriate amount of methylene chloride, and transferred to a separating funnel. Washed successively with distilled water and brine, dried over anhydrous magnesium sulfate (MgSO ₄ ) to remove water from the organic layer, and the organic layer was filtered. The organic matter obtained by filtration was concentrated under reduced pressure using a rotary distillation apparatus and separated by flash chromatography (hexane: ethyl acetate = 1: 1) to obtain Compound (1-2) (1.1 g, 4.3 mmole, 63%).

The reaction of Step 1 is as shown in Scheme 1 below.

[Reaction Scheme 1]

(Step 2)

To a 100 mL round bottom flask under nitrogen was added the compound (1-2) (1 g, 3.8 mmol), diphenyl picrylhydrazyl (10 mg, 0.6 mmol), and methacrylic acid acid (7 mL, 78 mmol) were added and stirred. Then, 3 drops of triethylamine (TEA) was added, and the mixture was stirred at 100 for 4 hours. After completion of the reaction, a dark brown reaction solution was obtained. The reaction solution was transferred to a separatory funnel, washed 5 times with 20 wt% NaHCO ₃ aqueous solution and treated with water / ethyl acetate (water / EA). The organic layer of the treated product was distilled to remove the solvent and then IsoGMA was prepared (1.23 g, 2.9 mmole, 75%) by flash chromatography of hexane: ethyl acetate (1: 2, v / v).

The reaction of Step 2 is shown in Reaction Scheme 2 shown below.

[Reaction Scheme 2]

Manufacturing example  2: TEGDMA  Compound manufacturing

TEGDMA (95%) was purchased from Sigma-Aldrich (Milwaukee, Wis.).

Manufacturing example  3: UDMA  Compound manufacturing

UDMA was purchased from Esstech Inc (Essington, Pa.) Under the code name X-850-0000.

Example  One: Isosobaid  Derivative compound composition ( IsoGMA: TEGDMA: UDMA = 4: 3: 3) Production

2 g of the compound (IsoGMA) prepared according to Preparation Example 1, 1.5 g of TEGDMA (95%, Sigma-Aldrich) and 1.5 g of UDMA (X-850-0000) were weighed and then camphorquinone and ethyl 4- (dimethylamino) benzoate 1% by weight of the initiator mixed at a weight ratio of 1: 2 was added, and the mixture was mixed at 2000 rpm for 90 seconds using a planetary vacuum mixer to prepare a mixture having a composition ratio of IsoGMA: TEGDMA: UDMA = 4: 3: 3. 7.5 g of barium aluminosilicate as a filler was added to the mixture, and the resulting mixture was mixed with a planetary vacuum mixer at 2000 rpm for 30 seconds to prepare an isosorbide derivative compound composition.

Example  2: Isosobaid  Preparation of derivative compound composition (IsoGMA: TEGDMA: UDMA = 6: 1: 3)

Except that the mixture of IsoGMA: TEGDMA: UDMA = 6: 1: 3 (3 g of IsoGMA, 0.5 g of TEGDMA, and 1.5 g of UDMA) was used instead of the mixture of Example 1, A derivative compound composition was prepared.

Example  3: Isosobaid  Production of derivative compound composition (IsoGMA: TEGDMA: UDMA = 5: 3: 2)

Except that the mixture of IsoGMA: TEGDMA: UDMA = 5: 3: 2 (IsoGMA 2.5 g, TEGDMA 1.5 g, UDMA 1 g) was used instead of the mixture of Example 1, A derivative compound composition was prepared.

Example  4: Isosobaid  Derivative compound composition  ( IsoGMA: TEGDMA = 9: 1) Production

The isosorbide derivative composition was prepared in the same manner as in Example 1, except that a mixture of IsoGMA: TEGDMA = 9: 1 (4.5 g of IsoGMA, 0.5 g of TEGDMA) was used instead of the mixture of Example 1.

