JP2006193438A - Dental repairing material kit and its using method - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a dental repairing material which allows ready preparation of a resin frame material providing paste easy to build up and exhibiting good adaptability to an abutment tooth and is suitable for enhancing impact resistance of dental repairing materials such as a hard resin, a hybrid resin, a resin inlay or a resin onlay, and a lining material kit such as a composite resin. <P>SOLUTION: The dental repairing material kit comprises a dental repairing material composition (D) and a low viscous composition (E) in an uncontacted state with the dental repairing material composition (D), where the dental repairing material composition (D) comprises 100 pts.wt. of a polymerizable monomer (A), 1-900 pts.wt. of a filler (B) including an inorganic short fiber (B1), and a polymerization initiator (C) and the low viscous composition (E) comprises an organic solvent (E0) and/or a soluble polymerizable monomer (E1) having a boiling point within the range of 30-130°C under pressure of 1 atm and has viscosity of at most 30,000 mPa×s at 25°C. <P>COPYRIGHT: (C)2006,JPO&NCIPI

Description

  The present invention relates to a dental restorative material kit suitable for actually using a dental restorative material composition and a method for using the same. More particularly, the present invention relates to a dental restorative material kit having a dental restorative material composition suitably used for, for example, preparation of a dental frame and a crown backing material, and a method of using the same. In addition, the present invention relates to a dental restorative material kit and a method for using the same, in a form that is easy to use according to the actual use form of such a dental restorative material composition. Furthermore, the present invention provides a dental restorative kit particularly suitable for forming frame materials and crown lining materials with improved mechanical strength, in particular impact and fracture resistance, and dental restorations thereof. The present invention relates to a method of actually using a material kit.

  Resin-based dental restoration materials such as resin inlays, resin onlays, artificial teeth, hard crown resins, hybrid resins for crowns, composite resins, etc. are easy to operate and can synchronize color with natural teeth. In recent years, it has been frequently used in place of metal-based dental restorations because of its good aesthetics, easy restoration, and improved mechanical properties.

  Such resin-based dental restorative materials are usually provided in the form of a paste mainly composed of a (meth) acrylate-based polymerizable monomer, an inorganic particulate filler, and a photopolymerization initiator. However, the operability of the paste, aesthetics before and after curing, mechanical properties, impact resistance, and other performances, the type of (meth) acrylate-based polymerizable monomer, the type of filler or It is known that it greatly depends on the shape, particle size distribution, particle size, filling rate and the like.

For example, as a (meth) acrylic acid ester polymerizable monomer, Japanese Patent Application No. 58-174452 (
Patent Document 1) proposes a dental material containing a specific di (meth) acrylic ester, and describes that the use of this polymerizable monomer improves the mechanical properties of the cured product. Yes.

  Japanese Patent Laid-Open No. 2000-80013 (Patent Document 2) discloses a cured product obtained by previously combining inorganic oxide fine particles having an average particle size of 1 μm or less and a polymerizable monomer in advance of several μm or more. Describes a method using a composite powder of an inorganic oxide and a polymer obtained by pulverization.

  By using such a composite powder, the filling rate of the filler can be increased compared with the case where the inorganic oxide fine powder is blended alone, so that the mechanical strength is maintained while maintaining the operability of the paste. It is described that it is possible to prevent a decrease in the above. However, in a dental restoration material using a specific polymerizable monomer described in the above publication or a dental restoration material in which an inorganic oxide is combined with a polymer, the mechanical strength is increased, but the oral cavity As for the problems related to the fracture of the dental restorative material that occurs during the mounting, there is not yet a sufficient solution.

  Therefore, in order to prevent breakage when using the above-mentioned dental restorative agent, it is used as a restoration for a crown such as a hard resin anterior crown used for anterior teeth. When using a metal frame material with excellent mechanical properties on the back side of the hard crown resin, the resin and metal are combined to improve the mechanical properties and occlusion. A method is adopted in which the resin is not used as much as possible in the portion where the pressure is applied, and the restoration of the restoration for the crown is prevented.

However, in recent years, as the performance of dental resins has improved, resin jacket crowns that do not use metal at all have begun to spread, and restoration materials for crowns called hybrid ceramics for the restoration of molars and the like that are subject to high occlusal pressure Have already started to be used, and in the actual dental treatment, the resin for the crown has begun to be used.

However, in the actual oral cavity, there still remains a problem that the restoration of a crown restoration or breakage occurs due to the weakness of mechanical properties, particularly impact resistance.
Therefore, clinical application of a method for improving the impact resistance of a frame material by using a polymethacrylate sheet instead of a metal as a frame material of a hard resin for a crown is being studied. However, because the adhesion between the sheet used here and the hard resin is not sufficient, the sheet may peel off at the joint surface, and the sheet as described above is faithful to the shape of the abutment tooth model. The method using this sheet has a problem in operability, for example, it is very difficult to mold together.

  Therefore, in the field of dental restoration, resin jacket crowns, resin crowns, resin inlays, resin onlays, which are particularly excellent in mechanical properties such as mechanical toughness, impact resistance and fracture resistance of resin-based dental restoration materials, Artificial teeth, composite resins, etc. are desired.

Under such a demand, as a method for increasing the strength of a known restoration material for a crown, Japanese Patent Laid-Open No. 5-310525 (Patent Document 3) discloses that a converging yarn of long fibers such as glass fibers and aramid fibers is acrylic. A resin composition for reinforcing a hard resin jacket crown impregnated with a resin is disclosed, and JP-A-5-97625 (Patent Document 4) discloses a fiber reinforced resin in an uncured or semi-cured state as a ring. A resin-made crown material molded into the above is disclosed. When the frame material is formed using these materials, the destruction of the hard resin for the crown is remarkably reduced. However, when applying the above composition, etc., it is necessary to press the frame material with the abutment tooth model with a finger so that the frame material is in contact with the abutment tooth model. There is a tendency for problems to occur in adhesion to the skin.

In order to solve this problem, JP-A-6-157231 (Patent Document 5) describes a composition for a hard resin crown containing an acrylic resin and an inorganic fiber whisker. Since this composition is a paste, it has the advantage that a frame material with good compatibility can be produced simply by placing it on an abutment tooth model and then curing it. However, since it contains a fibrous filler, The properties are very poor, and stringing is likely to occur when building a plaster model with a building jig such as a spatula or brush, and problems are likely to occur when building a frame material with the paste adhering to the spatula. In addition, since the operability is not good as described above, it is difficult to make the thickness of the frame material paste constant, and this thickness unevenness greatly affects the occurrence of color unevenness, and the crowns to be placed thereon are arranged. This not only deteriorates the color tone of the hard resin for use in the machine, but also causes a decrease in the mechanical strength of the hard resin for the crown due to the uneven thickness of the frame material that reinforces the mechanical strength. These problems also occur when backing this paste in a concave gypsum model to reinforce a resin inlay or resin onlay.
Japanese Patent Laid-Open No. 58-17445 JP 2000-80013 A JP-A-5-310525 JP-A-5-97625 JP-A-6-157231

  The present invention suitably uses a dental restorative material kit and a dental restorative material kit capable of accurately producing a frame or a crown lining material suitable for improving the mechanical properties of a dental restorative material. Its purpose is to provide a method of use.

  In addition, the present invention can suitably manufacture a crown lining material used for improving mechanical strength such as impact resistance or fracture resistance of a dental filler such as a composite resin. An object of the present invention is to provide a dental restorative material kit and a method for suitably using the dental restorative material kit.

The dental restorative material kit of the present invention is a dental restorative composition comprising a dental restorative material composition (D) and a low viscosity composition (E) in a non-contact state with the dental restorative material composition (D). A restoration kit,
The dental restorative material composition (D) comprises a polymerizable monomer (A) and a filler (B1) containing inorganic short fibers (B1) with respect to 100 parts by weight of the polymerizable monomer (A). ); 1 to 900 parts by weight and a polymerization initiator (C),
The low-viscosity composition (E) contains an organic solvent (E0) and / or a soluble polymerizable monomer (E1) whose boiling point at 1 atm is in the range of 30 ° C. to 130 ° C. The viscosity composition (E) is characterized in that the viscosity at 25 ° C. is 30,000 mPa · s or less.

In addition, the present invention, when building up a dental restorative material composition using a building jig,
As the dental restorative material composition, a polymerizable monomer (A) and a filler (B) containing inorganic short fibers (B1) with respect to 100 parts by weight of the polymerizable monomer (A); 1 Use a dental restorative material composition (D) comprising ~ 900 parts by weight and a polymerization initiator (C),
Low viscosity with an organic solvent (E0) and / or soluble polymerizable monomer (E1) having a boiling point of 30 to 130 ° C. at 1 atm and a viscosity at 25 ° C. of 30,000 mPa · s or less A dental restorative material composition (D), characterized in that the dental restorative material composition (D) is built up in a planned construction portion using a building-up jig to which a viscosity composition (E) is previously attached. And a method for using a dental restorative material kit comprising a low-viscosity composition (E).

Here, the amount of the polymerization initiator (C) in the dental restorative material composition (D) is the polymerizable monomer (A) 1
It is preferably within the range of 0.1 to 10 parts by weight with respect to 00 parts by weight.
Part of the organic solvent (E0) is added to the dental restorative material composition (D) constituting the dental restorative material kit of the present invention, and the total weight of the dental restorative material composition (D) The ratio (ΣE0 / ΣD) of the total weight (ΣE0) of the organic solvent (E0) in the dental restorative material composition (D) to (ΣD) may be 0.75 or less. .

Further, a part of the filler (B) is added to the low viscosity composition (E) constituting the dental restorative material kit of the present invention, and the total weight (ΣE) of the low viscosity composition (E). ) To the total weight (ΣB) of the filler (B) in the low-viscosity composition (E) (ΣB / ΣE) may be 0.33 or less.

Furthermore, a part of the polymerization initiator (C) is added to the low viscosity composition (E) constituting the dental restorative material kit of the present invention, and the total weight of the low viscosity composition (E) ( The ratio (ΣC / ΣE) of the total weight (ΣC) of the polymerization initiator (C) in the low-viscosity composition (E) to ΣE) is in the range of 0.0001 to 0.1 It may be.

  The polymerizable monomer (A) is a polyfunctional (meta) having at least one skeleton selected from the group consisting of (a1) a tricyclodecane skeleton, (a2) an aromatic ring skeleton, and (a3) a polycarbonate skeleton. ) It is preferable that it contains at least one acrylate compound.

Here, the polymerizable monomer (A) forming the dental restorative material composition (D) is (a1) a polyfunctional (meth) acrylate compound having a tricyclodecane skeleton or (a2) an aromatic ring. Multifunctional ((
When it is a (meth) acrylate compound, this (a1) polyfunctional (meth) acrylate compound having a tricyclodecane skeleton or (a2) a polyfunctional (meth) acrylate compound having an aromatic ring is represented by the following formula (1): It is preferable that it is a compound which has a structure represented by these.
CH ₂ = CZ ¹ -CO ₂ -G _a -O CONH-R-NHCO-Y-CONH-R-NHCO ₂ -G _a -O ₂ CZ ¹ C = H ₂ C
... (1)
However, in the above formula (1), Z ¹ each independently represents a hydrogen atom or a methyl group, G is _{- (CH 2) -, -} (CH 2 CHR 1) -, and - (CHR ¹ CH ₂ )-Is any group selected from the group consisting of-, R ¹ represents an alkyl group having 1 to 10 carbon atoms, a represents each independently an integer of 1 to 10, and R represents each independently. Any of the groups represented by the following formulas (2) to (5):

  Y is a group having a tricyclodecane skeleton represented by the following formula (6) or a group having an aromatic ring skeleton represented by the following formula (7).

In the above formula (6), X is —O— or — [O (CH ₂ ) ₅ OCO] —, and represents an integer of m + n = 2-10.

In the above formula (7), G is _{- (CH 2) -, -} (CH 2 CHR 1) -, and, - (CHR1CH ₂₎ - is any group selected from the group consisting of, R ¹ is carbon represents the number of 1 to 10 alkyl group, more I is Arikiriden group having 1 to 4 carbon atoms, a cyclohexylidene group, -O -, - S -, - SO 2 -
Or -CO- and an integer of m + n = 2-10.

Further, the polymerizable monomer (A) forming the dental restorative material composition (D) has (a1) a polyfunctional (meth) acrylate compound having a tricyclodecane skeleton or (a2) an aromatic ring. In the case of a polyfunctional (meth) acrylate compound, this (a1) polyfunctional (meth) acrylate compound having a tricyclodecane skeleton or (a2) a polyfunctional (meth) acrylate compound having an aromatic ring is represented by the following formula: A compound having a structure represented by (8) is preferred.
CH ₂ = CZ ¹ -CO ₂ -G _a -O- [CO-G _a O] _b -CONH-RNHCO-Y-CONH-R-NHCO- [OG _a -OC-] _b -OG _a -O ₂ CZ ¹ C = CH ₂
... (8)
However, in the above formula (8), Z ¹ each independently represents a hydrogen atom or a methyl group, G is _{- (CH 2) -, -} (CH 2 CHR 1) -, and, - (CHR ¹ CH ₂ ) any group selected from the group consisting of-, R ¹ represents an alkyl group having 1 to ¹ carbon atoms, a and b each independently represent an integer of 1 to 10; Independently, any group represented by the above formulas (2) to (5), Y is a tricyclodecane skeleton represented by the above formula (6), or an aromatic ring skeleton represented by the above formula (7) It is group which has.

Further, when the polymerizable monomer (A) forming the dental restorative material composition (D) is (a3) a polyfunctional (meth) acrylate compound having a polycarbonate skeleton, this (a3 It is preferable that the polyfunctional (meth) acrylate compound having a polycarbonate skeleton is a compound having a structure represented by the following formula (9).
CH ₂ = CZ ¹ -CO ₂ -G _a -O ₂ CNH-R-NHCO ₂ G _a -CO ₂ D _a -O- [CO ₂ -G _a -O] _b CO ₂ -G _a -O ₂ CNH- R-NHCO ₂ -G _a -CO ₂ -Z ¹ C = CH ₂
... (9)
However, in the above formula (9), Z ¹ each independently represents a hydrogen atom or a methyl group, G is _{- (CH 2) -, -} (CH 2 CHR 1) -, and, (- CHR ¹ CH ₂ ) is any group selected from the group consisting of-, R ¹ represents an alkyl group having 1 to 10 carbon atoms, a and b each independently represents an integer of 1 to 10, and R is Each independently represents any group represented by the above formulas (2) to (5), and Y represents a tricyclodecane skeleton represented by the above formula (6) or an aromatic ring represented by the above formula (7). D is a group having a skeleton, and D is a methylene group or an isopropylene group.

  The inorganic short fiber (B1) contained in the filler (B) forming the dental restorative material composition (D) constituting the dental restorative material kit of the present invention has an average fiber length in the range of 5 to 1000 μm. It is preferable that the inorganic short fibers have an average fiber diameter in the range of 0.1 to 100 μm and an average fiber length / average fiber diameter ratio in the range of 3 to 10,000.

The dental restorative material composition (D) constituting the dental restorative material kit of the present invention has an average particle diameter of 0.001 to 100 μm as the filler (B) in addition to the inorganic short fibers (B1). The particulate filler (B2) is preferably contained in an amount of 0.1 to 50 parts by weight with respect to 100 parts by weight of the polymerizable monomer (A).

Further, the dental restorative material composition (D) constituting the dental restorative material kit of the present invention,
(D _A 1) _A 10 mm × 25 mm × 1.5 mm ^t test piece S _A 1 made of a cured product formed using the dental restorative material composition (D) was placed on a test piece of a repeated impact test apparatus. Placed on the part (between spans = 20 mm),
(D _A 2) wherein the dental restorative material composition in the cured product of 10 mm × 25 mm × thickness 0.5 mm ^t consisting of (D), crown restorative materials flexural strength 80 ± 20 MPa with a thickness of 1.0 mm ^t _A test piece S _A 2 laminated with
Place the restoration material for the crown on the impact weight side and place it on the test piece placement part (span interval = 20 mm) of the repeated impact test device.
When each test piece was subjected to repeated impacts under the conditions that the diameter of the tip of the impact weight was 5.6 mm, the impact load was 134 g, the drop distance was 10 mm, and the repetition cycle was 56 times / min. It is preferable to have a composition capable of forming a cured product in which the number of impacts leading to destruction of the test pieces S _A 1 and / or S _A 2 is 1400 times or more.

Further, the dental restorative material composition (D) constituting the dental restorative material kit of the present invention,
(D _B 1) Impact strength measured in a Charpy impact test by a flatwise method on an 80 mm × 10 mm × 2 mm ^t unnotched test piece S _B 1 made of a cured product of the dental restorative material composition (D), and (D _B 2) consists of the dental restorative composition cured product of the (D) 80mm × 10mm × thickness 1.0 mm ^t
In addition, the impact strength measured by the Charpy impact test by the flatwise method on the test piece S _B 2 laminated with a 1.0 mm- ^t bending strength restoration material of 80 ± 20 MPa exceeds 11 kJ / m ² It is preferable to have a composition capable of forming a cured product.

  Further, the organic solvent (E0) constituting the dental restorative material kit of the present invention is at least one kind selected from the group consisting of a hydroxyl group-containing compound, a ketone group-containing compound, an ester group-containing compound and an ether group-containing compound. Preferably, the soluble polymerizable monomer (E1) is a group consisting of a glycol group, an alkynyl group, an alkyl group, a carbamoyl group, a group having an aromatic ring, and a group having a heterocyclic ring. A polymerizable monomer having at least one kind of group selected from is preferable.

