JP6584338B2 - Curable composition - Google Patents

Description

  The present invention relates to a curable composition, particularly a curable composition useful as a dental restorative material.

  Various dental restoration materials are used in dental treatment. For example, in the restoration of a tooth damaged by caries, fracture, or the like, a photocurable composite filling restoration material called a composite resin is generally used because of its ease of operation and high aesthetics. Such a composite resin is usually composed of a polymerizable monomer, a filler, and a polymerization initiator. Conventionally, as the polymerizable monomer used in the composite resin, a (meth) acrylate radically polymerizable monomer has been used because of its good photopolymerizability, and recently, cationic polymerization without inhibition of polymerization by oxygen. It has also been reported to use sex monomers.

  Restoration using a dental composite resin is indistinguishable from natural teeth and is in harmony with the surroundings, enabling restoration with high aesthetics. However, in an environment that emits ultraviolet light, short-wavelength visible light, or the like, the repaired site appears black, placing a mental burden on the patient. In order to improve this drawback, it has been proposed to add a fluorescent agent to a dental composite resin. Among the fluorescent agents used at this time, phthalate ester fluorescent agents are easily available, emit fluorescent light similar to natural teeth, and have exceptional aesthetic features, and are therefore advantageously used. (For example, Patent Document 1).

  On the other hand, diagnosis of a damaged site of a tooth using X-ray contrast is important in the field of tooth treatment. In order to meet this demand, there is a use of a filler having high X-ray contrast properties. Metal oxides such as zirconia, alumina, ytterbium trifluoride, composite oxides mainly composed of silica and zirconia, silica and titania, silica and barium oxide have X-ray contrast properties. An inorganic filler is also known.

  By the way, it goes without saying that tooth restoration materials are required to have aesthetic properties, and for that purpose, it is required to have transparency as close as possible to the natural tooth. However, X-ray contrast-enhanced metal oxides usually have a higher refractive index than the polymerizable monomers described above, and when these are blended directly into a composite resin, the opacity of the cured product is higher than that of natural teeth. Will be significantly stronger. Therefore, in the dental restorative material, it is useful that the inorganic filler having X-ray contrast properties has high X-ray contrast properties and is easy to obtain transparency close to natural teeth, such as ytterbium trifluoride. Rare earth compound particles.

JP-T-2002-520347

  The inventors of the present invention are capable of highly esthetic restoration that is indistinguishable from natural teeth, and that have a fluorescence similar to that of natural teeth, and have a high X-ray contrast property. Developed.

  However, according to the study by the present inventors, when the photopolymerization initiator composed of the amine compound and the phthalate ester fluorescent agent and a filler having high X-ray contrast properties are combined in a curable composition, It turned out that yellow discoloration generate | occur | produces in the state of the composition of this, and the state of the hardening body after hardening, and may cause a problem in actual use. Specifically, it was found that strong discoloration occurs when an acidic filler having a high X-ray contrast property and a strong surface acid point is used.

  When used as a dental composite resin, it is common to prepare multiple types of materials that are adjusted in color with pigments, dyes, etc. so that they can be selected and filled and restored according to the natural color. Is. However, the yellow discoloration as described above cannot be adjusted to a color tone close to that of natural teeth, and even if it can be adjusted, only a dark color tone can be adjusted, which causes a problem that restoration in harmony with natural teeth cannot be performed.

  In the above situation, the present invention is a curable composition comprising a combination of a photopolymerization initiator comprising a fluorescent agent containing the amine compound and a phthalate ester, and an acidic filler having X-ray contrast properties. An object of the present invention is to develop a high X-ray contrast property in which the polymerization activity of the curable composition is well maintained and the fluorescence of a fluorescent agent containing a phthalate ester is also well expressed. .

  The present inventors have intensively studied to solve the above problems. As a result, it has been found that such a problem is caused by the formation of a yellow colored substance due to the coexistence of a fluorescent agent containing an amine compound and a phthalate ester and an acidic filler. As a result, the inventors have found that the above problems can be solved, and have completed the present invention.

That is, the present invention has an X-ray contrast property comprising (A) a polymerizable monomer, (B) an amine compound, (C) a fluorescent agent containing a phthalate ester, and (D) inorganic particles containing a fluorine atom. A fluorescent agent containing 0.01 to 3.0 parts by mass of the (B) amine compound and (C) a phthalate ester with respect to 100 parts by mass of the (A) polymerizable monomer. It is a curable composition containing 1 to 100 parts by mass of an acidic filler having X-ray contrast properties , comprising 0.0005 to 0.05 parts by mass and inorganic particles containing (D) fluorine atoms .

The curable composition of the present invention has fluorescence close to that of a natural tooth, and the natural tooth and the cured product of the curable composition can be easily distinguished by high X-ray contrast. Therefore, it is extremely useful as a curable composition used for dental restorative materials such as dental composite resins and hard resins.

  Hereinafter, each component of the curable composition of this invention is demonstrated.

<(A) Polymerizable monomer>
The (A) polymerizable monomer is a component that is polymerized and cured. A preferred (A) polymerizable monomer is a component that polymerizes and cures by irradiation with light or the like in the presence of a polymerization initiator (F) polymerization initiator and (B) an amine compound described later.

  There is no restriction | limiting in particular as said (A) polymeric monomer, According to the objective, it selects suitably. Among these, (meth) acrylate-based polymerizable monomers that do not have acidic groups (sulfonic acid groups, carboxyl groups, phosphoric acid residues, etc.) are suitable for curing speed, mechanical properties of cured products, water resistance, and color resistance. In particular, a polyfunctional (meth) acrylate polymerizable monomer having a plurality of polymerizable functional groups is preferable.

  The polyfunctional (meth) acrylate polymerizable monomer is not particularly limited and may be appropriately selected depending on the intended purpose, but is preferably a water-insoluble compound having a solubility in water at 20 ° C. of 5% by mass or less. .

  Examples of the water-insoluble compound include the following (I) bifunctional polymerizable monomer, (II) trifunctional polymerizable monomer, and (III) tetrafunctional polymerizable monomer described in detail below. Can be mentioned.

(I) Bifunctional polymerizable monomer Examples of the (I) bifunctional polymerizable monomer include (i) aromatic compound-based monomers and (ii) aliphatic compound-based monomers.

(I) Aromatic compound type As the above (i) aromatic compound type, for example, 2,2-bis (methacryloyloxyphenyl) propane, 2,2-bis [4- (3-methacryloyloxy) -2-hydroxypropoxyphenyl] propane ("bis-GMA"), 2,2-bis (4-methacryloyloxyphenyl) propane, 2,2-bis (4-methacryloyloxypolyethoxyphenyl) propane ("D-2 .6E "), 2,2-bis (4-methacryloyloxydiethoxyphenyl) propane, 2,2-bis (4-methacryloyloxytetraethoxyphenyl) propane, 2,2-bis (4-methacryloyloxypentaethoxyphenyl) ) Propane, 2,2-bis (4-methacryloyloxydipropoxyphenyl) pro Pan, 2 (4-methacryloyloxydiethoxyphenyl) -2 (4-methacryloyloxytriethoxyphenyl) propane, 2 (4-methacryloyloxydipropoxyphenyl) -2- (4-methacryloyloxytriethoxyphenyl) propane, 2 , 2-bis (4-methacryloyloxypropoxyphenyl) propane, 2,2-bis (4-methacryloyloxyisopropoxyphenyl) propane and acrylates corresponding to these methacrylates; 2-hydroxyethyl methacrylate, 2-hydroxypropyl methacrylate, Methacrylates such as 3-chloro-2-hydroxypropyl methacrylate or vinyl monomers having a hydroxyl group such as acrylate corresponding to these methacrylates, and diisocyanate methylbenzene Emissions, etc. diadduct obtained from adducts of a diisocyanate compound having an aromatic group such as 4,4'-diphenylmethane diisocyanate.