Example  5: Isosobaid  Derivative compound composition  ( IsoGMA: TEGDMA = 8: 2) Production

The isosorbide derivative compound composition was prepared in the same manner as in Example 1, except that a mixture of IsoGMA: TEGDMA = 8: 2 (4 g of IsoGMA, 1 g of TEGDMA) was used instead of the mixture of Example 1.

Example  6: Isosobaid  Derivative compound composition  ( IsoGMA: TEGDMA = 7: 3) Manufacturing

The isosorbide derivative compound composition was prepared in the same manner as in Example 1 except that a mixture of IsoGMA: TEGDMA = 7: 3 (IsoGMA: 3.5 g, TEGDMA: 2.5 g) was used instead of the mixture of Example 1.

Comparative Example  One: BisGMA: TEGDMA  Composition manufacturing

(BisGMA: TEGDMA = 6: 4 weight ratio (wt%)) was prepared by quantifying 3 g of the compound represented by the following formula (4) (BisGMA) and 2 g of the compound represented by the following formula (5) 1 wt% of camphorquinone and ethyl 4- (dimethylamino) benzoate in an amount of 1: 2 by weight was added and mixed at 2000 rpm for 90 seconds using a planetary vacuum mixer. 7.5 g of barium aluminosilicate as a filler was added to the prepared mixture and mixed at 2000 rpm for 30 seconds with a planetary vacuum mixer to prepare a dental filling material.

[Chemical Formula 4]

[Chemical Formula 5]

Comparative Example  2: IsoGMA  Composition manufacturing

Except that the IsoGMA prepared according to Preparation Example 1 was used instead of the mixture (BisGMA: TEGDMA = 6: 4 weight ratio (wt%)) of Comparative Example 1, .

[Test Example]

Test Example  1: Compressive Strength Analysis according to Composition Ratio of Composition

Figure 1 shows the compressive strength results of the compositions of Examples 1 to 3, which are compositions comprising both IsoGMA, TGEDMA and UDMA, and the compositions of Examples 4 to 6, which are compositions comprising IsoGMA and TGEDMA.

Specimens for measuring the compressive strength were prepared by filling a cylindrical (Φ x L = 4 x 6 mm) SUS mold with a prepared resin mixture and using a 3M ESPE Elipar ^TM S10 was irradiated with visible light for 40 seconds on the front and back surfaces using a spot cure apparatus. The prepared compressive strength specimens were subjected to measurements according to the International Standard Test (ISO4049) at Lord Sell 5000N, crosshead speed 1 mm / min, using universal testing machine (UTM) Shimadzu AGS-X.

According to this, the compositions of Examples 1 to 3 and Example 5 showed high compressive strength. In particular, the compressive strength of the composition of Example 1 having a ratio of IsoGMA, TGEDMA and UDMA of 4: 3: 3 was found to be the highest, and it was analyzed to be an optimal composition ratio that can improve the compressive strength.

Test Example  2: Compressive Strength and Flexural Strength Analysis

3 and Table 1 show the results of flexural strength and compressive strength analysis of the compositions prepared according to Comparative Examples 1 and 2 and Examples 1 and 5.

Specimens for measuring the compressive strength were prepared by filling a cylindrical (Φ x L = 4 x 6 mm) SUS mold with a prepared resin mixture and using a 3M ESPE Elipar ^TM The specimen was irradiated with visible light for 40 seconds on the front and back sides using a S10 spot cure apparatus. For the flexural strength measurement, specimens were filled in a rectangular parallelepiped (H x W x L = 2 x 2 x 25 mm) SUS mold and irradiated with visible light for 20 sec each by dividing each side with a spot cure device , And the other side was irradiated by the same method. The compressive strength of the specimens was measured at Lord Sell 5000N, crosshead speed 1mm / min using a universal testing machine UTM (Universal Testing Machine) Shimadzu AGS-X. The strength was measured. Measurement was carried out according to the international standard test (compression strength: ISO9917, flexural strength: ISO4049).