  The dental restorative material kit of the present invention is a material for forming a frame formed between an abutment tooth and a crown material, or a crown lining, when a crown material is mounted on the surface of an abutment tooth. Can be used as material forming material

  Resin-based frame that dramatically improves the mechanical strength of dental restoration materials such as hard resin for crowns or the mechanical properties of dental filling materials such as composite resins by using the dental restoration material kit of the present invention Or a lining material can be manufactured easily. In particular, by using the dental restorative material kit of the present invention, a resin-based frame or back that dramatically improves the mechanical strength such as impact resistance and fracture resistance of the dental restorative material or dental filling material. The dressing material can be easily produced.

Further, the dental restorative material kit of the present invention is a package of the dental restorative material composition (D) and the low-viscosity composition (E) individually, and the low-adhesive composition (E ) Is applied to build up the dental restorative composition (D), so that the dental restorative composition (D) does not adhere to the build-up jig, and the dental restorative composition (D) There is no stringing phenomenon. Furthermore, the dental restorative material composition (D) can be uniformly built up, the mechanical strength of the obtained frame material, crown lining material, etc. can be made constant, and the overall mechanical strength can be improved. Further, the frame material or crown lining material formed using the dental restorative material kit of the present invention does not contain a volatile organic solvent, and the formed frame material or crown back is formed. The dressing has almost no organic solvent odor.

Next, the method for using the dental restorative material kit and the dental restorative material kit of the present invention will be specifically described.
The dental restorative material kit of the present invention comprises a dental restorative material composition (D) and a low viscosity composition (E), and the dental restorative material composition (D) and the low viscosity composition (E) Is in a non-contact state.

The dental restorative material composition (D) constituting the dental restorative material kit of the present invention includes a polymerizable monomer (A), a filler (B) containing inorganic short fibers, and a polymerization initiator (C ) And are contained.
The polymerizable monomer (A) contained in the dental restorative material composition (D) constituting the dental restorative material kit of the present invention includes a reactive compound, (a1) a tricyclodecane skeleton (meta ) Acryl
Any compound among (a) a (meth) acrylate compound having an aromatic ring skeleton and (a3) a (meth) acrylate compound having a polycarbonate skeleton can be used.

Examples of reactive compounds used in the present invention include (i) monofunctional polymerizable monomers, (ii) bifunctional polymerizable monomers, (iii) trifunctional polymerizable monomers, (iv) Examples thereof include polymerizable monomers having a functionality or higher, and examples thereof include (meth) acrylic acid ester compounds.

Examples of (i) monofunctional polymerizable monomers that can be used in the present invention are shown below.
(i) Monofunctional polymerizable monomer
Examples of (i) monofunctional polymerizable monomers include methyl (meth) acrylate, ethyl (meth) acrylate, n-butyl (meth) acrylate, isopropyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, n -Lauryl (meth) acrylate, n-stearyl (meth) acrylate, behenyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxy-3-phenoxypropyl (meth) acrylate, tetrafurfuryl (meth) acrylate , Glycidyl (meth) acrylate, methoxyethylene glycol (meth) acrylate, methoxydiethylene glycol (meth) acrylate, methoxy-triethylene glycol (meth) acrylate, methoxypolyethylene glycol (meth) acrylate, ethoxyethylene glycol (meth) acrylate, ethoxydie Tylene glycol (meth) acrylate, ethoxytriethylene glycol (meth) acrylate, ethoxypolyethylene glycol (meth) acrylate, phenoxyethylene glycol (meth) acrylate, phenoxydiethylene glycol (meth) acrylate, phenoxytriethylene glycol (meth) acrylate, phenoxypolyethylene Glycol (meth) acrylate, cyclohexyl (meth) acrylate, benzyl (meth) acrylate, 3-chloro-2-hydroxypropyl (meth) acrylate, isobornyl (meth) acrylate, dicyclopentanyl (meth) acrylate, dicyclopentenyl ( (Meth) acrylate, dicyclopentenyloxyethyl (meth) acrylate, N- (meth) acryloylmorpholine, trifluoroethyl (meth) acrylate, Perfluorooctyl (meth) acrylate, .gamma. (meth) acryloyloxy propyl trimethoxy silane, .gamma. (meth) acrylate may be mentioned (meth) acrylic acid ester-based polymerizable monomers such as acryloyloxyethyl methyl dimethoxy silane. These can be used alone or in combination.

  Further, an acidic group-containing polymerizable monomer can also be used as the reactive compound. Examples of such acidic group-containing polymerizable monomer include a phosphoric acid group-containing polymerizable monomer and a pyrophosphate group-containing monomer. Examples thereof include a polymerizable monomer, a thiophosphate group-containing polymerizable monomer, a carboxylic acid group-containing polymerizable monomer, and a sulfonic acid group-containing polymerizable monomer.

Examples of the phosphate group-containing polymerizable monomer that can be used in the present invention include 2- (meth) acryloyloxyethyl dihydrogen phosphate, 3- (meth) acryloyloxypropyl dihydrogen phosphate, 10- (Meth) acryloyloxydecyl dihydrogen phosphate, 12- (meth) acryloyl oxide decyl dihydrogen phosphate, (meth) acryloyloxyethyl phenyl phosphate, (8- (meth) acryloyloxy) octyl-3-phosphonopropinate And other polymerizable monomers. These can be used alone or in combination.

Examples of pyrophosphate group-containing polymerizable monomers that can be used in the present invention include di [2- (meth) acryloyloxyethyl pyrophosphate], di [4- (meth) acryloyloxyethyl pyrophosphate], Examples thereof include polymerizable monomers such as di [8- (meth) acryloyloxyethyl pyrophosphate] and di [12- (meth) acryloyloxyethyl pyrophosphate]. These can be used alone or in combination.

Examples of the thiophosphate group-containing polymerizable monomer that can be used in the present invention include 2- (meth) acryloyloxyethyl dihydrogenthiophosphate, 3- (meth) acryloyloxypropyl dihydrogenthiophosphate, Examples thereof include polymerizable monomers such as 10- (meth) acryloyloxydecyl dihydrogen thiophosphate and 12- (meth) acryloyl oxide decyl dihydrogen thiophosphate. These can be used alone or in combination.

  Examples of carboxylic acid group-containing polymerizable monomers that can be used in the present invention include (meth) acrylic acid, 4- (meth) acryloyloxyethyloxycarbonylphthalic acid, 4- (meth) acryloyloxybutyloxy Carbonylphthalic acid, 4- (meth) acryloyloxyoctyloxycarbonylphthalic acid, 4- (meth) acryloyloxydecyloxycarbonylphthalic acid and their anhydrides, 6- (meth) acryloylaminohexylcarboxylic acid, 8- ( Examples thereof include polymerizable monomers such as (meth) acryloylaminohexylcarboxylic acid and 11- (meth) acryloyloxy-1,1-undecanedicarboxylic acid. These can be used alone or in combination.

Examples of the sulfonic acid group-containing polymerizable monomer that can be used in the present invention include 2- (meth) acrylamidoethylsulfonic acid, 3- (meth) acrylamidopropylsulfonic acid, 4- (meth) acrylamidobutylsulfone. Examples thereof include polymerizable monomers such as acid and 10- (meth) acrylamide decylsulfonic acid. These can be used alone or in combination.

In the present invention, among the above (i) monofunctional polymerizable monomers, phenoxyethylene glycol (meth) acrylate, phenoxydiethylene glycol (meth) acrylate, phenoxytriethylene glycol (meth) acrylate, phenoxypolyethylene glycol (Meth) acrylate, N- (meth) acryloylmorpholine, isobornyl (meth) acrylate is preferably used, and further, a group consisting of phenoxydiethylene glycol (meth) acrylate, N- (meth) acryloylmorpholine and isobornyl (meth) acrylate It is particularly preferable to use a compound selected from 1 alone or in combination of two or more.
(Ii) Bifunctional polymerizable monomer (ii) Bifunctional polymerizable monomers that can be used in the present invention include aromatic compounds and aliphatic compounds, which should be used here. Examples of aromatic compounds that can be used include 2,2-bis ((meth) acryloyloxyphenyl) propan, 2,2-bis [4- (3- (meth) acryloyloxy) -2-hydroxypropoxyphenyl] Propane, 2,2-bis (4- (meth)
(Acryloyloxypolyethoxyphenyl) propane, 2,2-bis (4- (meth) acryloyloxydiethoxyphenyl) propan, 2,2-bis (4- (meth) acryloyloxytetraethoxyphenyl) propane, 2,2- Bis (4- (meth) acryloyloxypentaethoxyphenyl) propan, 2,2-bis (4- (meth) acryloyloxydipropoxyphenyl) propan, 2- (4- (meth) acryloyloxydiethoxyphenyl) -2 -(4- (meth) acryloyloxydiethoxyphenyl) propan, 2- (4- (meth) acryloyloxydiethoxyphenyl) -2- (4- (meth) acryloyloxyditriethoxyphenyl) propan, 2- (4 -(Meth) acryloyloxydipropoxyphenyl) -2- (4- (meth) acryloyloxy-triethoxyphenyl) propane, 2,2-bis (4- (meth) acryloyloxy Propoxyphenyl
) Propane, 2,2-bis (4- (meth) acryloyloxyisopropoxyphenyl) propane;
Hydroxyl-containing (meth) acrylate compounds such as 2-hydroxyethyl (meth) acrylate, 2-hydroxyethylpropyl (meth) acrylate, 3-chloro-2-hydroxypropyl (meth) acrylate and diisocyanate methylbenzene or 4,4 -A diadduct obtained by addition reaction with a diisocyanate compound having an aromatic group such as diphenylmethane diisocyanate. These can be used alone or in combination.

In the present invention, (ii) examples of the aliphatic compound used as the bifunctional polymerizable monomer include ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, triethylene glycol di (meth) ) Acrylate, tetraethylene glycol di (meth) acrylate, pentamethylene glycol di (meth) acrylate, hexaethylene glycol di (meth) acrylate, nonaethylene glycol di (meth) acrylate, propylene glycol di (meth) acrylate, dipropylene glycol Di (meth) acrylate, tripropylene glycol di (meth) acrylate, tetrapropylene glycol di (meth) acrylate, pentapropylene glycol di (meth) acrylate, hexpropylene glycol di (meth) acrylate, nona Ethylene glycol-based or propylene glycol-based di (meth) acrylates such as propylene glycol di (meth) acrylate; or cyclic, linear, branched aliphatic (meth) acrylates such as ethoxylated cyclohexane di (meth) acrylate and A di (meth) acrylate compound bonded with ethylene glycol or propylene glycol;
Neopentyl glycol di (meth) acrylate, tricyclodecane dimethanol di (meth) acrylate, 1,4-butanediol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, 1,9-nonanediol Aliphatic di (meth) acrylate compounds such as di (meth) acrylate and 1,12-dodecanediol di (meth) acrylate;
Hydroxyl-containing (meth) acrylate compounds such as 2-hydroxyethyl (meth) acrylate, 2-hydroxyethylpropyl (meth) acrylate, 3-chloro-2-hydroxypropyl (meth) acrylate, hexamethyldiisocyanate, trimethylhexamethylene Adducts obtained by addition reaction with diisocyanate compounds such as diisocyanate, diisocyanate methylcyclohexane, isophorone diisocyanate, methylenebis (4-cyclohexylisocyanate);
And di (2- (meth) acryloyloxypropyl) phosphate. These can be used alone or in combination.

  Further, a polyester di (meth) acrylate compound represented by the following formula (10) in which one or more ester groups are bonded between di (meth) acrylate groups can also be used.

In the above formula (10), Z ² is a hydrogen atom or a methyl group, W is (i) an alkylene group having 1 to 20 carbon atoms,
(B) an alkylene group having 1 to 20 carbon atoms having an alkyl group having 1 to 20 carbon atoms in the side chain;
(C) a group in which 1 to 5 cyclohexane is inserted between groups having 1 to 20 carbon atoms, (d) a group in which 1 to 20 ethylene glycol or propylene glycol are bonded,
(E) A group in which an aromatic ring is inserted into a group in which 1 to 20 ethylene glycol or propylene glycol are bonded.

In the present invention, among the above (ii) bifunctional polymerizable monomers, ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, tetraethylene glycol Di (meth) acrylate, nonaethylene glycol di (meth) acrylate, tripropylene glycol di (meth) acrylate, tetrapropylene glycol di (meth) acrylate, neopentyl glycol di (meth) acrylate, ethoxylated cyclohexane di (meth) acrylate Can be used particularly preferably.
(Iii) Trifunctional polymerizable monomer In the present invention, examples of the trifunctional polymerizable monomer (iii) that can be used as the polymerizable monomer (A) include trimethylolpropan tri (meth). Acrylate, trimethylolethane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, dipentaerythritol tri (meth) acrylate, ethoxylated trimethylolpropantri (
(Meth) acrylate, propoxylated trimethylolpropan tri (meth) acrylate,
And tris (2- (meth) acryloxyethyl isocyanurate). These can be used alone or in combination.

In the present invention, among the above (iii) trifunctional polymerizable monomers, trimethylolpropane tri (meth) acrylate and ethoxylated trimethylolpropane tri (meth) acrylate are particularly preferably used.
(iv) Tetrafunctional or higher polymerizable monomer In the present invention, the tetrafunctional or higher functional polymerizable monomer that can be used as the polymerizable monomer (A) includes pentaerythritol tetra (meta). ) Acrylate, ethoxylated pentaerythritol tetra (meth) acrylate, propoxylated pentaerythritol tetra (meth) acrylate, dipentaerythritol tetra (meth) acrylate, ethoxylated pedin taerythritol tetra (meth) acrylate, propoxylated dipentaerythritol tetra ( Tetra (meth) acrylate compounds such as (meth) acrylate, ditrimethylolpropanetetra (meth) acrylate, ethoxylated ditrimethylolpropanetetra (meth) acrylate, ethoxylated ditrimethylolpropanetetra (meth) acrylate;
Diisocyanate compounds having an aliphatic between diisocyanates such as hexamethyl diisocyanate, trimethylhexamethylene diisocyanate, diisocyanate methylcyclohexane, isophorone diisocyanate, methylene bis (4-cyclohexyl isocyanate);
An adduct obtained by addition reaction of a diisocyanate compound having an aromatic group such as diisocyanate methylbenzene or 4,4, -diphenylmethane diisocyanate with glycidol di (meth) acrylate;
Dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (
And (meth) acrylate.

  A monofunctional or higher functional adduct obtained by addition reaction of a compound having 1 to 3 isocyanate groups bonded to a triisocyanurate ring and a (meth) acrylate containing a hydroxyl group can also be used. These can be used alone or in combination.

In the present invention, among the above (iv) tetrafunctional or higher polymerizable monomers, ditrimethylolpropane tetra (meth) acrylate and dipentaerythritol hexa (meth) acrylate are particularly preferably used.

In the present invention, as the polymerizable monomer (A), (a1) a polyfunctional (meth) acrylate compound having a tricyclodecane skeleton, (a2) a polyfunctional (meth) having an aromatic ring skeleton It is preferable to use an acrylate compound and (a3) a polyfunctional (meth) acrylate compound having a polycarbonate skeleton. By using the polymerizable monomer (A) containing such a polyfunctional (meth) acrylate compound (AL), the mechanical properties of the frame material or crown lining material described later, particularly toughness Is significantly improved. Note that the above-described skeleton may be combined in the polyfunctional (meth) acrylate compound (AL).

Here, polyfunctional means having two or more, preferably two copolymerizable functional groups in one compound molecule. The copolymerizable group is preferably located at the molecular chain end, preferably a vinyl group or a vinylidene group, and particularly preferably a (meth) acryloyl group. The polyfunctional (meth) acrylate compound (AL) is preferably a urethane compound in which a molecular group contains a urethane group. The polyfunctional (meth) acrylate compound (AL) in the present invention may include a compound that may be classified as an oligomer. However, such definition is complicated and is practically used in the present invention. Since they are not very useful, they are collectively considered as monomers. In addition, when the polymerization monomer (A) contains the polyfunctional (meth) acrylate compound (AL), the effect of improving the impact resistance of the dental restorative material or the dental filler is enhanced, so that it is particularly preferably used. The

Hereinafter, each case having the (a1) to (a3) skeleton will be sequentially described with respect to the polyfunctional (meth) acrylate compound (AL).
First, (a1) a polyvalent (meth) acrylate compound having a tricyclodecane skeleton and (a2) an aromatic ring that can be blended as the polymerizable monomer (A) constituting the dental restorative material kit of the present invention The polyfunctional (meth) acrylate compound having a skeleton will be described.

  At least two polyfunctional (meth) acrylate compounds having (a1) a tricyclodecane skeleton and (a2) polyfunctional (meth) acrylate compounds having an aromatic ring skeleton that can be used in the present invention are used. It is a polymerizable compound having a (meth) acryl group.

The (a1) polyfunctional (meth) acrylate compound having a tricyclodecane skeleton and the (a2) polyfunctional (meth) acrylate compound having an aromatic ring skeleton that can be used in the present invention are a tricyclodecane skeleton or an aromatic Other residues or skeletons are not limited as long as they have a ring skeleton, but for example, compounds described in JP-A-8-27236 can be preferably used. Specifically, in the following formula (1) The compound (A1) having the structure represented is preferable.
CH ₂ = CZ ¹ -CO ₂ -G _a -OCONH-R-NHCO-Y-CONH-R-NHCO ₂ -G _a -O ₂ CZ ¹ C = H ₂ C
... (1)
In the above formula (1), Z ¹ is each independently a hydrogen atom or a methyl group, and G is-
(CH ₂ ) —, — (CH ₂ CHR ¹ ) —, and — (CHR ¹ CH ₂ ) — are any group selected from the group consisting of R ¹ is an alkyl group having 1 to 10 carbon atoms. A represents an integer of 1 to 10 independently.

  R is independently any group represented by the following formulas (2) to (5).