(Ii) Aliphatic compound-based (ii) Aliphatic compound-based compounds include, for example, ethylene glycol dimethacrylate, diethylene glycol dimethacrylate, triethylene glycol dimethacrylate (“3G”), tetraethylene glycol dimethacrylate, Neopentyl glycol dimethacrylate, 1,3-butanediol dimethacrylate, 1,4-butanediol dimethacrylate, 1,6-hexanediol dimethacrylate and acrylates corresponding to these methacrylates; 2-hydroxyethyl methacrylate, 2-hydroxy Vinylates having hydroxyl groups such as methacrylates such as propyl methacrylate and 3-chloro-2-hydroxypropyl methacrylate or acrylates corresponding to these methacrylates 1,2-bis (3-methacryloyloxy), a diadduct obtained from an adduct of a monomer and a diisocyanate compound such as hexamethylene diisocyanate, trimethylhexamethylene diisocyanate, diisocyanate methylcyclohexane, isophorone diisocyanate, methylenebis (4-cyclohexylisocyanate); 2-hydroxypropoxy) ethyl and the like.

(II) Trifunctional polymerizable monomer Examples of the (II) trifunctional polymerizable monomer include trimethylolpropane trimethacrylate, trimethylolethane trimethacrylate, pentaerythritol trimethacrylate, and trimethylolmethane trimethacrylate. Examples thereof include methacrylates and acrylates corresponding to these methacrylates.

(III) Tetrafunctional polymerizable monomer Examples of the (III) tetrafunctional polymerizable monomer include pentaerythritol tetramethacrylate, pentaerythritol tetraacrylate; diisocyanate methylbenzene, diisocyanate methylcyclohexane, isophorone diisocyanate, hexamethylene. Examples thereof include a diadduct obtained from an adduct of a diisocyanate compound such as diisocyanate, trimethylhexamethylene diisocyanate, methylenebis (4-cyclohexylisocyanate), 4,4-diphenylmethane diisocyanate, tolylene-2,4-diisocyanate and glycidol dimethacrylate.

  As the polyfunctional (meth) acrylate polymerizable monomer, one kind may be used alone, or two or more kinds may be used in combination.

  Furthermore, if necessary, for example, monofunctional (meth) acrylate-based monomethacrylates such as methacrylates such as methyl methacrylate, ethyl methacrylate, isopropyl methacrylate, hydroxyethyl methacrylate, tetrahydrofurfuryl methacrylate, glycidyl methacrylate, and acrylates corresponding to these methacrylates. You may use together with a mer. The polymerizable monomer exemplified above corresponds to a water-insoluble compound having a solubility in water at 20 ° C. of 5% by mass or less.

  In the curable composition of the present invention, from the viewpoint of obtaining good cured product properties (mechanical strength, non-eluting properties, etc.), the compounding amount of the monomer other than the polyfunctional (meth) acrylate monomer is The total amount of the polymerizable monomer (A) is preferably 30% by mass or less, more preferably 10% by mass or less, and particularly preferably 5% by mass or less. However, in order to obtain the best cured product properties, the (A) polymerizable monomer preferably comprises only the polyfunctional (meth) acrylate monomer.

  In the present invention, when a plurality of types of polymerizable monomers are used, the total amount of the polymerizable monomers in (A) It shall be regarded as a mass part.

<(B) Amine compound>
The (B) amine compound is blended as a polymerization initiating component of the (A) polymerizable monomer.

  There is no restriction | limiting in particular as said (B) amine compound, According to the objective, it can select suitably. Any of a primary amine compound, a secondary amine compound, and a tertiary amine compound can be used. Among these, the tertiary amine compound is preferable from the viewpoint of odor and the like.

  In addition, the amine compound (B) is not particularly limited, and the organic group bonded to the nitrogen atom is an aliphatic group (however, it may have a substituent) (hereinafter, may be substituted). Both “(B1) aliphatic amine compound”) and amine compounds in which one or more aromatic groups are directly bonded to the nitrogen atom (hereinafter also referred to as “(B2) aromatic amine compound”) can be used. it can.

  (B) As the amine compound, at least one amine compound selected from the group consisting of (B1) an aliphatic amine compound and (B2) an aromatic amine compound may be used. Among these, it is preferable to contain both the (B1) aliphatic amine compound and the (B2) aromatic amine compound. Furthermore, as will be described later, it is more preferable to use a photoacid generator in combination as a polymerization initiator because curability is improved. When these are used in combination, the curing rate can be improved as compared with the case where only the aliphatic amine compound is blended, and the polymerized cured product is more suitable for ultraviolet rays such as sunlight than the case where only the aromatic amine compound is blended. Discoloration when exposed to light can be suppressed. Therefore, the combined use of an aliphatic tertiary amine compound and an aromatic tertiary amine compound is particularly preferable.

  There is no restriction | limiting in particular as said (B1) aliphatic amine compound, According to the objective, it can select suitably. Specifically, aliphatic primary amine compounds such as 2-ethylhexylamine, n-butylamine, n-hexylamine, n-octylamine; diethylamine, dibutylamine, diallylamine, diisopropylamine, di-2-ethylhexylamine, Aliphatic secondary amine compounds such as di-n-octylamine; triethylamine, triethanolamine, tributylamine, triallylamine, N, N-dimethylaminoethyl methacrylate, N, N-diethylaminoethyl methacrylate, N-methyldiethanolamine, Examples thereof include aliphatic tertiary amine compounds such as N-ethyldiethanolamine, triethanolamine, and tri (isopropanol) amine.

  Among these, the aliphatic tertiary amine compound in which two or more of three saturated aliphatic groups bonded to the nitrogen atom have an electron-withdrawing group as a substituent has a higher polymerization activity. And further excellent storage stability can be obtained. Among such aliphatic tertiary amine compounds, those having two electron-withdrawing group-substituted saturated aliphatic groups such as N-methyldiethanolamine and N-ethyldiethanolamine, triethanolamine, tri (isopropanol) amine and the like Those having 3 electron-withdrawing group-substituted saturated aliphatic groups are particularly preferred. In addition, as said aliphatic amine compound, it may be used individually by 1 type and may use 2 or more types together.

  There is no restriction | limiting in particular as said (B2) aromatic amine compound, According to the objective, it can select suitably, For example, aromatic primary amine compounds, such as aniline and toluidine; N-methylaniline, N-methyl Examples include aromatic secondary amine compounds such as -p-toluidine; aromatic tertiary amine compounds represented by the following general formula (1).