Compressive Strength ( MPa ) Flexural Strength ( MPa ) Comparative Example  One 326.7 138.9 Comparative Example  2 223.4 78.6 Example  5 258.8 120.2 Example  One 324.9 148.1

2 and Table 1, it was confirmed that the compositions of Examples 1 and 5 were superior to the composition of Comparative Example 2 in the compressive strength and flexural strength, and were similar to those of Comparative Example 1.

Test Example 3: Resin Shrinkage Analysis

Fig. 3 shows the results of the resin shrinkage analysis of the compositions prepared according to Comparative Examples 1 and 2 and Examples 1 and 5. Fig.

In order to measure the shrinkage rate, 1 mL of the composition was dropped onto a slide glass, covered with a stainless steel plate, and then irradiated with light under a slide glass to microscopically move the sample in the irradiated direction. Using a linear variable differential transducer (LVDT) Were measured.

According to the results, the compositions prepared according to Examples 1 and 5 have a relatively low hardening shrinkage ratio as compared with the composition of Comparative Example 1, and thus the stability is high.

Test Example 4: Analysis of Water Sorption (Water Sorption)

Figure 4 shows the results of the analysis of the water absorption of the compositions prepared according to Comparative Examples 1 and 2 and Examples 1 and 5.

Measurement specimens for measuring water absorption were prepared by filling a prepared resin mixture with a cylindrical SUS mold (Φ x L = 15 × 1 mm) and using a 3M ESPE Elipar ^™ S10 spot cure apparatus was used to irradiate visible light for 8 seconds around the center and center for 20 seconds, respectively. The water absorption measurement was carried out in accordance with the International Standard Test (ISO4049) as follows. The weight of the prepared specimens was measured, and the specimens were dried until the specimens were uniformly weighed. The weight of M ₀ and was wiped with a specimen of phosphate buffer solution (Phosphate buffer solution, PBS, pH = 7.41) was taken out after 10ml put in a containing vial was allowed to stand for 7 days 37 ℃ oven smooth the sample surface absorptive good paper. Then, it was put in a desiccator for 1 hour, dried and then weighed. At this time, the sample was dried until the weight of the sample became constant. This weight is called M ₇ . The water absorption was calculated by the following equation.

WS (/ / mm ³ ) = M ₇ - M ₀ / V

Where V is the initial volume of the sample.

According to this, the compositions of Examples 1 and 5 showed lower water absorption than the composition of Comparative Example 2. Therefore, it was confirmed that the physical properties of the composition prepared according to the production method of the present invention are improved.

Test Example 5: Dynamic Mechanical Analysis (DMA)

5 is a graph showing the thermal property change analysis result of the composition prepared according to Example 1. Fig.

In order to measure the change of thermal properties, the test specimens were filled in a rectangular parallelepiped (H x W x L = 1 x 2 x 35 mm) SUS mold, and each surface was divided into 5 equal parts using a spot cure apparatus for 20 seconds Visible light was irradiated and the other side was irradiated by the same method. The measurement was carried out at a frequency of 1 Hz and a heating rate of 3 / min in a range of 20-200 ° C using DMA-2980 manufactured by TA Instrument.

Referring to the results of FIG. 5, the glass transition temperature of the composition of Example 1 was found to be 139.86 ° C. As a result, it can be seen that the composition of Example 1 is very stable to thermal changes, and it is difficult to cause cracks due to thermal deformation at a temperature of 100 or less.

While the present invention has been particularly shown and described with reference to exemplary embodiments thereof, it is to be understood that the invention is not limited to the disclosed embodiments, but, on the contrary, It is possible.