Moreover, isocyanate residues other than the above (2) to (5) may be introduced as long as the performance of the present invention is exhibited. In addition, since the structure connected to the urethane bond is preferably derived from an isocyanate compound and expressed as an isocyanate residue as described above, the effect of the present invention is polyfunctional (meta). As long as the structure of the acrylate compound (AL) is the same, it is not limited by the production method because it is not affected by the production method. The same applies to “residues” in other descriptions in this specification.

Examples of isocyanate residues in the present invention include ethylene diisocyanate, propylene diisocyanate, lysine diisocyanate, hexamethylene diisocyanate, trimethylhexanemethylene diisocyanate (2 2,3-trimethyl and 2,3,3-trimethyl, and a mixture of both can be used.) Aliphatic isocyanate such as transcyclohexane diisocyanate, hydrogenated xylylene isocyanate, bicycloheptane triisocyanate, trimethyl Hexane diisocyanate, bicycloheptatriisocyanate, trimethylhexanemethylene diisocyanate (This compound has 2,2,3-trimethyl and 2,3,3-trimethyl, and a mixture of both can be used.) Residues obtained from aliphatic cyclic isocyanates such as ;
Obtained from aliphatic and aromatic polyisocyanates such as tolylene diisocyanate, toluylene isocyanate, toluylene diisocyanate, polymethyl polyphenyl polyisocyanate, polypropyl polyphenyl polyisocyanate, polymethylpropyl polyphenyl polyisocyanate Residues can be mentioned. Moreover, the residue obtained from the blocked polyisocyanate etc. from which the isocyanate group blocked by the heat of polymerization etc. is cancelled | released may be sufficient.

  Further, Y is preferably a group having a tricyclodecane skeleton represented by the following formula (6) or a group having an aromatic ring skeleton represented by the following formula (7).

Here, X in the formula (6) is —O— or — [O (CH ₂ ) ₅ OCO] —, and is preferably an integer of m + n = 2 to 10.

Here, G in the formula (7) is any group selected from the group consisting of — (CH ₂ ) —, — (CH ₂ CHR ¹ ) —, and — (CHR ¹ CH ₂ ) —, and I is carbon C1-4 of Arikiriden group, cyclohexylidene group, -O -, - S -, - SO 2 -, or a -CO-, it is preferable that an integer of m + n = 2~10.

In addition to the above (6) and (7), the following residues may be introduced as long as the performance of the present invention is exhibited. Specifically, ethylene glycol, diethylene glycol, propylene glycol, 1,4-butylene glycol, glycerin, hexanetriol, trimethylolpropane pentaerythritol, sorbitol, sucrose dipropylene glycol, neopentyl glycol, 1,4-butanediol, 1, 6-hexane glycol, decamethylene glycol, 1,10-decamethylene diol, 1,12-dodecamethylene diol, 1,2-polybutadiene polyol, 1,4-polybutadiene polyol, polychloroprene polyol, butadiene / acrylonitrile copolymer Polyols, aliphatic or cycloaliphatic polyalcohols such as polydimethylcycloxandicarbinol, methyleryl diethanolamine, ethyldiisopanolamine, triethanolamine, bis (p-amino) A polyether polyol residue obtained by addition polymerization of one or two aliphatic oxides such as ethylene oxide and propylene oxide to an aliphatic amine such as methane) methane or an aliphatic polyamine as an initiator; Esters of polyhydric alcohol and aliphatic polycarboxylic acid or alicyclic polycarboxylic acid such as malonic acid, maleic acid, succinic acid, adipic acid, glutaric acid, pimelic acid, sebacic acid, succinic acid, hexahydrophthalic acid, etc. Polyester polyol residues obtained by conversion to oxirane; and oxirane residues such as ethylene oxide, propylene oxide, butylene oxide; and propiolactone, butyrolactone, caprolactone, Plaxel series (manufactured by Daicel Chemical Industries, Ltd.) Polycaprolactone derivatives; Tylene glycol, diethylene glycol, propylene glycol, 1,4-butylene glycol, glycerin, hexanetriol, trimethylolpropane pentaerythritol, sorbitol, scroll dipropylene glycol, neopentyl glycol, 1,4-butanediol, 1,6-hexane glycol , Decamethylene glycol, 1,10-decamethylene diol, 1,2-polybutadiene polyol, 1,4-polybutadiene polyol, polychloroprene polyol, butadiene / acrylonitrile copolymer polyol, polydimethylcycloxandicarbinol, etc. And the like.

As the compound represented by the above formula (1),
In the formula (1), a urethane-based di (meth) acrylate compound (a1) having a tricyclodecane skeleton in which R is represented by the above formula (2) and Y is represented by the above formula (6), or
In the formula (1), a urethane di (meth) having a bisphenol A skeleton in which R is represented by the above formula (2), Y is the above formula (7), and E is an alkylidene group having 3 carbon atoms. An acrylate compound (a2) is preferred.

Furthermore, among these, it is particularly preferable to use a urethane (meth) acrylate compound (a2) having a bisphenol A skeleton because a cured product having excellent mechanical properties such as mechanical strength, impact resistance and toughness can be obtained.

Furthermore, the (a1) polyfunctional (meth) acrylate compound having a tricyclodecane skeleton and the (a2) polyfunctional (meth) acrylate compound having an aromatic ring skeleton have a structure represented by the following formula (8). It may be a compound.
CH ₂ = CZ ¹ -CO ₂ -G _a -O- [CO-G _a O] _b -CONH-RNHCO-Y-CONH-R-NHCO- [OG _a -OC-] _b -OG _a -O ₂ CZ ¹ C = CH ₂
... (8)
Z ^{1 in the} above formula (8) is each independently a hydrogen atom or a methyl group, and G is — (CH ₂ ) —, — (CH ₂ CHR ¹ ) —, and — (CHR ¹ CH ₂ ) —. Any one group selected from the group consisting of: R ¹ represents an alkyl group having 1 to 10 carbon atoms; a and b each independently represents an integer of 1 to 10; and R is each independently Any one of the groups represented by the above formulas (2) to (5), and Y is preferably a group represented by the above formula (6) or the above formula (7).

As such a compound represented by the above formula (8),
In the formula (8), R is represented by the above formula (2), Y is represented by the above formula (6), and a is 1
A compound having a tricyclodecane skeleton in which b is an integer of 1 to 10 and b is an integer of 1 to 6 is preferable.

  In addition to the above formulas (2) to (5), if the performance of the present invention is exhibited, the above aliphatic isocyanate residues, aliphatic cyclic isocyanate residues, aliphatic and aromatic polyisocyanate residues In addition, a blocked polyisocyanate residue or the like may be introduced.

Furthermore, in addition to the above formulas (6) and (7), residues such as the above polyether polyol residues and polyester polyol residues may be introduced as long as the performance of the present invention is exhibited.
Usually, the mechanical properties of the urethane (meth) acrylate compound cured product are superior to the mechanical properties of the (meth) acrylic ester compound cured product. However, since the viscosity before polymerization is higher than that of a (meth) acrylic acid ester compound or the like, it is difficult to handle alone. For this reason, it is generally used by diluting with a (meth) acrylic acid ester compound so as to have a desired viscosity. In this case, there may be a disadvantage that the characteristics such as mechanical properties and toughness of the cured body are deteriorated.

However, among the above (a1) polyfunctional (meth) acrylate compound having a tricyclodecane skeleton and (a2) polyfunctional (meth) acrylate compound having an aromatic ring skeleton, G is a methylene group, and a = 1 to 5 Of the formula (6) is — [O (CH ₂ ) ₅ OCO] —, and the compound represented by the integer of m + n = 2 to 5 is a urethane polyfunctional (meta Among the acrylate compounds, since the viscosity is not extremely high, the acrylate compound can be used alone, and since it is possible to suppress a decrease in mechanical strength and toughness of the cured product, it is particularly preferably used. Further, the polymerizable monomer (A) was formed using (a1) a polyfunctional (meth) acrylate compound having a tricyclodecane skeleton and (a2) a polyfunctional (meth) acrylate compound having an aromatic ring skeleton. When applied as a dental restorative frame material or crown lining material, the cured product can significantly improve the impact resistance of the crown lining material, frame material, or dental filler. it can. Furthermore, in a dental restorative material such as a dental restoration or a dental filler using these hardened bodies as a matrix resin, mechanical properties, particularly mechanical toughness, can be remarkably improved.

Here, the urethane bifunctional (meth) acrylate compound represented by the above formula (1) or the above formula (8) is often an oligomer. The average molecular weight of the oligomer is set in such a range that the paste operability is desired, the mechanical properties of the cured product are excellent, and the impact resistance is improved. The weight average molecular weight in terms of polystyrene is usually 1,000 to It is in the range of 10,000, preferably in the range of 1,000 to 8,000, more preferably in the range of 1,000 to 5,000.

Next, the polyfunctional (meth) acrylate compound (a3) containing a polycarbonate skeleton constituting the dental restorative material of the present invention will be described.
In the present invention, a polyfunctional (meth) acrylate compound having a polycarbonate skeleton described in JP-A-5-78435 or JP-A-5-140252 can be preferably used as this compound. The polyfunctional (meth) acrylate compound (a3) containing a polycarbonate skeleton is a polymerizable compound having at least two (meth) acryl groups in one molecule. Examples of the carbonate skeleton include 2 to 20 carbon atoms. And an aliphatic carbonate skeleton composed of any of linear, branched or cyclic, or a group represented by the following formula (10) as a main repeating unit.

In the formula (10), I is preferably an alkylidene group having 1 to 4 carbon atoms, a cyclohexylidene group, —O—, —S—, —SO ₂ —, or —CO—. Sometimes -C (CH _{3) 2} - it may be.

The molecular weight of the polyfunctional (meth) acrylate compound (a3) containing such a polycarbonate skeleton is in the range of 200 to 10,000, preferably 300 to 5,000. As specific examples of the polyfunctional (meth) acrylate compound (a3) containing such a polycarbonate skeleton,
A polyfunctional (meth) acrylate compound having a molecular weight of 200 to 10,000 esterified with (meth) acrylate or glycidyl (meth) acrylate having a hydroxyl group at the terminal and / or side chain;
Both polycarbonate oligomers having hydroxyl groups at the ends and side chains, and polycarbonates obtained by reacting (meth) acrylic acid ester having 1 to 2 hydroxyl groups at the ends and / or side chains with a diisocyanate compound in one step or two steps. A urethane-based polyfunctional (meth) acrylate compound having a molecular weight of 200 to 10,000 having a (meth) acrylate group via a urethane group at the terminal and / or side chain; and
Examples thereof include urethane polyfunctional (meth) acrylate compounds having a molecular weight of 200 to 10,000 obtained by reacting a carbonate oligomer having a hydroxyl group at the terminal and / or side chain with a (meth) acrylate compound having an isocyanate group. .

  Among these compounds, urethane di (meth) acrylate compounds having an aliphatic carbonate skeleton such as UN9000 series (manufactured by Negami Kogyo Co., Ltd.) having a viscosity at room temperature of tens of thousands to several million mPa · s are preferable. Available.

In addition to the polycarbonate group, the polyfunctional (meth) acrylate compound (a3) containing a polycarbonate skeleton includes the above-described polyether polyol group, polyester polyol group, polyester group derived from ε-caprolactone; polyethylene glycol group In addition, a known group or segment such as a polyalkylene glycol group such as a polypropylene glycol group, a linear, branched or cyclic alkylene group, a polyalkylene group, a group containing an aromatic ring or a heterocyclic ring is left. There is no problem even if it is contained as a group.

As the polyfunctional (meth) acrylate compound (a3) containing a polycarbonate skeleton, a compound having a structure represented by the following formula (9) is preferable.
CH ₂ = CZ ¹ -CO ₂ -G _a -O ₂ CNH-R-NHCO ₂ G _a -CO ₂ D _a -O- [CO ₂ -G _a -O] _b CO ₂ -G _a -O ₂ CNH- R-NHCO ₂ -G _a -CO ₂ -Z ¹ C = CH ₂
... (9)
In the above formula (9), each Z ¹ is independently a hydrogen atom or a methyl group, and G is-
(CH ₂ ) —, — (CH ₂ CHR ¹ ) —, and — (CHR ¹ CH ₂ ) — are any group selected from the group consisting of R ¹ represents an alkyl group having 1 to 10 carbon atoms. , A and b each independently represent an integer of 1 to 10, and R independently represents any group represented by the above formulas (2) to (5).

Here, in the above formula (9), D is preferably a methylene group or an isopropylene group,
Furthermore, when a and b are integers of 1 to 7, when applied as a frame material of a dental restoration material or a backing material of a dental filling material, the impact resistance of the restoration material for the crown or the dental filling material Can be significantly improved. Of course, the isocyanate residue or polyol residue described above may be introduced in addition to (2) to (5) as long as the performance of the invention is exhibited.

In the present invention, the polyfunctional (meth) acrylate compound (AL) used as the polymerizable monomer (A) is the above (a1) polyfunctional (meth) acrylate compound having a tricyclodecane skeleton, (a2) aromatic Any one of a polyfunctional (meth) acrylate compound having an aromatic ring skeleton and a polyfunctional (meth) acrylate compound having a polycarbonate skeleton may be used alone, or may be used in an appropriate mixture. . Further, (a1) a polyfunctional (meth) acrylate compound having a tricyclodecane skeleton, (a2) a polyfunctional (meth) acrylate compound having an aromatic ring skeleton, and (a3) a polyfunctional (meth) acrylate compound having a polycarbonate skeleton Some may be a polyfunctional (meth) acrylate compound having two or more of the above skeletons in one molecule. Moreover, in order to improve paste operability and impact resistance of the cured product, it may be used together with other polymerizable monomers.

Further, in some cases, for example, a part of the urethane bond (-OCONH-) in the above formulas (1), (8), and (9) is appropriately converted to an amide bond (-CONH-) or an ester bond (-COO-). You may use the compound substituted by etc.

In the present invention, as the polymerizable monomer (A), the above-mentioned (a1) polyfunctional (meth) acrylate compound having a tricyclodecane skeleton, (a2) a polyfunctional (meth) acrylate compound having an aromatic ring skeleton, and (a3) In the case where a polyfunctional (meth) acrylate compound having a polycarbonate skeleton and another polymerizable monomer are used in combination, the weight ratio of the other polymerizable monomer depends on the paste operability and the dental restorative material. Or mechanical properties such as the degree of improvement in impact resistance of dental fillers, etc. (a1) a polyfunctional (meth) acrylate compound having a tricyclodecane skeleton, (a2) an aromatic ring skeleton The amount of the other polymerizable monomer in 100 parts by weight of the total amount of the polyfunctional (meth) acrylate compound having (a3) and the polyfunctional (meth) acrylate compound having a polycarbonate skeleton and the other polymerizable monomer But usually 5 80 parts by weight, preferably 10 to 70 parts by weight, more preferably 20 to 60 parts by weight. Further, as the other polymerizable monomer, a monofunctional polymerizable monomer or a bifunctional polymerizable monomer is particularly preferable.
In the dental restorative material composition (D) of the present invention, a filler (B) containing inorganic short fibers (B1) is blended.

In the present invention, the inorganic short fibers (B1) used as the filler (B) are preferably short fibers obtained by pulverizing inorganic long fibers to an appropriate length by pulverization or the like, or needle-like bodies called whiskers. Specifically, short glass fibers called milled fibers such as C glass or E glass, wollastonite fibers mainly composed of calcium silicate, ceramic short fibers such as alumina fibers, slag short fibers, and the like are preferably used. Furthermore, short carbon fibers, short metal fibers, etc. can be used as long as the aesthetics after curing are not impaired. Moreover, as a whisker, a potassium titanate whisker, an aluminum borate whisker, etc. are used preferably.

  Among these, short glass fibers, short alumina fibers, wollastonite fibers, aluminum borate whiskers, etc. are preferred, and dental restorative composition (excellent aesthetics, mechanical strength, impact resistance to a cured product consisting of D) A glass short fiber is particularly preferably used for imparting properties such as properties, etc. The inorganic short fibers (B1) may be used in combination of two or more.

  The properties of the inorganic short fiber (B1) may be selected as appropriate depending on the thickness of the frame material or the crown lining material, etc., but the average fiber length is usually 5 to 1000 μm, preferably The average fiber diameter is usually from 0.1 to 100 μm, preferably from 0.1 to 80 μm, more preferably from 0.1 to 50 μm.

  The thickness of the frame material used for clinical use is generally 0.05 to 1 mm, preferably 0.1 to 0.5 mm. Therefore, if the fiber length or fiber diameter greatly deviates from the above range, the frame material tends to be thick. There is a tendency for compatibility with the abutment tooth to decrease. Conversely, if it is smaller than this range, the impact resistance of the restoration material for the crown tends to be difficult to be improved. In the case of whiskers, the average fiber length or the average fiber diameter is not referred to as the fiber, but is generally represented by the average major axis or the average minor axis. In the present invention, the average fiber length of the fiber = The average long diameter of the needle-like body and the average fiber diameter of the fiber = the short diameter of the needle-like body are defined, and the average fiber length and the average fiber diameter are described in a unified manner.

As the aspect ratio (average fiber length / average fiber diameter ratio) of the inorganic short fibers (B1) used as the filler (B) in the present invention is larger, the mechanical properties are improved. Therefore, the inorganic short fibers used in the present invention are improved. The aspect ratio of the fiber (B1) is usually in the range of 3 to 10,000, preferably 7 to 10,000, and more preferably 10 to 10,000. By using such inorganic short fibers (B1), the impact resistance of the prosthetic material for a crown can be remarkably improved. In addition, when the inorganic short fiber (B1) having an aspect ratio of less than 3 is used, the impact resistance improving effect tends to be slowed down.