  Among these, the tertiary aromatic amine compound is preferable from the viewpoint of odor, etc. in consideration of use as a dental product, and further exhibits high polymerization activity, stability to ambient light, and a short time due to irradiation light. The aromatic tertiary amine compound represented by the general formula (1) is particularly preferable in that it can maintain the polymerization curability of the polymer and can exhibit high cured product properties.

However, in said general formula (1), R < ¹ > and R < ² > shows an alkyl group or an aryl group mutually independently, R < ³ > is an alkyl group, an aryl group, an alkenyl group, an alkoxy group, and alkyloxy One of carbonyl groups is shown. Moreover, n shows the integer of 0-5. When n is 2 or more, the plurality of R ³ may be the same as or different from each other. Further, R3 may be bonded to each other to form a ring.

In the general formula (1), the alkyl group represented by R ^{1 to} R ³ is preferably an alkyl group having 1 to 6 carbon atoms, for example, methyl group, ethyl group, n-propyl group, i-propyl group, n -A butyl group, n-hexyl group, etc. can be mentioned. These alkyl groups may be substituted alkyl groups having a substituent. Examples of such substituted alkyl groups include halogen-substituted alkyl groups such as a fluoromethyl group and a 2-fluoroethyl group; 2-hydroxy Examples thereof include a hydroxyl group-substituted alkyl group such as an ethyl group. Especially, in said general formula (1), as R < ¹ > and R < ² >, a C1-C3 unsubstituted alkyl group (for example, a methyl group, an ethyl group, n-propyl group), 2-hydroxyethyl group is mentioned. Particularly preferred.

In the general formula (1), the aryl group represented by R ^{1 to} R ³ may have a substituent. Specific examples include those having 6 to 12 carbon atoms such as a phenyl group, a p-methoxyphenyl group, a p-methylthiophenyl group, a p-chlorophenyl group, and a 4-biphenylyl group.

In the general formula (1), the alkenyl group, alkoxy group and alkyloxycarbonyl group represented by R ³ may have a substituent.

  Examples of the alkenyl group include those having 2 to 12 carbon atoms such as vinyl group, allyl group, and 2-phenylethenyl group. As said alkoxy group, C1-C10 things, such as a methoxy group, an ethoxy group, a butoxy group, can be mentioned. Examples of the alkyloxycarbonyl group include those having 1 to 10 carbon atoms in the alkyloxy group such as methoxycarbonyl group, ethoxycarbonyl group, butoxycarbonyl group, amyloxycarbonyl group, and isoamyloxycarbonyl group. it can.

  In addition, when n = 1, the bonding position of R3 is preferably para, and R3 is preferably an alkyloxycarbonyl group. On the other hand, when n is 2 to 3, the bonding position is preferably at least one of the ortho position and the para position. In particular, the solar stability of the cured product can be improved by bonding a plurality of R3 to the ortho and para positions.

  Specific examples of the compound of the general formula (1) include N, N-dimethylaniline, N, N-dibenzylaniline, N, N-dimethyl-p-toluidine, N, N-diethyl-p-toluidine, N, N-di (β-hydroxyethyl) -p-toluidine, N, N-dimethylaminobenzoic acid, ethyl 4-N, N-dimethylaminobenzoate, amyl 4-N, N-dimethylaminobenzoate, etc. Can be mentioned.

  In addition, as said aromatic amine compound, it may be used individually by 1 type and may use 2 or more types together.

  Moreover, when using together the said (B1) aliphatic amine compound and the said (B2) aromatic amine compound, as these compounding ratio, as a mass ratio, the said (B1) aliphatic amine compound: Said (B2) aromatic Group amine compound = 1: 99 to 99: 1 is preferable, and 3:97 to 97: 3 is more preferable.

The compounding amount of the (B) amine compound must be 0.01 to 3 parts by mass with respect to 100 parts by mass of the (A) polymerizable monomer.
Especially, in order to exhibit the effect of this invention more, it is preferable that the compounding quantity of the said (B) amine compound shall be 0.02 mass part-2 mass parts. When (B1) the aliphatic amine compound and the (B2) aromatic amine compound are used in combination, the blending amount of the (B) amine compound is (B1) the aliphatic amine compound and the (B2) aromatic. The total amount with the group amine compound.

<(C) Fluorescent agent containing phthalate>
As the fluorescent agent containing the phthalate ester, known ones can be used without any limitation. A particularly preferred fluorescent agent containing a phthalate ester system is represented by the following general formula (2).

(In the formula, R ⁴ and R ⁵ are each independently an alkyl group, R ⁶ is a hydrogen atom, an amino group, or a hydroxyl group, and R ⁷ is an amino group or a hydroxyl group.)
As said alkyl group, a C1-C3 thing, such as a methyl group, an ethyl group, n-propyl group, i-propyl group, is preferable, and a C1-C2 thing is especially more preferable.

  Specific examples of the fluorescent agent containing a phthalate ester include dimethyl 2,5-dihydroxyterephthalate, diethyl 2,5-dihydroxyterephthalate, dimethylaminoterephthalate, diethylaminoterephthalate, and the like. 2,5-dihydroxyterephthalic acid A fluorescent agent containing a phthalate ester substituted with a hydroxyl group such as diethyl is more preferable because it emits fluorescence similar to natural teeth and exhibits strong color development. These fluorescent agents containing a phthalate ester may be used alone or in combination of two or more.

  The compounding quantity of the fluorescent agent containing the said phthalate ester must be 0.0005-0.05 mass part with respect to 100 mass parts of (A) polymerizable monomers.

  When the blending amount of the fluorescent agent containing a phthalate ester is less than 0.0005 parts by mass, sufficient fluorescence close to that of natural teeth cannot be obtained. On the other hand, when it exceeds 0.05 parts by mass, yellow coloration occurs due to the combined use of (B) an amine compound and (D) an acidic filler having X-ray contrast properties, which will be described later, and aesthetics that match the color tone of natural teeth. High repair becomes difficult. Therefore, in consideration of fluorescence, aesthetics, etc., the blending amount of the fluorescent agent containing the phthalate ester is 0.001 to 0.04 parts by mass with respect to 100 parts by mass of the (A) polymerizable monomer. It is preferable.

<(D) Acid filler having X-ray contrast>
The acidic filler having X-ray contrast properties (hereinafter also referred to as acidic filler) is a method in accordance with the X-ray contrast property test prescribed in JIST6514 on a sample piece compression molded to a thickness of 1.0 ± 0.1 mm. Is an acidic filler whose X-ray contrast properties are 2.0 mm aluminum plate or more. Since it has such a high X-ray contrast property, the dental restorative material obtained by using this has an X-ray contrast property and is advantageous in prognosis diagnosis.

  Here, in the X-ray contrast property test prescribed in JIST6514, an X-ray film is placed on a lead sheet having a thickness of 2.0 mm or more, and a test piece having a thickness of 1.0 mm and an X-ray contrast property are placed in the center of the film. When an X-ray with a tube voltage of 60 kVp is developed from a distance of 40 cm on the test piece, the aluminum plate, and the X-ray film, an image of the film portion and the aluminum plate portion around the test piece is developed. Is a test for comparing the darkness of the image of the test piece with the darkness of the image on the aluminum plate after the development and fixing, for an appropriate time such that the image appears completely, generally 0.3 seconds. The X-ray generator used for the measurement is a diagnostic integrated X-ray generator that conforms to the provisions of JISZ4711, and has the ability to transmit through a 1.5 mm aluminum plate at a tube voltage of 60 kVp.