Claims (14)

A compound represented by the following structural formula 1; And
A compound represented by the following structural formula 2;
≪ / RTI >
[Structural formula 1]

In formula 1,
R ¹ and R ² may be the same or different from each other and are each independently selected from a hydrogen atom, a C 1 to C 6 alkyl group, a C 2 to C 6 alkenyl group, a C 2 to C 6 alkynyl group, a C 5 to C 6 cycloalkyl group, and a C 6 to C 10 aryl group It is either.
[Structural formula 2]

In formula 2,
n is an integer of 2 to 5,
R ³ and R ⁴ may be the same or different and are each independently selected from a hydrogen atom, a C 1 to C 6 alkyl group, a C 2 to C 6 alkenyl group, a C 2 to C 6 alkynyl group, a C 5 to C 6 cycloalkyl group, and a C 6 to C 10 aryl group It is either. The method according to claim 1,
Wherein the composition is a compound represented by the following structural formula 3; ≪ / RTI >
[Structural Formula 3]

In Structure 3,
R ⁵ and R ^{6, which} may be the same or different, are each independently selected from a hydrogen atom, a C 1 to C 6 alkyl group, a C 2 to C 6 alkenyl group, a C 2 to C 6 alkynyl group, a C 5 to C 6 cycloalkyl group, and a C 6 to C 10 aryl group Any one,
R ⁷ and R ⁸ may be the same or different from each other and are each independently selected from a hydrogen atom, a C 1 to C 6 alkyl group, a C 2 to C 6 alkenyl group, a C 2 to C 6 alkynyl group, a C 5 to C 6 cycloalkyl group, and a C 6 to C 10 aryl group Any one,
and q is an integer of 1 to 10. The method according to claim 1,
n is 3. < Desc / Clms Page number 17 > The method according to claim 1,
Wherein R ¹ to R ⁴ may be the same or different from each other and are each independently a hydrogen atom or a methyl group. 5. The method of claim 4,
R ⁵ to R ⁸ may be the same or different from each other and are each independently a hydrogen atom or a methyl group. The method according to claim 1,
Wherein the composition further comprises a filler. The method according to claim 6,
Wherein the filler is selected from the group consisting of barium aluminosilicate, synthetic amorphous silica, crystalline silica, barium silicate, barium borosilicate, barium fluoroaluminoborosilicate fluoroaluminoborosilicate, barium aluminoborosilicate, strontium silicate, strontium borosilicate, strontium aluminoborosilicate, calcium silicate, aluminosilicate wherein the composition is at least one selected from the group consisting of alumino silicate, silicon nitrides, titanium dioxide, calcium hydroxyapatite, zirconia, and bioactive glass. . The method according to claim 1,
100 parts by weight of the compound represented by the structural formula 1; And
10 to 100 parts by weight of the compound represented by the structural formula 2; To
≪ / RTI > 9. The method of claim 8,
Wherein the composition further comprises 20 to 100 parts by weight of a compound represented by the following structural formula (3).
[Structural Formula 3]

In Structure 3,
R ⁵ and R ^{6, which} may be the same or different, are each independently selected from a hydrogen atom, a C 1 to C 6 alkyl group, a C 2 to C 6 alkenyl group, a C 2 to C 6 alkynyl group, a C 5 to C 6 cycloalkyl group, and a C 6 to C 10 aryl group Any one,
R ⁷ and R ⁸ may be the same or different from each other and are each independently selected from a hydrogen atom, a C 1 to C 6 alkyl group, a C 2 to C 6 alkenyl group, a C 2 to C 6 alkynyl group, a C 5 to C 6 cycloalkyl group, and a C 6 to C 10 aryl group Any one,
and q is an integer of 1 to 10. 9. The method of claim 8,
Wherein the composition further comprises a filler, wherein the filler content is 20 to 80 wt%, based on the composition comprising the filler. The method according to claim 1,
Wherein the compound represented by Formula 1 is a compound represented by Formula 1 below.
[Chemical Formula 1]

The method according to claim 1,
Wherein the compound represented by Formula 2 is a compound represented by Formula 2 below.
(2)

3. The method of claim 2,
Wherein the compound represented by Formula 3 is a compound represented by Formula 3 below.
(3)

A dental filler comprising the composition of claim 1.

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