In addition, the inorganic short fiber (B1) as described above is used to improve the affinity with the polymerizable monomer (A), so that γ- (meth) acryloxypropyltrimethoxysilane, γ- (meth) Silane coupling of acryloyloxypropylmethyldimethoxysilane, dimethyldichlorosilane, ω- (meth) acryloyloxyalkyltrimethoxysilane, trimethylchlorosilane, hexamethylenedisilazane, 3-aminopropylethoxysilane, 3-chloropropyltrimethoxysilane, etc. The surface of the inorganic oxide can be hydrophobized with a known surface treatment agent that is usually used as a surface treatment agent for inorganic oxides such as an agent, a silicium coupling agent, a titanium coupling material, and an alumina coupling agent. preferable.

  When inorganic short fibers (B1) are used after surface treatment, the amount of surface treatment agent is a characteristic value such as the specific area of inorganic short fibers (B1), the degree of improvement in impact resistance of prosthetic materials for crowns, etc. However, it is generally 0.1 to 20 parts by weight, preferably 0.1 to 15 parts by weight, more preferably 100 parts by weight of the inorganic short fibers (B1). Is in the range of 0.5 to 10 parts by weight.

The compounding amount of the filler (B) containing the inorganic short fibers (B1) in the dental restorative material composition (D) constituting the dental restorative material kit of the present invention is the polymerizable monomer (A) Usually 100 parts by weight
It is the range used as the quantity of -900 weight part, Preferably it is 5-500 weight part, More preferably, it is 10-120 weight part. By blending the filler (B) in such an amount, excellent toughness can be imparted to the resulting cured body.

In the dental restorative material composition (D) constituting the dental restorative material kit of the present invention, it is sufficient that the inorganic short fiber (B1) as described above is blended as the filler (B). In the case where the viscosity of the polymerizable monomer at 25 ° C. is 20,000 mPa · s (EH type) or less, the inorganic short fiber (B1) is used alone as the filler (B). (B1) and the polymerizable monomer (A) are likely to be phase-separated, and the storage stability may tend to decrease.

In such a case, in addition to the inorganic short fiber (B1) as the filler (B), the particulate filler (B2)
Can be added to suppress phase separation and improve storage stability.
Examples of the particulate filler (B2) used here include (a) inorganic oxide particles, (b) polymer particles, and (c) particles of a polymer and inorganic oxide composite. Then, inorganic oxide particles are preferable. Examples of the (a) inorganic oxide particles used here include metal oxides such as silica, alumina, titania, zirconia, silica and the periodic table Group I, Group II, Group III, Group Examples include composite oxides (eg, silica / titania, silica / zirconia, silica / strontium oxide, silica / barium oxide, silica / alumina, etc.) in combination with Group IV metal oxides.

In the present invention, when (b) polymer particles are blended as the particulate filler (B2), examples of polymer particles that can be used include homopolymers or copolymers of (meth) acrylate esters. Copolymer: Copolymer of styrene monomer such as (meth) styrene or α-methylstyrene and butadiene; Copolymer of acrylonitrile and butadiene, Copolymer of acrylonitrile, butadiene and styrene, Alkyl (meth) acrylate Copolymer of styrene monomer with vinyl acetate, copolymer of vinyl acetate, alkyl (meth) acrylate and styrene monomer, alkyl (meth) acrylate, styrene monomer and at least one hydroxyl group in the molecule (meth) Copolymers with acrylates, styrene / alkyl (meth) acrylate / butadiene copolymers, etc. Mention may be made of the Tomah particles. These can be used alone or in combination.

In the present invention, as the particulate filler (B2), when (c) particles of a composite of a polymer and inorganic oxide particles are used, examples of the particles of the composite include the above inorganic oxide powder. After uniformly kneading the polymer, a polymerizable monomer, and a thermal polymerization initiator such as benzoyl peroxide, the mixture is heated at a temperature of 60 to 200 ° C. under a pressure of 0.1 to 200 kgf / cm ² using a heat compression molding machine. It is possible to use composite particles produced by heat curing for minutes to several hours and pulverizing with a pulverizer such as a ball mill or a jet mill until a desired particle size or particle size distribution is obtained. The polymerizable monomer used here is preferably a polymerizable monomer having the above trifunctional or higher functional polymerizable monomer as a main component, and the inorganic oxide is a powder having an average particle size of 1 μm or less. Inorganic oxide particles are preferable, and colloidal silica called aerosil having an average particle diameter in the range of 0.001 to 0.05 μm or nano-sized inorganic oxide particles described above are particularly preferable.

  The composite particles of polymer and inorganic oxide particles may be used as they are or may be heat-treated. Further, in order to improve the affinity with the matrix monomer, it may be used after being surface-treated with a surface treatment agent such as the above-mentioned silane coupling agent, or a polymerizable monomer having an epoxy group such as glycidyl (meth) acrylate. Functional groups possessed by the composite particle, such as a monomer, a polymerizable monomer having a cyclic ether group such as tetrahydrofurfuryl (meth) acrylate, a polymerizable monomer having a hydroxyl group such as pentaerythritol tri (meth) acrylate, and the like. It can also be treated with a polymerizable monomer having a functional group capable of hydrogen bonding or covalent bonding. Even when the composite particle does not have a functional group, a surface treatment may be performed by reacting a polymerizable monomer with a double bond or a peroxide group or bond remaining in the composite.

There is no particular limitation on the shape of the particulate filler (B2) blended with the inorganic short fibers (B1) as the filler (B). It may be. The average particle size of the particulate filler (B2) used together with the inorganic short fibers (B1) as the filler (B) is usually 0.001 to 100 μm, preferably 0.001 to 50 μm, The dental restorative material constituting the dental restorative material kit of the present invention is preferably in the range of 0.001 to 10 μm, particularly when colloidal silica called aerosil having an average particle diameter of 0.001 to 0.1 μm is used. Not only the phase separation between the polymerizable monomer (A) and the filler (B) in the composition (D) is suppressed, but also a prosthetic material for a crown produced using the dental restorative material of the present invention. Or impact resistance, such as a dental filling material, can be improved.

The particulate filler (B2) used as the filler (B) in the present invention improves the impact resistance of the cured product formed from the dental restorative material composition (D), and further the dental use of the present invention. The dental restorative material composition (D) constituting the restorative material kit can be used in an amount within a range that can suppress the occurrence of phase separation. In the present invention, the amount of the particulate filler (B2) used is usually 0.1 to 50 parts by weight, preferably 0 with respect to 100 parts by weight of the inorganic short fibers (B1) blended as the filler (B). .5 to 40 parts by weight, more preferably 1 to 30 parts by weight. When the particulate filler (B2) is an inorganic oxide, it is preferable to use a material that has been hydrophobized by the hydrophobizing method described above. As the hydrophobically treated particulate filler (B2), when a commercially available product that has been subjected to a hydrophobic treatment is used, it may be used as it is, or may be further subjected to a hydrophobic treatment.

Further, as the filler (B) used in the present invention, as long as the impact resistance of the restoration material for the crown is not impaired, for example, a polymer whisker made of nylon, polyester, aramid fiber, p-oxobenzoin, etc. Polymer short fibers can also be blended. As such polymer short fibers, those usually having the same shape as the inorganic short fibers (B1) are preferable, and in this case, they are used in an amount within a range not impairing the effects of the present invention.

In the dental restorative material composition (D) of the dental restorative material kit of the present invention, the filler (B) as described above is contained in the dental restorative material composition (D) as described above. The polymerizable monomer (A) is used in an amount of 1 to 900 parts by weight, preferably 50 to 900 parts by weight, based on 100 parts by weight of the polymerizable monomer (A).

The dental restorative material composition (D) constituting the dental restorative material kit of the present invention contains a polymerization initiator (C).
The polymerization initiator (C) that can be used in the present invention includes a thermal polymerization initiator, a room temperature polymerization initiator, a photopolymerization initiator, etc., and a dental restorative material composition that constitutes the dental restorative material kit of the present invention. As the polymerization initiator (C) blended in the product (D), a photopolymerization initiator that can be cured only by irradiating light at a desired time is preferable. The blending amount of the polymerization initiator (C) is usually from 0.01 to 10 parts by weight, preferably from 0.1 to 5 parts by weight, more preferably from 0.1 to 100 parts by weight with respect to 100 parts by weight of the polymerizable monomer (A). It is the range of 1-3 weight part.

The photopolymerization initiator contained in the dental restorative material composition (D) constituting the dental restorative material kit of the present invention is a photosensitizer alone or a combination of a photosensitizer and a photopolymerization accelerator. Can be used.

Examples of photosensitizers include α-diketone compounds such as benzyl and camphorquinone, α-naphthyl, p, p'-dimethoxybenzyl, pentadione, 1,4-phenanthrenequinone, naphthoquinone, diphenyltrimethylbenzoylphosphine oxide and other ultraviolet light. These are known compounds that are excited by light or visible light to initiate polymerization, and these photosensitizers can be used alone or in combination. Of these, acylphosphine oxides such as camphorquinone and diphenyltrimethylbenzoylphosphine oxide or derivatives thereof are particularly preferably used.

Further, when using a photopolymerization initiator, it is preferable to use a photopolymerization accelerator in combination. Examples of the photopolymerization accelerator used here include p-toluenesulfinic acid or an alkali metal thereof; N, N-dimethylaniline, N, N-diethylaniline, N, N-dibenzylaniline, N, N-dimethyl-p-toluidine, pN, N-dimethylaminobenzoic acid, pN, N-diethylaminobenzoic acid, pN, N -Ethyl dimethylaminobenzoate, ethyl pN, N-diethylaminobenzoate, methyl pN, N-dimethylaminobenzoate, methyl pN, N-diethylaminobenzoate, pN, N-dimethylaminobenzaldehyde, pN, N-dimethylaminobenzoate 2-n-butoxyethyl acid, 2-n-butoxyethyl pN, N-diethylaminobenzoate, pN, N-dimethylaminobenzonitrile, pN, N-diethylaminobenzonitrile, pN, N-dihydroxyethylaniline, p-dimethyl Tertiary amines such as ruaminophenethyl alcohol, N, N-dimethylaminoethyl methacrylate, triethylamine, tributylamine, tripropylamine, N-ethylethanolamine;
Secondary amines such as N-phenylglycine and alkali metal salts of N-phenylglycine;
A combination of the tertiary amine or secondary amine with citric acid, malic acid, 2-hydroxypropanoic acid;
Barbituric acids such as 5-butylaminobarbituric acid, 1-benzyl-5-phenylbarbituric acid;
Examples include organic peroxides such as benzoyl peroxide and di-tert-butyl peroxide. These photopolymerization accelerators can be used alone or in combination.

In particular, tertiary fragrances in which nitrogen atoms are directly bonded to aromatics such as ethyl pN, N-dimethylaminobenzoate, 2-n-butoxyethyl pN, N-dimethylaminobenzoate, and N, N-dimethylaminoethyl methacrylate. Secondary amines such as aliphatic tertiary amines having polymerizable groups such as aromatic amines or N, N-dimethylaminoethyl methacrylate, N-phenylglycine, alkali metal salts of N-phenylglycine, etc. are preferably used. .

In particular, a combination of a photosensitizer and a photopolymerization accelerator is preferred when trying to quickly complete the curing of the dental restorative material composition of the present invention,
In particular, (I) camphorquinone,
(II) An ester compound of a tertiary aromatic amine in which a nitrogen atom is directly bonded to an aromatic group such as ethyl pN, N-dimethylaminobenzoate and pN, N-dimethylaminobenzoic acid 2-n-butoxyethyl, or N, A combination with an aliphatic tertiary amine having a polymerizable group such as N-dimethylaminoethyl methacrylate or a secondary amine such as N-phenylglycine or an alkali metal salt of N-phenylglycine;
(III) Combination with acylphosphine oxide;
(IV) A combination of acylphosphine oxide and p-toluenesulfinic acid or alkali metal salt;
(V) A combination of an ester compound of a tertiary aromatic amine in which a nitrogen atom is directly bonded to an aromatic and an acyl phosphine oxide or acyl phosphine oxide; (VI) a tertiary aromatic in which a nitrogen atom is directly bonded to an aromatic. A combination of an amine ester compound and an alkali metal salt of p-toluenesulfinic acid is preferably used. Although the compounding quantity of a polymerization accelerator will not be limited if photocuring performance is accelerated | stimulated, Usually, it is used in 1-200 weight part with respect to 100 weight part of photoinitiators.

As the polymerization initiator (C) used in the present invention, it is preferable to use a photopolymerization initiator as described above, but a thermal polymerization initiator or a redox initiator can also be used. Specific examples are shown below.

As the thermal polymerization initiator, organic peroxides, diazo compounds and the like can be preferably used. In order to carry out the polymerization efficiently in a short time, it is preferable to use a compound having a decomposition half-life at 80 ° C. of 10 hours or less.

Examples of organic peroxides that can be used in the present invention include diacyl peroxides such as acetyl peroxide, isobutyl peroxide, decanoyl peroxide, benzoyl peroxide, and succinic acid peroxide; diisopropyl peroxide Peroxydicarbonates such as di-2-ethylhexyl peroxydicarbonate and diallyl peroxydicarbonate; peroxy such as tert-butyl peroxyisobutyrate, tert-butyl neodecanate and cumene peroxyneodecanate Examples of the esters include peroxide sulfonates such as acetylcyclohexylsulfonyl peroxide.

Examples of diazo compounds that can be used in the present invention include 2,2′-azobisisobutyronitrile, 4,4′-azobis (4-cyanovaleric acid), 2,2′-azobis. (4-methoxy-2,4-
Dimethoxyvaleronitrile), 2,2′-azobis (2-cyclopropylpropionitrile) and the like. In the present invention, benzoyl peroxide and 2,2′-azobisisobutyronitrile are more preferable. In addition, a redox initiator that initiates polymerization at around room temperature, such as a combination of an organic peroxide and a reducing agent such as a tertiary amine, can also be used.

The thermal polymerization initiator, redox initiator or photopolymerization initiator may be used in combination.
The dental restorative material composition (D) constituting the dental restorative material kit of the present invention includes a polymerizable monomer (A), a filler (B), and a polymerization initiator (C) as described above. A part of the organic solvent (E0) that is packaged separately from the dental restorative composition (D) and formulated as a low viscosity composition (E) to be used together May be added to the dental restorative material composition (D), and the organic solvent in the dental restorative material composition (D) with respect to the total weight (ΣD) of the dental restorative material composition (D). (E0)
The ratio (ΣE0 / ΣD) of the total weight (ΣE0) is usually 0.75 or less, preferably 0.5 or less.

The viscosity of the dental restorative material composition (D) (viscosity of the paste) can be adjusted by blending such an amount of the organic solvent (E0).
The polymerizable monomer (A), the filler (B), and the polymerization initiator (C) that form the dental restorative material composition (D) of the present invention have a repeated impact test strength within a specific range. It is preferable that the composition be such that

In the present invention, this repeated impact test is performed using a test piece having a size of 10 mm × 25 mm × 1.5 mm ^t formed using the dental restorative material kit of the present invention. Specifically, a dental restorative material composition prepared by adding the above-mentioned polymerizable monomer (A), filler (B), polymerization initiator (C), and other components as necessary. (D) is defoamed under reduced pressure and then filled into a syringe or the like. Separately from this, a low-viscosity composition (E) is prepared as described later, and the required amount is collected in a sealed container.

The test piece can be produced by various methods using the dental restorative material composition (D) and the low viscosity composition (E) as described above.
Particularly in the present invention using a _{(D A 1) 10mm × 25mm} × 1.5mm t size possible Teflon ^TM mold manufacturing a test piece S _A 1 of preparing a test piece S _A 1 by photopolymerization. In particular,
10mm × 25mm × 1.5mm ^t voids a transparent glass plate on one surface of the formed Teflon ^TM mold contact of the air gap of the Teflon ^TM mold extruding the dental restorative material composition (D) from the syringe Then, smooth the surface with a construction tool such as a flat brush, a spatula, or a brush to which the low-viscosity composition (E) is adhered, and place a transparent glass plate thereon. Then, using a visible light irradiator, dental restorative material composition filled in the gap Teflon ^TM mold (D) by photopolymerization to form a cured product. The cured product can be manufactured test piece S _A 1 by punched Teflon ^TM mold.

The repeated impact test of the test piece S _A 1 formed in this way is performed using a repeated impact test apparatus shown in FIG. In FIG. 2, reference numeral 10 denotes a repeated impact test apparatus. In the present invention, the repeated impact test was conducted using a repeated impact test apparatus manufactured by Morimoto Seisakusho. In this repeated impact test apparatus 10, pedestals 12 and 14 are arranged 20 mm apart from each other, and an impact weight 16 made of SUS is installed in a substantially vertical direction above it. The impact weight 16 has a dome shape with a lower end 18 having a diameter of 5.6 mm, and the upper end is configured to be movable up and down by a driving device (not shown). In the repeated impact test, first, a test piece is handed over the top surfaces of the mounts 12 and 14 and bonded with double-sided tape (20 mm span). Next, the impact weight 16 is placed 10 mm away from the upper surface of the test piece, and an impact is repeatedly applied to the test piece from this position under conditions of an impact load of 134 g and an impact frequency of 56 times / minute. In this way, the impact test is performed using five test pieces until the hardened layer made of the hard resin of the test piece is cracked and broken, and the number of impacts at that time is measured to obtain an average value. The number of impacts of the test piece S _A 1 is rounded off.

In the present invention, a cured body (D) formed from the dental restorative material composition (D) as described above (
The number of impacts measured for the specimen S _A 1) is usually 1400 times or more, preferably 15
It is preferable to set the composition of the dental restorative material composition (D) to be 00 times or more, particularly preferably 2500 times or more.