  The X-ray contrast property test is a test for evaluating the X-ray contrast property of the cured body of a dental composite resin. In the present invention, the acidic filler itself having the X-ray contrast property is used. In order to evaluate this property, a method according to this measurement method is applied. The specimen used in the X-ray contrast test specified in JIST6514 is a hardened body of a composite resin for dental filling having a thickness of 1.0 ± 0.1 mm. An acidic filler compression-molded body compression-molded to 0.1 mm is used. In this compression molded body having a thickness of 1.0 ± 0.1 mm, the acidic filler is put in a mold having a shape of 1 cm × 1 cm or more and, for example, using a manual hydraulic press machine, the thickness is 1.0 ± 0.1 mm. It is produced by press molding to 0.1 mm and cutting out to 1 cm × 1 cm.

  In the X-ray contrast property test specified in JIST6514, it is only necessary to know that it has an X-ray opacity greater than that of an aluminum plate having a thickness of 2.0 mm. Is used. That is, if the image of the test piece is whiter than the image of the aluminum plate having a thickness of 2.0 mm, the test piece is evaluated as having higher X-ray contrast properties. In order to more clearly evaluate the strength of the X-ray contrast property of this test piece, the aluminum plate has not only a thickness of 2.0 ± 0.01 mm but also 1.0 ± 0.01 mm to 5.0 ±. It is preferable to prepare a plurality of different thicknesses at intervals of 0.5 mm within a range of up to 0.01 mm, and simultaneously measure and compare X-ray contrast properties on the same film. In this case, it is particularly preferable that the acidic filler of the present invention has an X-ray contrast property of 3.0 mm aluminum plate or more.

  The acidic filler having X-ray contrast properties of the present invention is characterized by having an acid point on the surface of the filler. Dental restoration materials often use a composite oxide of silica and metal oxide, which is a filler having a refractive index close to that of the polymerizable monomer used. Compared to silica, it is known that a complex oxide of silica and metal oxide forms a strong acid spot on the surface. Therefore, when used as a dental restorative material, a filler surface-treated with a silane coupling agent or the like is used for the purpose of improving the interfacial strength with a cured product formed by polymerization of a polymerizable monomer. . However, the surface treatment with the silane coupling agent can reduce the acid sites derived from the silanol groups of silica, but the strong acid sites derived from the composite oxide of silica and metal oxide remain. Furthermore, metal oxides that are not composite oxides with silica have low reactivity with silane coupling agents, and metal fluorides in particular have no reactive sites with silane coupling agents, and various problems occur due to their strong acid points. It has occurred.

  One of the problems is that yellow coloring occurs when a fluorescent agent containing an acidic filler, an amine compound, and a phthalate ester coexists. In particular, in the case of a composite oxide of silica and a metal oxide, the composite oxide containing a large amount of a metal oxide in order to provide high X-ray contrast properties is not affected by surface treatment with a silane coupling agent. Spots remained and yellow coloration occurred. That is, it has not been possible to obtain a restoration material having both high X-ray contrast properties and fluorescence close to natural teeth and having a color tone that matches natural teeth. As a result of the intensive studies by the inventors, by setting the blending amount of each component to an appropriate range, while blending an acidic filler having X-ray contrast properties, there is no coloring and fluorescence close to natural teeth. It has been found that a dental restorative material having a color tone is obtained.

  The acidic filler having X-ray contrast is not particularly limited as long as it has the X-ray contrast and has an acid point on the surface, and a known one can be used. It is preferably 10 or more and less than 30. By setting the Δa * value within this range, yellow coloring is suppressed even when a phthalate ester and an amine compound are used in combination, and it is suitable for natural teeth while prognostic diagnosis can be advantageously diagnosed by high X-ray contrast. It can be a highly aesthetic dental restoration material having color tone and fluorescence. In the present invention, the acid point of the acidic filler is represented by a Δa * value before and after dropping the indicator in anhydrous toluene. Methyl red is used as an indicator. When a silanol group or a stronger acid point is present, methyl red changes from orange to reddish purple, and the change is measured as Δa * value.

Here, the acid point measurement using an indicator may be carried out according to a conventional method, but is usually carried out by the following method. That is, first, after the filler was dried at 100 ° C. for 3 hours or more, stored in a desiccator containing diphosphorus pentoxide, 1 g of the filler was put in a sample tube bottle, and then 3 g of anhydrous toluene was added and shaken vigorously. Disperse so that there is no aggregate. After dispersion, the sample tube bottle is allowed to stand and the filler is allowed to settle. After complete settling, place the measurement hole of the color difference meter that has previously measured the standard on the white background so that it is positioned at the center of the bottom of the sample tube bottle, measure the color difference on the black background, The a * value is a * mb. After measuring the color difference, add a drop (about 0.016 g) of 0.004 mol / l methyl red anhydrous toluene solution stored under light shielding to the sample tube bottle, and after similarly shaking and standing, measure the color difference. The a * value at this time is a * mb, and the difference between a * before and after dropping of the methyl red solution is Δa * m, and the following formula (formula) Δa * m = a * ma−a * mb
This is a more demanding method.

  As the acidic filler having X-ray contrast properties of the present invention, known fillers can be used as long as they have X-ray contrast properties and are acidic by the above method. Specific examples include metal oxides such as zinc oxide, alumina, and zirconia, composite oxides such as silica-alumina, silica-titania, silica-magnesium oxide, and titania-zirconia, and metal fluorides such as ytterbium trifluoride. It is done.

  The refractive index of these acidic fillers is not particularly limited, and fillers having a refractive index in the range of 1.4 to 3.0 can be used. Among them, zirconia (refractive index of about 2.2) and alumina (refractive index of about 1.7) are preferable because they can impart high X-ray contrast properties in a small amount, but are polymerizable monomers for dental restorative materials. The refractive index is higher than (refractive index of about 1.5), transparency of the dental restorative material tends to be low, and aesthetics may be inferior. When such a filler is used, it is possible to improve aesthetics by using a nano-scale particle size smaller than the wavelength of visible light. Furthermore, it is close to the refractive index of the polymerizable monomer of the dental restorative material, and both X-ray contrast and aesthetics can be achieved without any of the above-mentioned measures. Therefore, ytterbium trifluoride (refractive index of about 1.5) Is more preferable.

  The acidic filler of the present invention may be surface-treated with a silane coupling agent. By the surface treatment with the silane coupling agent, the acidic filler is easily mixed with the polymerizable monomer in the dental restoration material, the filling rate of the filler is improved, and X-ray contrast properties and mechanical properties are excellent. It becomes a thing. In the acidic filler of the present invention, although the acidity of the index is suppressed by surface treatment with a silane coupling agent, the acidity is maintained within the above range because the strong acid point remains.

The shape of the acidic filler of the present invention is not particularly limited, and may be spherical or irregular. In addition, the particle size of the acidic filler of the present invention is preferably 0.001 to 100 μm, preferably 0.005 to 5 μm, considering that it is used for applications such as dental restoration materials. Is particularly preferable, and it is more preferably 0.01 to 1 μm. Although not particularly limited specific surface area is generally a 0.1~250m ² / g, preferably in the 1~200m ² / g.

  The compounding quantity of the acidic filler of this invention must be 1-100 mass parts with respect to 100 mass parts of said (A) polymeric monomers. When the acidic filler is 5 parts by mass or less, it is difficult to obtain X-ray contrast properties, and it may be difficult to distinguish the natural tooth from the restoration part. On the other hand, when the amount exceeds 100 parts by mass, discoloration by the phthalate ester and the amine compound becomes strong, and the aesthetics may be lost. Therefore, when X-ray contrast property, aesthetics, etc. are considered, it is preferable that the compounding quantity of an acidic filler is 10-80 mass parts with respect to 100 mass parts of said (A) polymeric monomers.

Preferred blending ratio of each component The feature of the present invention is that the blending ratio of (B) amine compound, (C) fluorescing agent containing phthalate ester, and (D) acidic filler is within a specific range, so This is because discoloration is suppressed while achieving both X-ray contrast properties. Therefore, the blending ratio of each component is preferably as follows. Specifically, the compounding ratio of (B) amine compound: (C) phthalate ester: (D) acidic filler is preferably in the range of 1: 0.0002 to 5: 4 to 10,000, and 1: 0. 0.001 to 3: 4 to 3000 is more preferable, and 1: 0.005 to 2: 5 to 400 is even more preferable.

<(E) Filler>
The (E) filler is blended for the purpose of imparting mechanical strength to the polymer cured product of the curable composition and reducing polymerization shrinkage and thermal expansion.

  The (E) filler is not particularly limited as long as it is other than the above-mentioned (D) acidic filler, can be appropriately selected according to the purpose, and a known inorganic filler or organic filler is used. Among these, the inorganic filler is preferable. (D) A material other than an acidic filler has a small acid point on the filler surface. Specifically, the Δa * value before and after dropping of methyl red is within 10 according to the acid point evaluation method described above. Say. In addition, the acid point on the filler surface can be appropriately selected by a surface treatment method using a known surface treatment agent.

  The material for the inorganic filler is not particularly limited, and examples thereof include metal oxides such as quartz, silica, alumina, silica titania, silica zirconia, lanthanum glass, barium glass, and strontium glass. In particular, silica-based composite oxides such as silica titania and silica zirconia are suitable because they can be prepared relatively easily by the sol-gel method and the refractive index can be easily adjusted by the mixing ratio of silica and metal oxide. . Moreover, you may mix | blend a well-known cation elution inorganic filler as dental inorganic fillers, such as silicate glass and fluoroaluminosilicate glass, as needed.

  In addition, a granular organic-inorganic composite filler obtained by adding the polymerizable monomer (A) to these inorganic fillers to form a paste, followed by polymerization and curing, and pulverizing them may be used. . There is no restriction | limiting in particular as a particle size of these (E) fillers, The filler of the average particle diameter of 0.01 micrometer-100 micrometers (preferably 0.01 micrometer-5 micrometers) generally used as a dental material is used. be able to. Among these, when the spherical inorganic filler is used, the surface smoothness of the obtained cured product can be improved.

  Moreover, there is no restriction | limiting in particular also as the refractive index of the said (E) filler, The refractive index of the range of 1.4-1.7 which is the refractive index of the inorganic filler used as a general dental material is used. The filler which has can be used. As the inorganic filler, a surface treatment agent typified by a silane coupling agent is used to improve the compatibility with the polymerizable monomer (A) and improve mechanical strength and water resistance. Preferably it is processed.

  Examples of the surface treatment method include known methods, and examples of the silane coupling agent include methyltrimethoxysilane, methyltriethoxysilane, methyltrichlorosilane, dimethyldichlorosilane, trimethylchlorosilane, Vinyltrichlorosilane, vinyltriethoxysilane, vinyltris (β-methoxyethoxy) silane, γ-methacryloyloxypropyltrimethoxysilane, γ-chloropropyltrimethoxysilane, γ-glycidoxypropyltrimethoxysilane, hexamethyldisilazane, etc. Can be mentioned.

  In addition, as said (E) filler, you may use individually by 1 type and may use 2 or more types together. There is no restriction | limiting in particular as a compounding quantity of the said (E) filler, Although it can select suitably according to the objective, The viscosity (operability) and hardening when it mixes with the said (A) polymeric monomer. In consideration of the mechanical properties of the body, the amount is preferably 50 parts by mass to 1500 parts by mass and more preferably 70 parts by mass to 1000 parts by mass with respect to 100 parts by mass of the polymerizable monomer (A).

<(F) Polymerization initiator>
The polymerization initiator is preferably blended in order to polymerize and cure the polymerizable monomer (A). The polymerization initiator is not particularly limited and may be appropriately selected depending on the intended purpose. In particular, in order to polymerize and cure (A) polymerizable monomers as the polymerizable monomer (A), radical polymerization is initiated. It is preferable that an agent is blended.

  The radical polymerization initiator for polymerizing and curing (meth) acrylates is not particularly limited. Any known radical polymerization initiator can be used. Specifically, in addition to a photo radical polymerization initiator (composition) capable of generating a polymerization initiating species by irradiation with ultraviolet rays, visible light, or infrared rays, two or more compounds under non-light irradiation A so-called chemical polymerization initiator composition capable of generating a polymerization initiating species by this reaction, a thermal polymerization initiator (composition) capable of generating a polymerization initiating species by heating, or the like can be used. Among them, in the dental use which is often cured in the oral cavity, a photo radical polymerization initiator (composition) or a chemical polymerization initiator composition is preferable, and from the point that it is not necessary to perform a mixing operation, a photo radical polymerization initiator (composition). Is preferred.