In addition to the above-described test piece S _A 1, (D _A 2) a cured product of a dental restoration material composition (D) having a size of 10 mm × 25 mm × 0.5 mm ^t , and 10 mm × 25 mm × 1.0 mm ^The number of impacts measured in the same manner as described above for a laminate (test piece S _A 2) with a restoration material for a crown having a bending strength of 80 ± 20 MPa of ^t size is usually 1400 times or more, preferably 1500 times or more. Particularly preferably, the composition of the dental restorative material composition (D) is set so as to be 2500 times or more.

(D _A 1) such specimen S _A 2 is a cured body of the and the dental restorative composition of the size of 10mm × 25mm × 0.5mm ^t using a Teflon ^TM mold similarly (D) Then, one of the arranged glass plates was removed, and methyl methacrylate / 2-hydroxyethyl methacrylate / 2 mol 2-hydroxyethyl was added to the surface of the cured body of the exposed dental restorative composition (D). Urethane dimethacrylate compound derived from 1 mole of trimethylhexamethylene diisocyanate (U-3) / 4-methacryloxypropyltrimellitic acid / copolymer powder of methyl methacrylate and ethyl methacrylate (Fujikura Kasei Kogyo Co., Ltd .: EMA35) / camphorquinone / N, N-dimethylaminobenzoate 2-n-butoxyethyl = 54.5 / 9.9 / 19.8 / 9.9 / 5.0 / 0.45 / 0.45 wt% , It is cured.

Next, a Teflon ^TM mold with a gap of 10 mm × 25 mm × 1.0 mm ^t is placed on the surface of the adhesive, and a restoration material paste for a crown having a bending strength of 80 ± 20 MPa after curing is applied to the mold. After filling the gap, the dental restoration material paste is cured by irradiating visible light to cure the dental restoration material composition (D) and the dental restoration material paste with a bending strength of 80 ± 20 MPa. _A test piece S _A 2 which is a laminate with the body can be formed.

The test piece formed in this manner is placed on the pedestals 12 and 14 with a span of 20 mm so that the cured material of the crown restoration material paste having a bending strength of 80 ± 20 MPa faces the impact weight 16. Repeat the impact test as above.

The "cured body of the restoration material paste for crowns with a bending strength of 80 ± 20 MPa" means a device equipped with Shimadzu EZ · Test with a tooth-shaped push rod and a lower folding core jig or a commonly used bending test. When a 30 mm x 3.0 mm x 3.0 mm ^t test piece is subjected to a three-point bending test at a room temperature of 20 mm between spans and a crosshead speed of 2 mm / min using a machine etc., the bending strength is 80 ± 20 MPa. Use a restoration material paste for a crown restoration having a bending characteristic within the range.

In the dental restorative material composition (D) of the present invention, the number of impacts of either the test piece S _A 1 or the test piece S _A 2 prepared as described above exhibits the above value. as long as, it is preferable both impact number of the test piece S _a 1 and test piece S _a 2 is indicative of the value as described above.

When measuring the number of impacts as described above, when performing a bending test by the above method on the cured body of the dental restoration material composition (D) constituting the dental restoration material kit of the present invention, the teeth The bending strength of the cured body of the crown restorative composition (D) is usually 40 MPa or more, preferably 50 MPa, particularly preferably 60 MPa, and the breaking strain is usually 3% or more, preferably 4% or more, particularly When the crown restorative composition (D) having a composition of preferably 5% or more is used, the impact resistance tends to be improved. It is predicted that there is a certain degree of correlation between the bending properties and the impact resistance. This dental restoration material composition (D) of the dental restoration material kit of the present invention is used for this dental treatment. When a cured body of a restoration material composition for a crown is laminated on the surface of the restoration material composition (D), the bending elastic strain of the cured body of the dental restoration material composition (D) is laminated thereon. It is desirable to adjust the composition of the dental restorative material composition (D) so as to exceed the bending fracture strain (generally less than 0.5 to 3%) of the above-mentioned restoration body for crown restoration.

The adhesive used for measuring the number of impacts of the two-layer laminate is such that the joint surface between the dental restorative material composition (D) and the hardened body of the dental restorative material with a strength of 80 ± 20 MPa is used. , Used to prevent delamination during the impact test. In general, when the dental restoration material kit of the present invention is used for the interior, and other crown restoration materials or dental fillers are used for the exterior to produce a dental material such as a jacket crown or an inlay. After the dental restorative material composition (D) constituting the dental restorative material kit of the present invention is cured, the surface layer of the hardened layer of the dental restorative material composition (D) is used for the placement of the dental material. The radicals are trapped in the air and there is always an unpolymerized layer. Since this unpolymerized layer plays the role of an adhesive when a dental material is built and cured thereon, when using the dental restorative material kit of the present invention, it is necessary to use the adhesive as described above. It is not always necessary.

Further, the dental restorative material composition (D) constituting the dental restorative material kit of the present invention is (D _B 1) 80 mm × 10 mm × 2 mm ^{t made} of a cured product of the dental restorative material composition (D). impact strength measured for the test piece S _B 1 unnotched Charpy impact test according flatwise method usually is a value of greater than 11 kJ / m ^2, more preferably 15 kJ / m ² or more, more preferably 17 kJ / m It is desirable to have a composition that can form a cured product of ² or more.

Furthermore, the dental restorative material composition (D) constituting the dental restorative material kit of the present invention is (D _B 2) 80 mm × 10 mm × thickness made of a cured product of the dental restorative material composition (D). to 1.0 mm ^t, impact strength measured for the thickness 1.0 mm ^t flexural strength 80 ± specimen S _B 2 to the crown restorative materials were laminated in 20MPa Charpy impact test according flatwise method, usually a value of greater than 11 kJ / m ^2, preferably 14 kJ / m ² or more, still more preferably those having formable composition the cured body is 16 kJ / m ² or more.

The above-mentioned test piece S _B 1 has a Teflon ^TM mold in which a gap of 80 mm × 10 mm × 2 mm ^t is formed, a transparent glass plate placed on one side, and the dental restorative material of the present invention in the mold gap. After filling the dental restoration material composition (D) (depressurized and degassed) that makes up the kit, and smoothing the surface with a build-up jig to which the low-viscosity composition (E) is adhered, the gap is filled. Dental restoration material composition (D)
A transparent glass plate is arranged so as to cover. Then, the dental restorative material composition filled in the gap of the mold to (D) is irradiated with visible light cured dental restorative material composition (D), a test piece S _B of by demolding from the mold 1 can be obtained.

In addition, the two-layer test piece S _B 2 is a Teflon ^TM in which a gap of 80 mm × 10 mm × 1 mm ^t is formed.
A transparent glass plate is placed on one side of the mold, and the dental restorative material composition (D) (under reduced pressure defoaming) constituting the dental restorative material kit of the present invention is filled in the gap of the mold, After smoothing the surface with a build-up jig to which the low-viscosity composition (E) is adhered, a transparent glass plate is placed so as to cover the dental restorative material composition (D) filled in the gap. After curing the dental restorative material composition (D) by irradiating visible light in the same manner as described above, the transparent glass plate on the visible light irradiation side is removed, and the dental restorative material composition (D) is cured. On the surface of the body, urethane dimethacrylate compound (U-3) / 4-methacryloxypropyl trimellit derived from methyl methacrylate / 2-hydroxyethyl methacrylate / 2 mol 2-hydroxyethyl and 1 mol trimethylhexamethylene diisocyanate Copolymer powder of acid / methyl methacrylate and ethyl methacrylate (manufactured by Fujikura Kasei Kogyo Co., Ltd .: EMA35) / camphorquinone / N, N-dimethylaminobenzoic acid 2-n-butoxyethyl = 54.5 / 9.9 / 19.8 / 9.9 An adhesive composed of /5.0/0.45/0.45% by weight is applied and cured.

Next, a Teflon ^TM mold having a gap of 80 mm × 10 mm × 1 mm ^t is placed on the surface of the adhesive, and a restoration material paste for a crown which has a bending strength of 80 ± 20 MPa after hardening is put in the gap of the mold. After filling, the dental restoration material paste is cured by irradiating visible light to cure the dental restoration material composition (D) and the dental restoration material paste cured body having a bending strength of 80 ± 20 MPa. A two-layer laminate test piece S _B 2 which is a laminate of

A frame material formed using the dental restorative material kit of the present invention by using the dental restorative material composition (D) whose impact strength measured by the Charpy impact test by the flatwise method satisfies the above conditions Alternatively, the mechanical properties, particularly impact resistance, of dental prosthetic materials such as dental lining materials can be dramatically improved.

The dental restorative material composition (D) constituting the dental restorative material kit of the present invention is, for example, a polymerizable monomer (A), a filler (B) containing inorganic short fibers (B1), and Defoaming which kneads the polymerization initiator (C) and other components as necessary using a mortar or a mixing device such as a kneader, revolving / spinning type agitator, etc., and defoams the resulting paste under reduced pressure After defoaming using an apparatus or the like, the sealed container is filled. The dental restorative material composition (D) thus produced is packaged independently so as not to come into contact with the low viscosity composition (E) described later. In addition, this dental restorative material composition (D) contains a polymerization initiator (C), and the reaction may proceed by contact with air or light irradiation. It is preferable to fill a container that blocks light transmission. Examples of such a container include a light-shielding syringe.

The dental restorative material kit of the present invention is formed from the dental restorative material composition (D) as described above and the low viscosity composition (E).
The low viscosity composition (E) constituting the dental restorative material kit of the present invention has a viscosity of 3 at 25 ° C.
It is a low-viscosity composition having a viscosity of 10,000 mPa · s or less, preferably in the range of 10,000 to 0.1 mPa · s. Such a low-viscosity composition (E) contains an organic solvent (E0) or a soluble polymerizable monomer (E1) whose boiling point at 1 atm is in the range of 30 ° C. to 130 ° C. Further, the organic solvent (E0) and the soluble polymerizable monomer (E1) may be mixed.

The organic solvent (E0) contained in the low viscosity composition (E) constituting the dental restorative material of the present invention,
An organic solvent having a boiling point measured at 1 atm within a range of 30 ° C to 130 ° C, preferably 40 ° C to 110 ° C, and such an organic solvent is usually a liquid at room temperature. Boiling point is 30 ° C
If the liquid organic solvent that is less than 1 is used alone, the organic solvent is instantly volatilized from the build-up jig at the time of the build-up described later. When an organic solvent exceeding 130 ° C is used alone, the dental restoration material after construction (D)
Since this organic solvent is likely to remain therein, the dental restoration material composition (D) and a known dental restoration material such as a hard resin for a crown or a dental filler to be deposited thereon are difficult to adhere. Therefore, problems such as inferior mechanical properties of the cured body of the dental restorative material composition (D) such as difficulty in expressing desired mechanical properties due to such poor adhesion may occur. In the present invention, the boiling point is a boiling point as a mixture when a plurality of organic solvents are used, and some organic solvents include azeotropic compounds. Means boiling point.

The organic solvent (E0) constituting the low-viscosity composition (E) in the present invention is an organic solvent that satisfies the above boiling point, and is (a) a hydroxyl group-containing compound, (b) a ketone group-containing compound, (c) Ester group-containing compounds, (2) ether group-containing compounds, (e) other organic solvents can be used.

Examples of (a) hydroxyl group-containing compounds that can be used as the organic solvent (E0) in the present invention include alcohols such as methanol, ethanol, n-propanol, isopropanol, n-butanol, isobutanol, and tert-butanol. Among these, methanol, ethanol, and isopropanol are preferable, and ethanol is particularly preferable.

  Examples of the (b) ketone group-containing compound that can be used as the organic solvent (E0) in the present invention include acetone, methyl ethyl ketone, diethyl ketone, and the like, and acetone is particularly preferable.

Examples of (c) ester group-containing compounds that can be used as the organic solvent (E0) in the present invention include methyl acetate, ethyl acetate, butyl acetate, methyl (meth) acrylate, ethyl (meth) acrylate, and n-butyl. (Meth) acrylate, isobutyl (meth) acrylate, and (meth) acrylate compounds shown in the examples of the polymerizable monomer such as tetrafurfuryl (meth) acrylate can be mentioned. Methyl methacrylate is preferred, and particularly preferred. Note that (meth) acrylate compounds such as methyl (meth) acrylate and ethyl (meth) acrylate are both ester group-containing compounds and have polymerizability, and in the present invention, an organic solvent (E0) At the same time, it is a compound that can also be a soluble polymerizable monomer (E1), but in the present invention, these compounds are defined as belonging to the organic solvent (E0).

  Examples of the (d) ether group-containing compound that can be used as the organic solvent (E0) in the present invention include diethyl ether, 1,4-dioxane, tetrahydrofuran and the like, and tetrahydrofuran is particularly preferable.

Examples of other organic solvents that can be used as the organic solvent (E0) in the present invention include 5 carbons such as n-pentane, iso-pentane, n-hexane, iso-hexane, and n-heptane. To 10 aliphatic hydrocarbons, aromatic hydrocarbons such as benzene and toluene, nitrile group-containing organic solvents such as acetonitrile and acrylonitrile, aldehyde group-containing compounds such as propionaldehyde and butyraldehyde, halogens such as methylene chloride and chloroform Examples thereof include group-containing organic solvents. In addition, the organic solvent (E0) used in the present invention may be a compound having a combination of a plurality of groups of the compounds described in (i) to (d) in one molecule.

As these organic solvents (E0), the above-mentioned compounds can be used alone or in combination.
The viscosity at 25 ° C. of the organic solvent (E0) as described above is 30,000 mPa · s or less, preferably 20,000 mPa · s or less, more preferably 10,000 mPa · s or less.

In the present invention, the low-viscosity composition (E) is a soluble polymerizable monomer having a viscosity at 25 ° C. of 30,000 mPa · s or less, preferably 20,000 mPa · s or less, particularly preferably 10,000 mPa · s or less. The body (E1) can also be used.

The soluble polymerizable monomer (E1) that can be used in the present invention has a viscosity at 25 ° C. of 30,000 mPa ·
It is adjusted to be s or less, preferably 20,000 mPa · s or less, particularly preferably 10,000 mPa · s or less. As the polymerizable monomer (E1), among the above-mentioned polymerizable compounds, those satisfying the above viscosity conditions, or those that satisfy the above viscosity conditions when used together with an organic solvent (E0). Can be used. Therefore, the low-viscosity composition (E) used in the present invention, as described above, can be used alone organic solvent (E0) having a specific boiling point, or soluble polymerization in this organic solvent (E0). Insoluble monomer (E1) is mixed with organic solvent (E0) and soluble polymerizable monomer (E1), or more than 30,000 mPa · s at 25 ° C., preferably 20,000 mPa · s. Hereinafter, it is particularly preferable to use a mixture adjusted to have a viscosity of 10,000 mPa · s or less.

Thus, when the viscosity at 25 ° C. of this low-viscosity composition (E) exceeds 30,000 mPa · s, the dental restorative material composition (D) is built up using a build-up jig brush by the method described later. At this time, due to the high viscosity (E1) itself causes stringing and is difficult to handle, and the dental restorative material composition (D) may be unevenly coated, etc.In the present invention, the soluble polymerizable monomer Examples of the body (E1) include the above (i) monofunctional polymerizable monomer, (ii) bifunctional polymerizable monomer, (iii) trifunctional polymerizable monomer, (iv) tetrafunctional or higher And a polyfunctional (meth) acrylate compound having at least one of (a1) tricyclododecane skeleton, (a2) aromatic ring skeleton, and (a3) polycarbonate skeleton. Can do.

Examples of compounds that can be suitably used as the soluble polymerizable monomer (E1) in the present invention are shown below.
Examples of (i) monofunctional polymerizable monomers that can be used as the soluble polysynthetic monomer (E1) in the present invention include the (meth) acrylic acid ester compounds described above. Among them, as aromatic compounds, 2,2-bis ((meth) acryloyloxyphenyl) propan, 2,2-bis [4- (3- (meth) acryloyloxy) -2-hydroxypropoxyphenyl] propane , 2,2-bis (4- (meth) acryloyloxypolyethoxyphenyl)
Propane can be mentioned, and as an aliphatic compound, ethylene glycol di (
(Meth) acrylate, diethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, tetraethylene glycol di (meth) acrylate, pentamethylene glycol di (meth) acrylate, hexaethylene glycol di (meth) acrylate, propylene glycol di (Meth) acrylate, dipropylene glycol di (meth) acrylate, tripropylene glycol di (meth) acrylate, tetrapropylene glycol di (meth) acrylate, pentapropylene glycol di (meth) acrylate, hexpropylene glycol di (meth) acrylate, Nonapropylene glycol di (meth) acrylate and other ethylene glycol or propylene glycol di (meth) acrylate, or ethoxylated cyclohexane di (meth) Di (meth) acrylate compounds in which cyclic, linear or branched aliphatics such as acrylate are combined with ethylene glycol or propylene glycol, as well as neopentyl glycol di (meth) acrylate, tricyclodecane dimethanol Di (meth) acrylate, 1,4-butanediol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, 1,9-nonanediol di (meth) acrylate, 1,12-dodecanediol di ( Aliphatic di (meth) acrylate compounds such as (meth) acrylate, or 2-hydroxyethyl (meth) acrylate, 2-hydroxyethylpropyl (meth) acrylate, and 3-chloro-2-hydroxypropyl (meth) acrylate And a hydroxyl group-containing (meth) acrylate compound corresponding to these (meth) acrylates and hexamethyldiethyl Cyanate, can be mentioned trimethyl hexamethylene diisocyanate, diisocyanate methyl cyclohexane, isophorone diisocyanate, as adduct is preferable examples obtained from the addition of a diisocyanate compound such as methylenebis (4-cyclohexyl isocyanate).