  Specific examples of such photo radical polymerization initiators include benzoin alkyl ethers such as benzoin methyl ether, benzoin ethyl ether and benzoin isopropyl ether, benzyl ketals such as benzyldimethyl ketal and benzyl diethyl ketal, 2-methyl- Α-amino such as 1- [4- (methylthio) phenyl] -2-morpholinopropan-1-one and 2-benzyl-2-dimethylamino-1- (4-morpholino) -2-butano-1-one Acetophenones, 4,4-bis (dimethylamino) benzophenone, 9-fluorenone, 3,4-benzo-9-fluorenone, 2-dimethylamino-9-fluorenone, 2-methoxy-9-fluorenone, 2-chloro-9 -Fluorenone, 2,7-dichloro-9-fluorenone, 2 Bromo-9-fluorenone, 2,7-dibromo-9-fluorenone, 2-nitro-9-fluorenone, 2-acetoxy-9-fluorenone, benzanthrone, anthraquinone, 1,2-benzanthraquinone, 2-methylanthraquinone, 2 -Ethylanthraquinone, 1-dimethylaminoanthraquinone, 2,3-dimethylanthraquinone, 2-tert-butylanthraquinone, 1-chloroanthraquinone, 2-chloroanthraquinone, 1,5-dichloroanthraquinone, 1,2-dimethoxyanthraquinone, 1, 2-diacetoxy-anthraquinone, 5,12-naphthacenequinone, 6,13-pentacenequinone, xanthone, thioxanthone, 2,4-dimethylthioxanthone, 2,4-diethylthioxanthone, 2-chlorothioxanthate 9 (10H) -acridone, 9-methyl-9 (10H) -acridone, diaryl ketones such as dibenzosuberenone, camphorquinone, benzyl, diacetyl, acetylbenzoyl, 2,3-pentadione, 2,3-octadione, Α-diketones such as 4,4′-dimethoxybenzyl, 4,4′-oxybenzyl, 9,10-phenanthrenequinone, acenaphthenequinone, 3-benzoylcoumarin, 3- (4-methoxybenzoyl) coumarin, 3-benzoyl-7-methoxycoumarin, 3- (4-methoxybenzoyl) 7-methoxy-3-coumarin, 3-acetyl-7-dimethylaminocoumarin, 3-benzoyl-7-dimethylaminocoumarin, 3,3′- Kemarino ketone, 3,3′-bis (7-diethylaminocoumarino) ketone, etc. Tocomarins, monoacylphosphine oxides such as 2,4,6-trimethylbenzoyldiphenylphosphine oxide, bis- (2,6-dichlorobenzoyl) phenylphosphine oxide, bis- (2,6-dichlorobenzoyl) -2,5- Dimethylphenylphosphine oxide, bis- (2,6-dichlorobenzoyl) -4-propylphenylphosphine oxide, bis- (2,6-dichlorobenzoyl) -1-naphthylphosphine oxide, bis (2,4,6-trimethylbenzoyl) ) Bisacylphosphine oxides such as phenylphosphine oxide, bis (2,6-dimethyloxybenzoyl) -2,4,4-trimethylpentylphosphine oxide, bis (η5-2,4-cyclopentadien-1-yl) Bis (2,6-difluoro-3-(1H-pyrrol-1-yl) phenyl) titanocene such as titanium or the like can be used. Especially, what has absorption in 370-500 nm is used suitably.

  In addition, although a reducing compound may be added to radical photopolymerization initiator, the (B) amine compound can be mentioned as the example. Furthermore, a photoacid generator may be used in addition to the photoradical polymerization initiator and the reducing compound. Examples of such a photoacid generator include diaryl iodonium salt compounds, sulfonium salt compounds, sulfonate ester compounds, halomethyl-substituted S-triazine conductors, pyridinium salt compounds, and the like.

  Among these, diaryliodonium salt compounds and sulfonium salt compounds are excellent in that the polymerization activity is particularly high. As specific examples of these diaryliodonium salt compounds and sulfonium salt compounds, those disclosed in, for example, JP-A-2004-196949 can be preferably used.

  The amount of these photoacid generators used is not particularly limited as long as the polymerization can be initiated by light irradiation, but an appropriate rate of polymerization progress and various physical properties of the resulting cured product (for example, weather resistance) In general, 0.001 to 10 parts by mass, preferably 0.05 to 5 parts by mass, is preferably used with respect to 100 parts by mass of the polymerizable monomer (A). Good.

  The photoacid generator as described above usually has many compounds that do not absorb in the near ultraviolet to visible range, and a special light source is often required to excite the polymerization reaction. Therefore, it is preferable that a compound having absorption in the near ultraviolet to visible region is further added as a sensitizer in addition to the photoacid generator.

  Examples of the compound used as such a sensitizer include acridine dyes, benzoflavine dyes, condensed polycyclic aromatic compounds such as anthracene and perylene, and phenothiazine. Among these sensitizers, a condensed polycyclic aromatic compound is preferable in terms of good polymerization activity, and a structure in which a saturated carbon atom having at least one hydrogen atom is bonded to the condensed polycyclic aromatic ring. Condensed polycyclic aromatic compounds having are preferred. As specific examples of the condensed polycyclic aromatic compound, those described in JP-A-2004-196949 described above can be preferably used.

  The addition amount of the condensed polycyclic aromatic compound also varies depending on the other components to be combined and the kind of the polymerizable monomer, but the amount of the condensed polycyclic aromatic compound is usually 0 with respect to 1 mol of the above-mentioned photoacid generator. 0.001 to 20 mol, and preferably 0.005 to 10 mol.

  Furthermore, it is preferable to add an oxidized photoradical generator in addition to the condensed polycyclic aromatic compound because the polymerization activity is further improved. An oxidized photoradical generator is a compound that generates radicals when excited by light irradiation, and is a so-called hydrogen abstraction type radical generator that generates radicals by extracting hydrogen from a hydrogen donor by excitation. Generates radicals by causing self-cleavage (self-cleaving radical generator), and then the radicals withdrawing electrons from the electron donor, and radicals that are excited by light irradiation and withdraw electrons directly from the electron donor. The photoradical generator is a mechanism that generates active radical species by excitation by light irradiation, such as the following. These oxidation type photo radical generators are not particularly limited, and known compounds may be used. However, in terms of higher polymerization activity when irradiated with light compared to other compounds, hydrogen abstraction type light radical generators may be used. A radical generator is preferable, and among them, a diaryl ketone compound, an α-diketone compound or a ketocoumarin compound in the above-mentioned photo radical polymerization initiator is particularly preferable.

  These oxidized photoradical generators can be used alone or in admixture of two or more. Moreover, although the addition amount varies depending on the other components to be combined and the kind of the polymerizable monomer, the photoradical generator is usually 0.001 to 20 mol relative to 1 mol of the photoacid generator described above. It is preferable that it is 005-10 mol.

On the other hand, even if it does not have a polymerization initiating ability itself, a dye that exhibits a high polymerization initiating ability may be used when a ternary initiator is combined with the reducing compound and the photoacid generator. . Examples of such a dye include coumarin dyes, porphyrin dyes, cyanine dyes, styryl dyes, and xanthene dyes.

  Other usable radical polymerization initiators other than photo radical polymerization initiators include, for example, benzoyl peroxide, p-chlorobenzoyl peroxide, tert-butylperoxy-2-ethylhexanoate, and tert-butyl peroxide. Peroxides such as oxydicarbonate and diisopropylperoxydicarbonate, azo compounds such as azobisisobutyronitrile, tributylborane, tributylborane partial oxide, 5-butylbarbituric acid, 1-benzyl-5-phenylbarbi Examples thereof include barbituric acids such as tool acid, and sulfinates such as sodium benzenesulfinate and sodium p-toluenesulfinate. It should be noted that any other available radical polymerization initiator other than these photoradical polymerization initiators and the reducing compound may be added.

  These radical polymerization initiators may be used alone or in combination of two or more. The addition amount of the radical polymerization initiator may be selected according to the purpose, but is usually 0.01 to 10 parts by mass with respect to 100 parts by mass of the polymerizable monomer (A), more preferably 0. Used at a ratio of 1 to 5 parts by mass. Generally, the greater the amount, the shorter the curing time by irradiation light, while the smaller the amount, the better the ambient light stability.

<Other ingredients>
Further, as the other components, a polymerization inhibitor may be blended for the purpose of obtaining storage stability of the curable composition, a pigment, a dye may be blended for the purpose of matching the color tone of the teeth, and an ultraviolet absorber may be blended for the purpose of preventing discoloration with respect to ultraviolet rays. And you may mix | blend a well-known additive for dental composite resin use.

<Manufacturing method>
Although the manufacturing method of the curable composition of this invention is not specifically limited, Preferably, (B) amine compound and the acidic filler which has (D) X-ray contrast property are made to contact previously. Although the detailed mechanism is unknown, the present inventors have found that the cause of discoloration is (D) the presence of acid points on the surface of the acidic filler, (C) unpaired electrons of phthalate ester are unevenly distributed, and (B) amine It is presumed that this is because (C) phthalate hydrogen is extracted by the compound and a colored substance is produced. Therefore, (D) discoloration is suppressed by previously adsorbing the (B) amine compound to the surface acid point of the acidic filler having X-ray contrast properties.

Accordingly, the following method, specifically, (B) an amine compound and (D) a mixing step of mixing an acidic filler having X-ray contrast properties, and (C) phthalate is added to the mixture obtained in the mixing step. It is preferable to produce the curable composition of the present invention by a production method including a blending step of blending a fluorescent agent containing an acid ester. The curable composition obtained by the above method is less likely to cause discoloration.

  Moreover, since the addition amount of the fluorescent agent containing (B) amine compound and (C) phthalate ester is less than the other components, (A) the polymerizable monomer is changed to (B) amine compound and (C) You may add and mix | blend with the fluorescent agent containing a phthalate ester. (A) Operability improves by mixing a polymerizable monomer. In addition, when using (E) filler, since it does not affect the discoloration of a curable composition so much, you may add (blend) in any process of a mixing process and a mixing | blending process.

  EXAMPLES Hereinafter, the present invention will be described more specifically with reference to examples, but the present invention is not limited to these examples.

(Each component and its abbreviations and abbreviations)
<(A) Polymerizable monomer>
2,2-bis [4- (3-methacryloyloxy) -2-hydroxypropoxyphenyl] propane (bis-GMA)
・ Triethylene glycol dimethacrylate (3G)

<(B) Amine compound>
(B1) Aliphatic amine compound / N, N-dimethylaminoethyl methacrylate (DMEM)
・ N-methyldiethanolamine (MDEOA)
・ Triethanolamine (TEOA)
(B2) Aromatic amine compound, ethyl 4-N, N-dimethylaminobenzoate (DMBE)
・ N, N-dimethyl-p-toluidine (DMPT)

<(C) Fluorescent agent containing phthalate>
・ Dimethylaminoterephthalate (DATP)
・ Diethyl 2,5-dihydroxyterephthalate (DHTP)

<(D) acidic filler and (E) filler>
-The filler used was shown in Table 1. The characteristics of each filler were evaluated using the following methods.

<(F) Polymerization initiator>
・ Camphorquinone (CQ)
2,4,6-Tris (trichloromethyl) -s-triazine (TCT)

<(Other ingredients)>
・ Hydroquinone monomethyl ether (HQME)

(Characteristic evaluation)
(1) Measurement of refractive index of filler The refractive index of each inorganic filler was measured by an immersion method using an Abbe refractometer (manufactured by Atago Co., Ltd.). That is, in a thermostatic chamber at 23 ° C., 1 g of inorganic filler is dispersed in 50 ml of anhydrous toluene in a 100 ml sample bottle. While stirring this dispersion with a stirrer, 1-bromotoluene was added dropwise little by little, the refractive index of the dispersion when the dispersion became the most transparent was measured, and the obtained value was taken as the refractive index of the inorganic filler. did.

(2) Measurement of acidity of filler surface (Δa * with methyl red)
After drying at 100 ° C. for 3 hours or more, 1 g of the composite oxide particles stored in a desiccator containing diphosphorus pentoxide is put in a sample tube having an inner diameter of about 16 mm, and then 3 g of anhydrous toluene is vigorously shaken to agglomerate. After being dispersed so as not to have any objects, the sample tube bottle was allowed to stand, and the composite oxide particles were allowed to settle. After complete settling, place the measurement hole of the color difference meter (TC-1800MKII, manufactured by Tokyo Denshoku Co., Ltd.), whose standard has been measured against a white background, in the center of the bottom of the sample tube bottle. The color difference was measured in the background, and the a * value at this time was defined as a * mb. After the color difference measurement, a drop (about 0.016 g) of an anhydrous toluene solution of 0.004 mol / l methyl red (Tokyo Kasei) stored in the dark is added to the sample tube bottle, and after shaking and standing in the same manner, The color difference was measured, and the a * value at this time was defined as a * ma. Δa * m was determined from the following (formula).
(Expression) Δa * m = a * ma−a * mb

(3) X-ray contrast evaluation test of filler alone A filler is filled in a 1 mm thick SUS mold having a filling portion of about 7 cm × 2 cm, and sandwiched between SUS plates of about 10 cm × 5 cm and 5 mm thick. The filler was added and compression-molded so that the thickness of the compact became 1 mm while repeating the press at about 50 kg / cm ² with a manual hydraulic press. Finally, it was pressed at about 150 kg / cm ² , and it was confirmed with a micrometer that the obtained molded body had a thickness of 1.0 ± 0.1 mm. This molded body was cut out to about 1 cm × 1 cm, and used as a test piece for an X-ray contrast test.

  Next, an X-ray film (Kodak ultra-sensitive dental X-ray film) is placed on a lead sheet having a thickness of 2.0 mm or more, the test piece is placed in the center of the film, and 1.0 mm around the test piece. An aluminum plate having a thickness of 1.0 mm in a range of ± 0.01 mm to 5.0 ± 0.01 mm is placed, and X with a tube voltage of 60 kVp is applied to the test piece, aluminum plate, and X-ray film from a distance of 40 cm. After irradiation with a wire (PANPASS-E manufactured by YOSHIDA) for 0.3 seconds, the film was developed and further baked on photographic paper. The test piece and the aluminum plate were compared, and the thickness of the aluminum plate showing the same black amount as the test piece was determined.

(4) X-ray contrast evaluation test of cured body The paste was filled in a mold made of polytetrafluoroethylene having holes of φ15 mm × 1.0 mm and pressed with a polypropylene film. A dental light irradiator (Tokuso Power Light, Tokuyama Dental Co., Ltd .; optical output density 600 mW / cm ² ) is closely attached to a polypropylene film and irradiated at 5 points for 30 seconds on one side, and the back side is similarly irradiated. Then, a cured body was produced. Except that the test piece was the above cured body, the evaluation was performed in the same manner as the X-ray contrast evaluation test of the filler alone, and the thickness of the aluminum plate was obtained.

(5) Fluorescence evaluation test A polytetrafluoroethylene mold having a 7 mmφ × 3.0 mm hole is filled with a paste and pressed with a polypropylene film, and a dental light irradiator (Tokuso Power Light, Tokuyama Dental Co., Ltd .; A light output density of 600 mW / cm ² ) was adhered to the polypropylene film and irradiated for 30 seconds to prepare a cured product. The obtained cured product was observed for its fluorescence emission state using an ultraviolet light irradiator (MINERALIGHT LAMP, Funakoshi Chemical Co., Ltd .; maximum absorption wavelength 366 nm). In particular, the case where excellent fluorescence was confirmed was evaluated as ◎, the case where favorable fluorescence was confirmed as ○, and the case where fluorescence was not confirmed as ×.