  Examples of the tri- or higher functional polymerizable monomer include the (meth) acrylic acid ester compounds described above. Among them, trimethylolpropan tri (meth) acrylate, pentaerythritol tri (meth) acrylate, dipenta Preferred examples of the erythritol tri (meth) acrylate are tetra- or higher functional polymerizable monomers such as pentaerythritol tetra (meth) acrylate and dipentaerythritol hexa (meth) acrylate. .

As described above, the low-viscosity composition (E) of the present invention can be used alone as an organic solvent (E0), or a soluble polymerizable monomer (E1) can be used alone, Further, the organic solvent (E0) and the soluble polymerizable monomer (E1) can be used in combination. That is, in the present invention, the low-viscosity composition (E) comprises an organic solvent (E0) having a specific melting point or a specific soluble polymerizable monomer (E1), and this low-viscosity composition (E) May be a mixture of an organic solvent (E0) and a soluble polymerizable monomer (E1).

The viscosity of the low-viscosity composition (E) of the present invention is the viscosity of the low-viscosity composition (E) itself, and when the low-viscosity composition comprises a specific organic solvent (E0), the specific solubility polymerizability When composed of the monomer (E1), it may consist of a mixture of a specific organic solvent (E0) and a soluble polymerizable monomer (E1), but the viscosity in the low-viscosity composition (E) of the present invention Is the viscosity of each of the organic solvent (E0) and the soluble polymerizable monomer (E1) when used alone, and the low viscosity composition (E) is a specific organic solvent (E0).
And the soluble polymerizable monomer (E1) are the viscosity of these mixtures.

When the viscosity of the low-viscosity composition (E) of the present invention exceeds 30,000 mPa · s, the composition (D) is applied to a build-up jig by the method described below, so that the low-viscosity composition is high due to the high viscosity. The product (E1) itself may be difficult to handle due to stringing, and the dental restorative material composition (D) may be unevenly coated.

As described above, the low-viscosity composition (E) of the present invention is a low-viscosity liquid consisting of the above components,
Basically, it consists of an organic solvent (E0) and / or a soluble polymerizable monomer (E1), but other components may be blended within the range not impairing the object of the present invention.

Examples of other components that can be blended in the low viscosity composition (E) of the present invention include a part of the filler (B) blended in the dental restorative composition (D). The ratio (ΣB / ΣE) of the total weight (ΣB) of the filler (B) in the low-viscosity composition (E) to the total weight (ΣE) of the low-viscosity composition (E) in this case is Usually, it is 0.33 or less, preferably 0.20 to 0.005. Examples of the filler (B) that can be blended in the low-viscosity composition (E) include a part of the inorganic short fibers (B1) and a particulate filler having an average particle diameter of 0.001 to 100 μm. A material (B2) can be mentioned.

Furthermore, a part of the polymerization initiator (C) may be added to the low viscosity composition (E) of the present invention, and the total weight (ΣE) of the low viscosity composition (E) used here. The ratio (ΣC / ΣE) of the total weight (ΣC) of the polymerization initiator (C) in the low-viscosity composition (E) in the range of 0.0001 to 0.1, preferably 0. It is in the range of 001 to 0.5.

The dental restorative material kit of the present invention comprises the dental restorative material composition (D) and the low viscosity composition (E) as described above, and the dental restorative material composition (D) and the low viscosity composition. (E) is packaged independently so that they do not contact each other. In the dental restorative material kit of the present invention, the dental restorative material composition (D) is preferably packed in a light-shielding syringe or the like and packaged in a state where it does not come into contact with air as described above. In packaging the product (E), the low-boiling compound contained in the low-viscosity composition (E) is packaged so that the viscosity of the low-viscosity composition (E) is not changed by transpiration. Further, when using the dental restorative material kit of the present invention of the present invention, the dental restorative material composition (D) is built up while adhering the low viscosity composition (E) to the build-up jig. A packaging material that does not cause a change in viscosity due to transpiration of a low-boiling compound from the low-viscosity composition (E) during the build-up operation is used. In general, the low-viscosity composition (E) is filled in an openable / closable sealed container, and a separate container for separating the required amount is prepared separately from the closed container, and the required amount of the low-viscosity composition (E) is prepared from the sealed container. When the dental restoration material composition (D) is built up by separating the product (E) into a sorting container, the adhesion of the low-viscosity composition (E) to the build-up jig is exclusively performed by this sorting. The low viscosity composition (E) dispensed in a container is used.

In the dental restorative material kit of the present invention, the dental restorative material composition (D) and the low-viscosity composition (E) are such that the dental restorative material composition (D) does not adhere to the build-up jig and The dental restoration material composition (D) can be used in a quantity ratio that does not cling to the device. The amount of the low-viscosity composition (E) used is usually about 0.01 to 10 g, preferably 0.0 to 1 g of the dental restorative material composition (D).
It is about 1 to 3 g. Therefore, for example, with respect to 100 parts by weight of the dental restorative material composition (D) sealed and filled in a syringe or the like, the amount of the low viscosity composition (E) supplied by being filled in a separate sealed container is Strictly speaking, it is 10 to 100 parts by weight, but the low-viscosity composition (E) once separated from the sealed container into the sorting container can be returned to the sealed container even if it is a single construction work. Since it is not preferable, the dental restorative material kit according to the present invention is 1.1 to 2 times the amount theoretically required to build the dental restorative material composition (D) because it is discarded. Amount, preferably 1
. 1 to 1.5 times the amount of the low viscosity composition (E) is supplied as a kit in combination with the dental restorative material composition (D).

Although the above explanation is focused on the aspect of building up the dental restorative material composition (D) while adhering the low-viscosity composition (E) dispensed in a sorting container to the building jig, As a build-up jig,
Use a flat brush, etc., and install a container for storing the low-viscosity composition (E) in the flat brush so that a certain amount of low-viscosity composition (E) is supplied to the tip of the flat brush. Thus, the dental restorative material composition (D) can be built up with the brush tip always impregnated with a certain amount of the low viscosity composition (E).

Whether the low viscosity composition (E) constituting the dental restorative material kit of the present invention is an organic solvent (E0) having a predetermined boiling point or a soluble polymerizable monomer (E1) having a specific viscosity A mixture of a specific viscosity composed of an organic solvent (E0) and a soluble polymerizable monomer (E1), and in such a state that the low-viscosity composition (E) is adhered to the surface of the build-up jig, By treating the restoration material composition (D), the dental restoration material composition (D) does not adhere to the surface of the build-up jig, and the dental restoration material composition (D) does not adhere to the build-up jig. Therefore, the dental restorative material composition (D) can be uniformly built up on the surface of the abutment tooth model, which is a portion to which the dental restorative material composition (D) is to be applied.

Next, a method for using the dental restorative material kit of the present invention will be described.
The dental restorative material kit of the present invention comprises a dental restorative material composition (D) and a low viscosity composition (E) as described above, and this dental restorative material composition (D) is used as an abutment tooth model. The dental restorative composition (D) and the dental restorative composition (D) can be formed by using a build-up jig with a low-viscosity composition (E) attached to the surface of the material to form a frame material or a crown lining material. Build up.

Such a built-up dental restorative composition (D) is usually in the form of a paste, and if there is no low viscosity composition (E) on the surface of the build-up jig, the dental restorative composition (D) Adheres to the build-up jig and the dental restorative material composition (D) cannot be applied uniformly. Therefore, when this dental restorative material composition (D) is built without the low viscosity composition (E), unevenness occurs in the build-up thickness, and this unevenness causes the frame material or crown lining. Due to uneven build-up of the dental restorative material composition (D), such as a material, the strength of the frame material or the crown crown material becomes non-uniform.

In contrast, with the low-viscosity composition (E) attached to the surface of the build-up tool, attach the low-viscosity composition (E) to a construction tool such as a flat brush attached to a syringe or a metal spatula. Even if the dental restoration material composition (D) is built up, the dental restoration material composition (D) does not cling to the build-up jig, and the surface of the build-up jig has a dental restoration. The material composition (D) does not adhere.

Therefore, by building up the dental restoration material composition (D) using the dental restoration kit of the present invention, it is possible to build up a frame material, a crown lining material, and the like having a uniform thickness. And since the dental frame material or crown lining material formed using the dental restorative material kit of the present invention has high homogeneity, in cooperation with the dental material arranged on this surface Bonding can be performed with a certain high mechanical strength.

  When using the dental filler kit of the present invention, it is possible to use, as a build-up jig, a build-up jig that is usually used for building up a dental composition such as a flat brush, a metal spatula, a brush, or a spatula. A device for automatically supplying a low-viscosity composition (E) that can supply a constant amount of the low-viscosity composition (E) as described above to the tip portion of such a conventionally used build-up jig. May be incorporated.

Hereinafter, the dental restorative material kit and the manufacturing method thereof according to the present invention have been described focusing on the optimum form. However, the dental restorative kit of the present invention further includes the dental restorative material composition (D).
Alternatively, the low-viscosity composition (E) may contain other components such as powders, organic and inorganic pigments, stabilizers, and fragrances as long as the characteristics of the present invention are not impaired.

In addition,
Even when a crown restoration material or dental filling material that does not use a frame material or crown lining material is applied clinically, it may break for a certain period of time depending on how the occlusal pressure is applied and the form of the restoration material. There are some cases that do not fold. Therefore, in such a case, the dental restorative material composition (D) constituting the dental restorative material kit of the present invention is used together with the low viscosity composition (E) to obtain a frame material or a tooth. If applied to the crown lining material, it is thought that it will be more difficult to break, and according to the inventor's calculations, the crown specimen is the same specimen shape but the frame material is not used, and the crown restoration material or dental filling material is singly cured. Comparing the impact resistance of the body, it is also known that the impact resistance of the two-layer structure formed as described above preferably has an impact resistance of 1.5 times or more. .
〔Example〕
Hereinafter, the dental restorative material kit and the method of using the same according to the present invention will be specifically described with reference to Examples, but the present invention is not limited to these Examples.

The following (U-1), (U-2), and (U-3) were used as polyfunctional (meth) acrylate compounds having a tricyclodecane skeleton or an aromatic skeleton.
・ Compound (U-1)
The product name: (UMF04) (manufactured by Shin-Nakamura Chemical Co., Ltd.) was used as the compound (U-1).

The weight average molecular weight in terms of styrene of this compound (U-1) is about 2,900.
Structural formula:
CH ₂ = CZ ¹ -CO ₂ -G _a -O-CONH- ^R R ^L -NHCO-Y-CONH- ^L R ^R -NHCO ₂ -G _a -O ₂ CZ ¹ C = H ₂ C
... (1)
In the above formula (1), Z ¹ is a hydrogen atom, G is a methylene group, a is 2, ^L R ^R is a group represented by the following formula (2), ^R R ^L Is the reverse of the combination.

  Furthermore, Y is a group represented by the following formula (6).

In the above formula (6), ^L X ^R is — [O (CH ₂ ) ₅ OCO] —, ^R X ^L is a bond whose left and right are reversed, and m + n is 2.
・ Compound (U-2)
A compound having the following structural formula was used as the compound (U-2).
Structural formula:
CH ₂ = CZ ¹ -CO ₂ -G _a -O CONH-R-NHCO-Y-CONH-R-NHCO ₂ -G _a -O ₂ CZ ¹ C = H ₂ C
... (1)
In the above formula (1), Z ¹ is a methyl group, G is a methylene group, a is 2, R
Is a group represented by the above formula (2).
Furthermore, Y is a group represented by the following formula (7).

In the above formula (7), G is an ethylene group, I is —C (CH ₃ ) ₂ —, and m + n is 2.
・ Compound (U-3)
As the compound (U-3), product name: (UA-1223FM) (manufactured by Shin-Nakamura Chemical Co., Ltd.) was used.
CH ₂ = CZ ¹ -CO ₂ -CH ₂ CH ₂ -O- [CO- (CH ₂ ) ₅ O] ₃ -CONH- ^R R ^L -NHCO-Y-CONH- ^L R ^R -NHCO- [O (CH ₂ ) ₅ -OC-] ₃ -O-CH ₂ CH ₂ -O ₂ CZ ¹ C = CH ₂
(11)
Here, Z ¹ is a methyl group, R is a group represented by the above formula (2), Y is a group represented by the above formula (6), and in the above formula (6), X Is — [O (CH ₂ ) ₅ OCO] —, and m + n is 2.

The following (U-4) and (U-5) were used as polyfunctional (meth) acrylate compounds having a polycarbonate skeleton.
・ Compound (U-4)
The product name: (UN-9000SN) (manufactured by Negami Industrial Co., Ltd.) was used as the compound (U-4).
CH ₂ = CZ ¹ -CO _2- (CH (CH ₃ ) CH ₂ ) -OCONH- ^R R ^L -NHCO _2- (CH ₂ ) ₅ CO ₂ (CH ₂ ) ₆ O [CO ₂ (CH ₂ ) ₆ O ] _n CO ₂ (CH ₂ ) ₆ O ₂ CNH- ^L R ^R -NHCO _2- (CH ₂ (CH ₃ ) CH) -CO ₂ -Z ¹ C = CH ₂
(12)
Here, Z ¹ is a hydrogen atom, ^L R ^R and ^R R ^L are groups represented by the above formula (2), and n is an integer of 3.
・ Compound (U-5)
The product name: (UN-9000SM) (manufactured by Negami Kogyo Co., Ltd.) was used as the compound (U-5).
The structural formula is the same except that Z ^{1 of} U-4 is changed to a methyl group.

  Table 1 shows a list of polymerizable monomers used in Examples and Comparative Examples other than (U-1) to (U-5).

  Table 2 shows the polymerizable monomer compositions used in Examples and Comparative Examples.

Ii) The polymerizable monomer composition contains 0.3 parts by weight of a visible light polymerization initiator (camphorquinone) and a visible light polymerization accelerator (N, N) with respect to 100 parts by weight of the polymerizable monomers. -Dimethylaminobenzoic acid 2-n-butoxyethyl) 0.3 parts by weight are dissolved.
[Production Example 1]
Preparation of Hydrophobized Inorganic Short Fiber (MF-150) 100 g of E glass fiber (EFH150-01: Central Glass Fiber Co., Ltd.) having an average fiber length of 150 μm and an average fiber diameter of 10 μm was suspended in 800 g of ethanol, and γ-methacryloxypropyl 3 g of trimethoxysilane (hereinafter referred to as γ-MET), purified water
5 g was added and refluxed for 2 hours. After removing the solvent with an evaporator, it was hydrophobized by heat treatment at 80 ° C. for 24 hours in a nitrogen atmosphere to produce a hydrophobized inorganic short fiber (MF-150).
[Production Example 2]
Preparation of hydrophobic inorganic short fiber (MF-75) 100 g of E glass fiber (EFH75-01: Central Glass Fiber Co., Ltd.) having an average fiber length of 75 μm and an average fiber diameter of 10 μm was suspended in 800 g of ethanol, and 3 g of γ-MET was purified. 1.5 g of water was added and refluxed for 2 hours. After removing the solvent with an evaporator, it was hydrophobized by heat treatment at 80 ° C. for 24 hours in a nitrogen atmosphere to produce hydrophobized inorganic short fibers (MF-75).

In a mortar, 7 g of the polymerizable monomer composition (M-1) described above is added as a component containing the polymerizable monomer (A) and the polymerization initiator (C), and the hydrophobicity is the filler (B). Colloidal Silka (Product name: R8
12 (manufactured by Nippon Aerosil Co., Ltd.), primary particle size 0.007 μm) was added and kneaded in a lump, and then 2.5 g of hydrophobic inorganic short fiber (MF-150) as filler (B) was added. The paste, which is a dental restorative material composition (D) used in the kit of the present invention, was prepared while kneading in small portions. The obtained paste was degassed under reduced pressure and filled into a syringe for New Metacolor Inphysopaque (Sun Medical Co., Ltd.) having a tip inner diameter of φ1.8 mm.

0.1 g of the dental restorative material composition (D) (paste) was squeezed out and attached to the crown portion of the abutment tooth model shown in FIG.
A flat brush attached to New Metacolor Infice (manufactured by Sun Medical Co., Ltd.) is immersed in a glass bottle containing acetone (boiling point: 56 ° C./760 mmHg) which is the low viscosity composition (E) of the present invention. After 0.1 g is adhered to the surface, the dental restoration material composition (D) paste is stretched using a flat brush, and then coping with a thickness of about 0.5 mm on the abutment tooth model. Material composition (D)
A frame material made of paste was built. In addition, each time the acetone as the low-viscosity composition (E) volatilized during the build-up, the build-up operation was performed while 0.1 g of acetone as the low-viscosity composition (E) was reattached to the flat brush.

There was no adhesion of the dental restoration material composition (D) paste on the flat brush at the time of building up, and it was easy to build up, and the unevenness of the frame material was visually observed to evaluate the thickness unevenness. I was not able to admit. Moreover, as a result of evaluating the odor of the frame material by a sensory test after 5 minutes at room temperature after construction, it was found that acetone odor was not recognized and acetone was volatilized and removed from the frame material.
[Comparative Example 1]
In Example 1, except that acetone, which is a low viscosity composition (E), was not attached to a flat brush, an attempt was made to build up a paste, which is a dental restorative composition (D), on an abutment tooth model. However, the paste was clinging to the flat brush, the operability was very poor and it was difficult to build up, and in addition, uneven thickness unevenness was observed in the built-up dental restorative material composition (D).

In Example 1, instead of a flat brush, a metal spatula PFIAB1 (manufactured by HU-FREDY) was used, and the low viscosity composition (E) acetone 0. A frame material made of the dental restorative material composition (D) was constructed in the same manner except that 1 g was adhered.