(6) Color tone evaluation test Measured according to JIS Z8729. Specifically, a curable composition is filled into a 1.0 mm thick polyacetal mold having a 7 mm diameter through-hole, pressed with a polypropylene film, and a dental light irradiator (Toxo Powerlite, The product was irradiated with light at a light output density of 600 mW / cm ² manufactured by Tokuyama Dental Co., Ltd. for 30 seconds. About the obtained hardened | cured material, the color tone in the reflected light at the time of irradiating the standard light C was measured on the white background conditions using the color difference meter (the Tokyo Denshoku Co., Ltd. product: TC-1800MKII), and CIELab color system was used. The brightness L * and the chromaticity a * and b *, respectively, were obtained. In order to evaluate yellow discoloration, b * indicating blue-yellow was compared. In addition, it showed that it was a yellow color tone, so that b * was large, b * was a color tone judged to be white within 10, and b * was 15 or more and it was a clear yellow color tone.

(7) Hardness of cured body (Vickers hardness)
A paste was filled in a mold made of polytetrafluoroethylene having a thickness of 7 mm and having a through-hole of 7 mmφ, and pressure-welded with a polypropylene film. A cured body was prepared by attaching an irradiation port of a dental light irradiator (Tokuso Power Light, Tokuyama Dental Co., Ltd .; light output density 600 mW / cm ² ) to a polypropylene film and irradiating it for 10 seconds, and this was used as a test piece. . Using a Vickers indenter with a micro hardness tester (MHT-1 type, manufactured by Matsuzawa Seiki Co., Ltd.), the diagonal length of the recess formed in the test piece with a load of 100 gf and a load holding time of 30 seconds was obtained.

(Examples 1-17, Comparative Examples 1-4)
A polymerizable monomer composed of bis-GMA (60 parts by mass) and 3G (40 parts by mass) is M-1, M-1 is 100 parts by mass, HQME is 0.15 parts by mass as a polymerization inhibitor, and a table. A curable composition comprising a polymerization initiator, an amine compound, a phthalate containing a phthalate ester, an acidic filler and a filler shown in 2 was stirred and mixed using an agate mortar in the dark to prepare a paste-like composition. . Characteristic evaluation was performed using the obtained composition, and the results are shown in Table 2.

(Examples 18 and 19)
In Example 18, the amount of each component was the same as in Example 2, and the composition was prepared by changing the production method as follows. A matrix m-1 was prepared by dissolving 0.075 parts by mass of HQME as a polymerization inhibitor and the polymerization initiator and amine compound shown in Table 2 with respect to 50 parts by mass of the polymerizable monomer M-1. A matrix m-2 was prepared by dissolving 0.075 parts by mass of HQME as a polymerization inhibitor and a phthalate ester shown in Table 2 with respect to 50 parts by mass of the polymerizable monomer M-1. . In the dark, an agate mortar was used to stir and mix the acidic filler shown in Table 2 and the matrix m-1. Next, the filler and matrix m-2 shown in Table 2 were added, and the mixture was further stirred and mixed to prepare a paste-like composition. In Example 19, the compounding amount of each component was the same as in Example 3, and a curable composition was obtained by the same production method as in Example 18. Using the obtained composition, the characteristics were evaluated, and the results are shown in Table 2.

  As shown in the said Tables 2-4, the curable composition of Examples 1-18 can obtain the hardened | cured material which is not colored while having high X-ray contrast property and the fluorescence close | similar to a natural tooth. Yes.

  On the other hand, the curable compositions of Comparative Examples 1 to 4 cannot achieve both high X-ray contrast properties, good fluorescence, and good color tone without coloring.

  That is, with respect to the curable composition of Example 1, the curable composition of Comparative Example 1 has an excessive amount of (C) a fluorescent agent containing a phthalate ester, and (B) an amine compound and (D) It is considered that strong coloring was caused by the combined use with the acidic filler.

  Further, (C) the curable composition of Comparative Example 2 that does not contain a fluorescent agent containing a phthalate ester has high X-ray contrast properties and a good color tone without coloring, but has no fluorescence and is aesthetic. It is inferior.

  Further, (D) the curable composition of Comparative Example 3 containing no acidic filler has extremely low X-ray contrast, and (D) the curable composition of Comparative Example 4 containing excessive acidic filler has a high X-ray contrast. Although it shows the property, strong coloring occurs.

  Therefore, from the comparison of the curable compositions of Examples 1 to 18 and Comparative Examples 1 to 4, the blending amount of (B) amine compound, (C) fluorescent agent containing phthalate ester, and (D) three components of acidic filler It was shown that a colored cured product having high X-ray contrast and good fluorescence close to that of natural teeth can be obtained by making the range of the present invention.

  Furthermore, the curable composition of Examples 15 and 16 in combination with (F) a photoacid generator as a polymerization initiator is compatible with high X-ray contrast properties, good fluorescence, and good color tone without coloring. The hardness of the cured product is improved, making it more useful and superior as a dental composite resin.

  Further, in Examples 18 and 19 in which the method for producing the curable composition of Examples 2 and 3 was changed, coloring was further suppressed, and a cured product having a good color tone could be obtained. It is considered that the conversion of the phthalate ester into a colored substance was suppressed by changing the production method and contacting the amine compound (B) with the acidic filler having (D) X-ray contrast properties in advance.

Claims (7)

(A) a polymerizable monomer,
(B) an amine compound,
(C) a fluorescent agent containing a phthalate ester, and (D) an inorganic filler containing fluorine atoms, including an acidic filler having X-ray contrast properties, and (A) 100 parts by mass of the polymerizable monomer, 0.01-3.0 parts by mass of the (B) amine compound, 0.0005-0.05 parts by mass of the fluorescent agent containing the (C) phthalate ester, and (D) inorganic particles containing fluorine atoms. comprising, a curable composition containing 1 to 100 parts by weight of acidic filler having a X-ray contrast property.   The curable composition according to claim 1, wherein the (B) amine compound contains at least one amine compound selected from the group consisting of (B1) an aliphatic amine compound and (B2) an aromatic amine compound. The curable composition according to claim 1 or 2 , wherein the (D) acidic filler having X-ray contrast properties made of inorganic particles containing fluorine atoms is ytterbium trifluoride. Furthermore, (E) filler other than the acidic filler which has X- ray contrast property is contained, 50-1500 mass parts of this (E) filler is contained with respect to 100 mass parts of said (A) polymeric monomers. The curable composition as described in any one of -3 . The curable composition according to any one of claims 1 to 4 , further comprising (F) a polymerization initiator, wherein the (F) polymerization initiator includes an α-diketone compound and a photoacid generator. A dental restorative material containing the curable composition according to any one of claims 1 to 5 . It is a manufacturing method of the curable composition of Claim 1, Comprising:
(B) A mixing step of mixing an acidic filler having X-ray contrast properties, which is composed of an amine compound and (D) inorganic particles containing fluorine atoms, and (C) a phthalate ester is contained in the mixture obtained in the mixing step The manufacturing method of the curable composition which has a mixing | blending process which mix | blends a fluorescent agent.