There was no adhesion or stickiness of the dental restorative material composition (D) on the metal spatula, it was easy to build up, and no unevenness in the thickness of the frame material was observed. Moreover, as a result of evaluating the acetone odor by the evaluation method of Example 1, it was found that the acetone odor was not recognized and acetone was volatilized and removed from the frame material.
[Comparative Example 2]
In Example 2, except that acetone, which is a low viscosity composition (E), was not attached to a metal spatula, a paste, which is a dental restorative material composition (D), was similarly built on the abutment tooth model. The paste adhered to the spatula and stringing was recognized, so that the operability was poor and it was difficult to build up. In addition, uneven thickness was observed in the dental restoration material composition (D) that had been built up.

In Example 1, ethanol (boiling point: 7) was used instead of acetone, which is a low-viscosity composition (E).
Except that 6 ° C./760 mmHg) was used, a paste was formed as a dental restorative material composition (D) built in the same manner to form a frame material.

  Thus, when forming the frame material, the build-up operation was evaluated in the same manner as in Example 1, and the thickness unevenness and ethanol odor of the obtained frame material were evaluated in the same manner as in Example 1. There was no clinging and adhesion of the paste to the flat brush at the time of building up, it was easy to build up, and no unevenness in the thickness of the frame material was observed. Moreover, the ethanol odor was not recognized by the obtained flame | frame material.

In Example 1, a frame material was formed in the same manner except that methyl methacrylate (boiling point: 101 ° C./760 mmHg) was used instead of acetone, which is the low-viscosity composition (E).

When forming the frame material in this manner, the build-up operation was evaluated in the same manner as in Example 1, and the build-up operation was evaluated in the same manner as in Example 1 for the obtained frame material. In the same manner as in Example 1, the thickness unevenness and methyl methacrylate odor were evaluated. There was no clinging and adhesion of the paste to the flat brush at the time of building up, it was easy to build up, and no unevenness in the thickness of the frame material was observed. Also, no methyl methacrylate odor was observed.

In Example 1, instead of acetone, which is a low viscosity composition (E), ethyl acetate (boiling point:
A frame material was formed in the same manner except that 77 ° C./760 mmHg) was used.
When forming the frame material in this manner, the build-up operation was evaluated in the same manner as in Example 1, and the build-up operation was evaluated in the same manner as in Example 1 for the obtained frame material. In the same manner as in No. 1, thickness unevenness and ethyl acetate odor were evaluated. There was no clinging and adhesion of the paste to the flat brush at the time of building up, it was easy to build up, and no unevenness in the thickness of the frame material was observed. Also, no ethyl acetate odor was observed.

  In Example 1, instead of acetone, which is a low-viscosity composition (E), the polymerizable multimeric composition (M-1) was dissolved in acetone in an amount of 20% by weight as the low-viscosity composition (E). A frame material was formed in the same manner except that the solvent used (viscosity: 3000 mPa · s / 25 ° C.) was used.

When forming the frame material in this manner, the build-up operation was evaluated in the same manner as in Example 1, and the build-up operation was evaluated in the same manner as in Example 1 for the obtained frame material. In the same manner as in No. 1, thickness unevenness and acetone odor were evaluated. There was no clinging and adhesion of the paste to the flat brush at the time of building up, it was easy to build up, and no unevenness in the thickness of the frame material was observed. Also, no acetone odor was observed.
[Comparative Example 3]
In Example 1, a frame material was formed in the same manner except that xylene having a boiling point of 144 ° C. (760 mmHg pressure condition) was used instead of acetone as the low-viscosity composition (E).

  In this way, when forming the frame material, the build-up operation was evaluated in the same manner as in Example 1, and the thickness unevenness and xylene odor of the obtained frame material were evaluated in the same manner as in Example 1. There was no clinging and adhesion of the paste to the flat brush at the time of build-up, it was easy to build up, and no unevenness in the thickness of the frame material was observed, but it was found that xylene remained in the formed frame material.

Dental restorative material composition was filled in a syringe in Example 1 (D), 10mm diameter of the one side was covered with glass and extruded into a Teflon ^TM mold thickness 2 mm. A double-sided tape on which a hole having a diameter of 4.8 mm is formed is placed on the surface of the dental restorative material composition (D) extruded from the syringe, and the surface of the dental restorative material composition (D) in the hole portion. Was smoothed using a flat brush to which 0.1 g of acetone, which is a low-viscosity composition (E), was attached.

After leaving at room temperature for 3 minutes, a hard resin paste for crowns (New Metacolor Infispace, manufactured by Sun Medical Co., Ltd., A3-B) is formed on the surface of the dental filler composition (D) at the opening. ) And irradiated with light for 1 minute using a visible light irradiator (α-Light) manufactured by Morita Manufacturing Co., Ltd., to harden the dental filler composition (D) and the hard resin paste for the crown. .

Attempts were made to peel the joint surface between the hard resin cured crown and the hardened body of the dental filler composition (D) produced in Example 1 with tweezers. It turns out that it has adhered enough.
[Comparative Example 4]
In Example 7, instead of acetone, which is a low-viscosity composition (E), a cured product of a dental filler composition (D) and a dental crown, except that xylene having a boiling point of 144 ° C. was used. The hard resin cured body was joined. When the hardened resin body for a crown and the cured body of the dental filler composition (D) thus obtained were peeled off with tweezers, the hardened resin body for a crown was peeled off with tweezers. It was found that the hard resin cured body for the crown peeled off, and the bonding state between the two was insufficient.

  In Example 7, the dental filler composition (D) was similarly prepared except that ethanol having a boiling point of 78 ° C. (under 760 mmHg pressure condition) was used instead of acetone as the low boiling point composition (E). The cured body and the hard resin cured body for a crown were joined.

Attempts were made to peel the joint surface between the hardened resin for the crown and the hardened material of the dental filler composition (D) thus obtained with tweezers. I understood that.

In Example 7, the dental filler composition (D) was similarly used except that methyl methacrylate having a boiling point of 101 ° C. (under 760 mmHg pressure condition) was used instead of acetone as the low boiling point composition (E). The hardened body and the hard resin hardened body for a crown were joined.

Attempts were made to peel the joint surface between the hardened resin for the crown and the hardened material of the dental filler composition (D) thus obtained with tweezers. I understood that.

  In Example 7, the dental filler composition (D) was similarly used except that ethyl acetate having a boiling point of 77 ° C. (under 760 mmHg pressure condition) was used instead of acetone as the low boiling point composition (E). The hardened body and the hard resin hardened body for a crown were joined.

Attempts were made to peel the joint surface between the hardened resin for the crown and the hardened material of the dental filler composition (D) thus obtained with tweezers. I understood that.

7 g of the polymerizable monomer composition (M-1) is put in a mortar, and 0.2 g of hydrophobic colloidal silka (product name: R812 (manufactured by Nippon Aerosil Co., Ltd.), primary particle size: 0.007 μm) is added all at once. After kneading, a small amount of 2.5 g of aluminum borate whisker (average fiber length: 10 μm, average fiber diameter: 1.0 μm, product name: YS-4, manufactured by Shikoku Kasei Co., Ltd.) as an inorganic short fiber filler The paste was added while kneading each time to prepare the dental restorative material composition (D) of the present invention. The obtained pate was degassed under reduced pressure and filled into a syringe for new metacolor infinite stop (Sun Medical Co., Ltd.) having a tip inner diameter of φ1.8 mm.

0.1 g of the dental restorative material composition (D) (paste) was squeezed out and attached to the crown portion of the abutment tooth model shown in FIG.
A flat brush attached to New Metacolor Infice (manufactured by Sun Medical Co., Ltd.) is immersed in a glass bottle containing acetone (boiling point: 56 ° C./760 mmHg) which is the low viscosity composition (E) of the present invention. After 0.1 g is adhered to the surface, the dental restoration material composition (D) paste is stretched using a flat brush, and then coping with a thickness of about 0.5 mm on the abutment tooth model. Material composition (D)
A frame material made of paste was built. In addition, when acetone, which is the low-viscosity composition (E), volatilizes during the build-up, the build-up operation was performed while 0.1 g of acetone, which is the low-viscosity composition (E), was reattached to the flat brush.

There was no adhesion of the dental restoration material composition (D) paste on the flat brush at the time of building up, and it was easy to build up, and the unevenness of the frame material was visually observed to evaluate the thickness unevenness. I was not able to admit. Moreover, as a result of evaluating the odor of the frame material by a sensory test after 5 minutes at room temperature after construction, it was found that acetone odor was not recognized and acetone was volatilized and removed from the frame material.

A frame was obtained in the same manner as in Example 1 except that the dental restorative material composition (D) containing the hydrophobic short staple fiber (MF-75) was used instead of the hydrophobic short staple fiber (MF-150). The material was built up.

There was no adhesion or stickiness of the dental restorative material composition (D) on the flat brush, it was easy to build and no unevenness in the thickness of the frame material was observed. Moreover, as a result of evaluating the acetone odor by the evaluation method of Example 1, it was found that the acetone odor was not recognized and acetone was volatilized and removed from the frame material.

In Example 1, the polymerizable monomer composition (M-1) was used instead of the polymerizable monomer composition (M-1).
Prepare the dental restorative material composition (D) in the same way except using -7), build the frame material in the same way except using this dental restorative material composition (D), and build up operation. And uneven thickness,
Odor was evaluated in the same manner as in Example 1. There was no clinging or sticking of the paste to the brush at the time of building up, it was easy to build up, and no unevenness in the thickness of the frame material was observed. Also, no acetone odor was observed.

The dental restorative material composition (D) filled in the syringe in Example 1 was extruded into a Teflon ^TM mold gap in which a gap of 10 mm × 25 mm × 0.5 mm ^t was formed with one side covered with transparent glass, Using a flat brush impregnated with 0.1 g of acetone, which is a low-viscosity composition (E), the dental restorative composition (D) was homogenized in the voids. Then, the dental restorative material composition (D) by placing a transparent glass to the open surface of the voids of the Teflon ^TM mold which is filled with a visible light irradiator from the outside of the transparent glass (alpha-Light, Morita Seisakusho The dental restorative composition (D) in the Teflon ^TM mold cavity is polymerized by irradiating visible light for 3 minutes using a product of 10 mm × 25 mm × 0.5 mm ^t dental filler composition ( A cured product of D) was formed.

Next, the transparent glass on the irradiated surface side is removed, and methyl methacrylate / 2-hydroxyethyl methacrylate / U-3 / 4-methacryloxypropyl trimellitic acid / on the cured body of the dental restorative material composition (D) Copolymer powder of methyl methacrylate and ethyl methacrylate (manufactured by Fujikura Kasei Kogyo Co., Ltd .: EMA35) / camphorquinone / N, N-dimethylaminobenzoic acid 2-n-butoxyethyl = 54.5 / 9.9 / 19.8 / 9.9 / 5.0 An adhesive composed of /0.45/0.45 wt% was applied and photopolymerized with α-Light for 1 minute.

Teflon ^{TM with} a gap of 10mm x 25mm x 1mm ^t on the formed adhesive
The mold is placed, a hard resin to the gap (New meth color in office paste, Sun Medical Co., Ltd. (A3-B)), and filled with Supachara, covering the both surfaces of the Teflon ^TM mold in transparent glass , New metacolor Infis hardened material and dental restorative composition (D) for repeated impact test after photopolymerization for 3 minutes with visible light irradiator (Morita, α-Light)
) And a test piece (10 mm × 25 mm × 1.5 mm ^t ) composed of a two-layer structure.

Next, a repeated impact test was performed on the test piece manufactured as described above using a repeated impact test apparatus as shown in FIG.
FIG. 2 is a schematic side view showing a repeated impact test apparatus, and 10 represents the repeated impact test apparatus as a whole. As the repeated impact test apparatus 10, a repeated impact test apparatus manufactured by Morimoto Seisakusho was used. In the repeated impact test apparatus 10, gantry 12 and 14 are arranged at a distance of 20 mm, and an impact weight 16 made of SUS is installed in a substantially vertical direction above it. The impact weight 16 has a dome shape with a lower end 18 of φ5.6 mm, and the upper end is configured to be movable up and down by a driving device (not shown). In the repeated impact test, first, a test piece is handed over the top surfaces of the mounts 12 and 14 and bonded with double-sided tape (20 mm span). At this time, the test piece is arranged so that the impact surface (upper surface) is on the hard resin side. Next, the impact weight 16 is placed 10 mm away from the upper surface of the test piece, and an impact is repeatedly applied to the test piece from this position under conditions of an impact load of 134 g and an impact frequency of 56 times / minute. In this way, an impact test was conducted until cracks occurred in the hardened layer made of the hard resin of the test piece, and the number of impacts at that time was measured.

  The results are shown in Table 3. The number of repeated impacts is rounded to the first decimal place.

In Example 14, the polymerizable monomer composition (M) used as a component containing the polymerizable monomer (A) blended in the dental restorative material composition (D) produced in Example 1 1) A dental restorative material composition (D) was produced using a polymerizable monomer composition (M-2) in place of this, and this dental restorative material composition (D) was used. A test piece was produced in the same manner as in Example 14, and the impact test was repeatedly performed on this test piece. The results are shown in Table 3.

In Example 14, the polymerizable monomer composition (M) used as a component containing the polymerizable monomer (A) blended in the dental restorative material composition (D) produced in Example 1 -1) Instead of producing a dental restorative material composition (D) using a polymerizable monomer composition (M-3), this dental restorative material composition (D) was used. A test piece was produced in the same manner as in Example 14, and the impact test was repeatedly performed on this test piece. The results are shown in Table 3.

In Example 14, instead of the dental restorative material composition (D) produced in Example 1, a polymerizable monomer composition (M-1) as a component containing a polymerizable monomer (A) in a mortar 7 g), and as a filler (B), 0.2 g of hydrophobic colloidal silka (product name: R812 (manufactured by Nippon Aerosil Co., Ltd.), primary particle size: 0.007 μm) is added and kneaded in a lump. As (B), 2.5 g of aluminum borate whisker (average fiber length: 10 μm, average fiber diameter: 1.0 μm, product name: YS-4, manufactured by Shikoku Kasei Kogyo Co., Ltd.) was added while kneading little by little. A test piece was produced in the same manner as in Example 14 except that a dental filler composition (D) produced by defoaming the paste obtained under reduced pressure was used by filling a syringe. This test piece was repeatedly impacted in the same manner as in Example 14. Test was carried out. The results are shown in Table 3.

In Example 14, instead of the dental restorative material composition (D) produced in Example 1, a polymerizable monomer composition (M-1) as a component containing a polymerizable monomer (A) in a mortar 7 g), and as a filler (B), 0.2 g of hydrophobic colloidal silka (product name: R812 (manufactured by Nippon Aerosil Co., Ltd.), primary particle size: 0.007 μm) is added all at once and kneaded. Dental filler prepared by adding 2.5 g of hydrophobic inorganic short fibers (MF-75) as a filler (B) while kneading little by little, forming a paste, and defoaming the resulting paste under reduced pressure A test piece was produced in the same manner as in Example 14 except that the composition (D) was filled in a syringe and used, and the test piece was repeatedly impact tested in the same manner as in Example 14. The results are shown in Table 3.

In Example 14, instead of the dental restorative material composition (D), the polymerizable monomer composition (M-1) contained in the dental restorative material composition (D) was used as the polymerizable monomer composition. The impact test was repeated in the same manner as in Example 14 except that the dental restorative material composition (D) changed to the product (M-4) was used.
The results are shown in Table 3.

In Example 14, instead of the dental restorative material composition (D), the polymerizable monomer composition (M-1) contained in the dental restorative material composition (D) was used as the polymerizable monomer composition. The impact test was repeated in the same manner as in Example 14 except that the dental restorative material composition (D) changed to the product (M-5) was used. The results are shown in Table 3.

In Example 14, instead of the dental restorative material composition (D), the polymerizable monomer composition (M-1) contained in the dental restorative material composition (D) was used as the polymerizable monomer composition. The impact test was repeated in the same manner as in Example 14 except that the dental restorative material composition (D) changed to the product (M-6) was used. The results are shown in Table 3.

In Example 14, instead of the dental restorative material composition (D), the polymerizable monomer composition (M-1) contained in the dental restorative material composition (D) was used as the polymerizable monomer composition. The impact test was repeated in the same manner as in Example 14 except that the dental restorative material composition (D) changed to the product (M-7) was used. The results are shown in Table 3.

In Example 14, instead of the dental restorative material composition (D), the polymerizable monomer composition (M-1) contained in the dental restorative material composition (D) was used as the polymerizable monomer composition. The impact test was repeated in the same manner as in Example 14 except that the dental restorative material composition (D) changed to the product (M-8) was used. The results are shown in Table 3.

7 g of the polymerizable monomer composition (M-1) is put in a mortar, and 0.2 g of hydrophobic colloidal silka (product name: R812 (manufactured by Nippon Aerosil Co., Ltd.), primary particle size: 0.007 μm) is added all at once. After kneading, 2.5 g of hydrophobized inorganic short fibers (MF-150) were added while kneading little by little to make a paste, and this paste was defoamed under reduced pressure to obtain a dental restorative composition (D). The dental restoration material composition (D) was prepared and filled into the syringe.

The dental restorative material composition (D) is extruded into a Teflon ^TM mold having a transparent glass on one side and a void of 80 mm × 10 mm × 2 mm ^t formed, and 0.1 g of acetone as a low viscosity composition (E) is extruded. The dental restorative material composition (D) was homogenized in the voids using a flat brush impregnated with. Then, the Teflon ^TM mold by placing a transparent glass to the surface being opened, covering the dental restorative material composition (D), a visible light irradiator (Morita Seisakusho, alpha-Light) 3 minutes using Irradiated with visible light to obtain a cured body of the dental restorative material composition (D). Using this cured body (80 mm × 10 mm × 2 mm ^t : no notch) as a specimen for Charpy test, the impact strength was measured by the flatwise method.

The Charpy impact tester used here is a product name: Charpy digital impact tester DG-UB type (manufactured by Toyo Seiki Seisakusho).
The test piece formed as described above was measured for impact strength by the flatwise method using the Charpy digital impact tester, and as a result, the impact value was 19 KJ / m ² .

The dental filler composition (D) prepared in Example 19 was covered with transparent glass on one side, 80 mm
× 10mm × 1mm ^t Extruded into the gap of Teflon ^TM mold with gap formed, and dental restoration material composition in the gap using a flat brush impregnated with 0.1g of acetone, which is a low viscosity composition (E) Product (D) was homogenized. Then, the dental restorative material composition (D) by placing a transparent glass to the open surface of the voids of the Teflon ^TM mold which is filled with a visible light irradiator from the outside of the transparent glass (alpha-Light, Morita Seisakusho the dental restorative composition in the gap Teflon ^TM mold was irradiated with visible light for 3 minutes using Ltd.) (D) by polymerizing a dental filling material of ^{80mm × 10mm × 1mm t (D} ) A cured product was formed.

Next, the transparent glass on the irradiated surface side is removed, and methyl methacrylate / 2-hydroxyethyl methacrylate / U-3 / 4-methacryloxypropyl trimellitic acid / on the cured body of the dental restorative material composition (D) Copolymer powder of methyl methacrylate and ethyl methacrylate (manufactured by Fujikura Kasei Kogyo Co., Ltd .: EMA35) / camphorquinone / N, N-dimethylaminobenzoic acid 2-n-butoxyethyl = 54.5 / 9.9 / 19.8 / 9.9 / 5.0 An adhesive composed of /0.45/0.45 wt% was applied and photopolymerized with α-Light for 1 minute.

A Teflon ^TM mold with a gap of 80 mm × 10 mm × 1 mm ^t is placed on the surface of the adhesive formed in this manner, and a hard resin (New Metacolor Infispace, manufactured by Sun Medical Co., Ltd. (A3-B)) is used. After filling with a spatula and covering both sides with transparent glass, photopolymerization is further performed for 3 minutes with a visible light irradiator (Morita Manufacturing Co., Ltd., α-Light), and a specimen for a Charpy impact test (80 mm x 10 mm x 2 mm ^t : no notch). As a result of conducting a Charpy impact test on this test piece in the same manner as in Example 24, the impact value was 15 KJ / m ² .

Instead of the polymerizable monomer composition (M-1) contained in the dental restorative material composition (D) of Example 1, the same amount of the polymerizable monomer composition (M-5) was used. Then, a dental restorative material composition (D) was produced, defoamed under reduced pressure, and then filled into a syringe for New Metacolor Inphistop opaque having a diameter of 1.8 mm.

Separately, low viscosity composition containing 99.8% by weight of 3G, 0.1% by weight of camphorquinone and 0.1% by weight of 2-n-butoxyethyl N, N-dimethylaminobenzoate Object (E)
Was prepared. The viscosity at 25 ° C. of this low viscosity composition (E) was 9 mPa · s. 0.005 g of this low-viscosity composition (E) was collected in a glass bottle.

The dental restorative composition (D) from the syringe to the crown part of the abutment tooth model as shown in FIG.
Was adhered by extrusion. Put the flat brush attached to New Meta Color Inphis (manufactured by Sun Medical Co., Ltd.) into the glass bottle containing the low-viscosity composition (E), and impregnate the flat brush with 0.005 g of the low-viscosity composition (E). I let you.

Using this flat brush, the dental restorative material composition (D) was stretched to form a paste frame material on the abutment tooth model with a thickness of about 0.5 mm. There was no adhesion of the paste to the flat brush at the time of build-up, and the build-up operation was easy. The thickness unevenness was evaluated by visually observing the unevenness of the frame material, but no thickness unevenness was observed.

  In Example 26, the buildability was examined in the same manner except that the amount of the low-viscosity composition (E) dispensed into the glass bottle was changed to 0.05 g. During the build-up, there was no paste sticking to the flat brush, and the build-up operation was completed easily. Moreover, there was no thickness unevenness of the frame material visually.

In Example 26, instead of 3G, 0.01 g of di (methacryloxyethyl) trimethoxyhexanediurethane (UDMA: viscosity 10,000 mPa · s / 25 ° C.) and camphorquinone were used as the low-viscosity composition (E). was prepared ^{1 × 10 -5 g, N,} N- dimethylamino benzoic acid 2-n-butoxyethyl 1 × 10 ^-5 g low viscosity composition containing (E), were collected 0.01g minutes in a glass bottle . The viscosity at 25 ° C. of this low-viscosity composition (E) was 10,000 mPa · s.

In Example 26, the buildability was examined in the same manner except that a low-viscosity composition containing UDMA prepared as described above was used as the low-viscosity composition (E). During the build-up, there was no paste sticking to the flat brush, and the build-up operation was completed easily. Moreover, there was no thickness unevenness of the frame material visually.

When the dental restorative material composition (D) and the low viscosity composition (E) are in a non-contact state, the dental restorative material kit of the present invention is used when the dental restorative material composition (D) is used. The dental restorative composition (D) is prepared by adhering the low viscosity composition (E) to a construction jig such as a brush, brush, spatula, spatula, etc. and handling the dental restorative composition (D). ) Does not adhere to the build-up jig, the dental restorative material composition (D) does not pull on the thread, and when forming the frame material, the dental restorative material composition of the present invention (D) can be applied uniformly.

FIG. 1 is a diagram showing an example of an abutment tooth model used in the present invention. FIG. 2 is a schematic side view showing a repeated impact test apparatus used in the present invention.

Explanation of symbols

DESCRIPTION OF SYMBOLS 10 ... Repeat impact test apparatus 12 ... Base 14 ... Base 16 ... Impact weight 18 ... Lower end part

Claims (18)

A dental restorative material kit comprising a dental restorative material composition (D) and the low-viscosity composition (E) in a non-contact state with the dental restorative material composition (D),
The dental restorative material composition (D) comprises a polymerizable monomer (A) and a filler (B1) containing inorganic short fibers (B1) with respect to 100 parts by weight of the polymerizable monomer (A). ); 1 to 900 parts by weight and a polymerization initiator (C),
The low-viscosity composition (E) contains an organic solvent (E0) and / or a soluble polymerizable monomer (E1) whose boiling point at 1 atm is in the range of 30 ° C. to 130 ° C. A dental restorative material kit, wherein the viscosity composition (E) has a viscosity at 25 ° C of 30,000 mPa · s or less. The amount of the polymerization initiator (C) in the dental restorative material composition (D) is such that the polymerizable monomer (A) 100
2. The dental restorative material kit according to claim 1, wherein the kit is in a range of 0.1 to 10 parts by weight with respect to parts by weight. Part of the organic solvent (E0) is added to the dental restorative material composition (D), and the dental restorative material composition with respect to the total weight (ΣD) of the dental restorative material composition (D) The dental restorative material kit according to claim 1, wherein the ratio (ΣE0 / ΣD) of the total weight (ΣE0) of the organic solvent (E0) in the product (D) is 0.75 or less. . Part of the filler (B) is added to the low-viscosity composition (E), and the total viscosity (ΣE) of the low-viscosity composition (E) in the low-viscosity composition (E) The dental restorative material kit according to claim 1, wherein the ratio (ΣB / ΣE) of the total weight (ΣB) of the filler (B) is 0.33 or less. A part of the polymerization initiator (C) is added to the low viscosity composition (E), and the low viscosity composition (E)
The ratio (ΣC / ΣE) of the ratio of the total weight (ΣC) of the polymerization initiator (C) in the low-viscosity composition (E) to the total weight (ΣE) of 0.0001 to 0.1 2. The dental restorative material kit according to claim 1, wherein the dental restorative material kit is inside.   The polymerizable monomer (A) constituting the dental restorative material composition (D) is (a1) a polyfunctional (meth) acrylate compound having a tricyclodecane skeleton, (a2) a polyfunctional monomer having an aromatic ring skeleton. The at least one polyfunctional (meth) acrylate compound selected from the group consisting of a functional (meth) acrylate compound and a polyfunctional (meth) acrylate compound having a (a3) polycarbonate skeleton is included. The dental restoration material kit according to item 1. The polymerizable monomer (A) forming the dental restorative material composition (D) is (a1) a polyfunctional (meth) acrylate compound having a tricyclodecane skeleton or (a2) a polyfunctional having an aromatic ring. The (meth) acrylate compound, the (a1) polyfunctional (meth) acrylate compound having a tricyclodecane skeleton or (a2) a polyfunctional (meth) acrylate compound having an aromatic ring is represented by the following formula (1): The dental restorative material kit according to claim 1 or 6, wherein the dental restorative material kit is a compound having the following structure:
CH ₂ = CZ ¹ -CO ₂ -G _a -O CONH-R-NHCO-Y-CONH-R-NHCO ₂ -G _a -O ₂ CZ ¹ C = H ₂ C
... (1)
(However, in the above formula (1), Z ¹ each independently represents a hydrogen atom or a methyl group, G is _{- (CH 2) -, -} (CH 2 CHR 1) - and - (CHR ¹ CH ₂ )-Is any group selected from the group consisting of:-R ¹ represents an alkyl group having 1 to 10 carbon atoms, a is each independently an integer of 1 to 10 and R is independently Any of the groups represented by the following formulas (2) to (5):

Y is a group having a tricyclodecane skeleton represented by the following formula (6) or a group having an aromatic ring skeleton represented by the following formula (7);

(In the above formula (6), X is —O— or — [O (CH ₂ ) ₅ OCO] —, and represents an integer of m + n = 2 to 10);

(In the above formula (7), G is any group selected from the group consisting of — (CH ₂ ) —, — (CH ₂ CHR ¹ ) — and — (CHR ¹ CH ₂ ) —), and R ¹ is represents an alkyl group having 1 to 10 carbon atoms, further, I is, Arikiriden group, cyclohexylidene group having 1 to 4 carbon atoms, -O -, - S -, - SO 2
-Or -CO-, m + n = 2 to 10 represents an integer. )). The polymerizable monomer (A) forming the dental restorative material composition (D) is (a1) a polyfunctional (meth) acrylate compound having a tricyclodecane skeleton or (a2) a polyfunctional having an aromatic ring. The (meth) acrylate compound, the (a1) polyfunctional (meth) acrylate compound having a tricyclodecane skeleton or the (a2) polyfunctional (meth) acrylate compound having an aromatic ring is represented by the following formula (8): The dental restorative material kit according to claim 1 or 6, wherein the dental restorative material kit is a compound having a structure as described above;
CH ₂ = CZ ¹ -CO ₂ -G _a -O- [CO-G _a O] _b -CONH-RNHCO-Y-CONH-R-NHCO- [OG _a -OC-] _b -O-G _a -O ₂ CZ ¹ C = CH ₂
... (8)
(However, in the above formula (8), Z ¹ each independently represents a hydrogen atom or a methyl group, G is _{- (CH 2) -, -} (CH 2 CHR 1) -, and, - (CHR ¹ CH ₂ ) — is any group selected from the group consisting of R ¹ represents an alkyl group having 1 to 10 carbon atoms, a and b each independently represent an integer of 1 to 10; Each independently represents any group represented by the following formulas (2) to (5):

Y is a group having a tricyclodecane skeleton represented by the following formula (6) or a group having an aromatic ring skeleton represented by the following formula (7);

(In the above formula (6), X is —O— or — [O (CH ₂ ) ₅ OCO] —, and represents an integer of m + n = 2 to 10);

(In the above formula (7), G is any group selected from the group consisting of — (CH ₂ ) —, — (CH ₂ CHR ¹ ) —, and — (CHR ¹ CH ₂ ) —), and R ¹ Represents an alkyl group having 1 to 10 carbon atoms, and I is an alkylidene group, cyclohexylidene group, —O—, —S—, —SO ₂ —, or —CO— having 1 to 4 carbon atoms. M + n = 2 represents an integer of 2 to 10)). The polymerizable monomer (A) forming the dental restorative material composition (D) is (a3) a polyfunctional (meth) acrylate compound having a polycarbonate skeleton, and has the (a3) polycarbonate skeleton. The dental restorative material kit according to claim 1 or claim 6, wherein the polyfunctional (meth) acrylate compound is a compound having a structure represented by the following formula (9):
CH ₂ = CZ ¹ -CO ₂ -G _a -O ₂ CNH-R-NHCO ₂ G _a -CO ₂ D _a -O- [CO ₂ -G _a -O] _b CO ₂ -G _a -O ₂ CNH- R-NHCO ₂ -G _a -CO ₂ -Z ¹ C = CH ₂
... (9)
(However, in the above formula (9), Z ¹ each independently represents a hydrogen atom or a methyl group, G is _{- (CH 2) -, -} (CH 2 CHR 1) -, and, - (CHR ¹ CH ₂ ) — is any group selected from the group consisting of R ¹ represents an alkyl group having 1 to 10 carbon atoms, a and b each independently represent an integer of 1 to 10, and R is Each independently represents any group represented by the following formulas (2) to (5):

Y is a group having a tricyclodecane skeleton represented by the following formula (6) or a group having an aromatic ring skeleton represented by the following formula (7);

(In the above formula (6), X is —O— or — [O (CH ₂ ) ₅ OCO] —, and represents an integer of m + n = 2 to 10);

(In the above formula (7), G is any group selected from the group consisting of — (CH ₂ ) —, — (CH ₂ CHR ¹ ) —, and — (CHR ¹ CH ₂ ) —), and R ¹ Represents an alkyl group having 1 to 10 carbon atoms, and I is an alkylidene group, cyclohexylidene group, —O—, —S—, —SO ₂ —, or —CO— having 1 to 4 carbon atoms. M + n = 2 represents an integer of 2 to 10);
D is a methylene group or an isopropylene group. ). The inorganic short fibers (B1) contained in the filler (B) have an average fiber length in the range of 5 to 1000 μm, an average fiber diameter in the range of 0.1 to 100 μm, and an average fiber length. 2. The dental restorative material kit according to claim 1, wherein the ratio of / average fiber diameter is in the range of 3 to 10,000. In addition to the inorganic short fibers (B1), the filler (B) has an average particle size of 0.001 to 10
0 to 50 μm of particulate filler (B2) is added in an amount of 0.1 to 50 parts per 100 parts by weight of the polymerizable monomer (A).
The dental restorative material kit according to any one of claims 1 to 4, wherein the kit is contained in an amount of parts by weight. The dental restorative material composition (D) is
(D _A 1) _A 10 mm × 25 mm × 1.5 mm ^t test piece S _A 1 made of a cured product formed using the dental restorative material composition (D) was placed on a test piece of a repeated impact test apparatus. Placed on the part (between spans = 20 mm),
(D _A 2) wherein the dental restorative material composition in the cured product of 10 mm × 25 mm × thickness 0.5 mm ^t consisting of (D), crown restorative materials flexural strength 80 ± 20 MPa with a thickness of 1.0 mm ^t _A test piece S _A 2 laminated with
Place the restoration material for the crown on the impact weight side and place it on the test piece placement part (span interval = 20 mm) of the repeated impact test device.
When each test piece was subjected to repeated impacts under the conditions that the diameter of the tip of the impact weight was 5.6 mm, the impact load was 134 g, the drop distance was 10 mm, and the repetition cycle was 56 times / minute, The dental restorative material kit according to claim 1, wherein the dental restorative material kit has a composition capable of forming a cured product having an impact number of 1400 times or more leading to destruction of the test pieces S _A 1 and / or S _A 2. The dental restorative material composition (D) is
(D _B 1) Impact strength measured in a Charpy impact test by a flatwise method on an 80 mm × 10 mm × 2 mm ^t unnotched test piece S _B 1 made of a cured product of the dental restorative material composition (D), and (D _B 2) consists of the dental restorative composition cured product of the (D) 80mm × 10mm × thickness 1.0 mm ^t
Furthermore, the impact strength measured by the Charpy impact test by the flatwise method on the test piece S _B 2 laminated with a 1.0 mm- ^t bending strength restoration material of 80 ± 20 MPa exceeds 11 kJ / m ² The dental restorative material kit according to claim 1, which has a composition capable of forming a cured product.   The organic solvent (E0) is at least one compound selected from the group consisting of a hydroxyl group-containing compound, a ketone group-containing compound, an ester group-containing compound, and an ether group-containing compound. The dental restorative material kit according to item.   The soluble polymerizable monomer (E1) is at least one group selected from the group consisting of a glycol group, an alkynyl group, an alkyl group, a carbamoyl group, a group having an aromatic ring, and a group having a heterocyclic ring. The dental restorative material kit according to claim 1, wherein the kit is a polymerizable monomer containing   The dental restoration material kit is a frame material forming material formed between the abutment tooth and the crown material when the crown material is mounted on the surface of the abutment tooth. The dental restoration material kit according to any one of Items 1 to 15.   The dental restorative material kit according to any one of claims 1 to 15, wherein the dental restorative material kit is a forming material of a crown lining material. When building up a dental restoration material composition using a build-up jig,
As the dental restorative material composition, a polymerizable monomer (A) and a filler (B) containing inorganic short fibers (B1) with respect to 100 parts by weight of the polymerizable monomer (A); 1 Use a dental restorative material composition (D) comprising ~ 900 parts by weight and a polymerization initiator (C),
Low viscosity with an organic solvent (E0) and / or soluble polymerizable monomer (E1) having a boiling point in the range of 30 ° C. to 130 ° C. at 1 atm and a viscosity at 25 ° C. of 30,000 mPa · s or less A dental restorative material composition (D), characterized in that the dental restorative material composition (D) is built up in a planned construction portion using a building-up jig on which the viscosity composition (E) has been previously attached. And a method for using a dental restorative material kit comprising a low-viscosity composition (E).

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