JP2002128621A - Dental polymer hybrid filler, method for producing the same and dental composition containing the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a filler capable of providing a dental composition with excellent characteristics such as polishing properties, surface lubricity, glossiness, excellent mechanical strength, surface hardness and durability, to provide a method for producing the filler and to obtain a dental composition containing the filler. SOLUTION: This polymer hybrid filler comprises (a) an oligomer and/or a polymer containing at least one or more silyl groups in the molecule and (b) a poly(organo)siloxane condensate obtained by hydrolyzing or partially hydrolyzing and (co)condensing an (organo)silane compound represented by formula (I) and/or a low condensate of the (organo)silane compound alone in the presence or absence of a metal or the (organo)silane compound in the presence of a metal hydroxide sol. A method for producing the polymer hybrid filler is provided. A dental composition comprises the filler.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a polymer hybrid filler which can be used as a filler in a dental composition such as a crown material, a filling material, a prosthetic material and an adhesive material in the dental field, a method for producing the same, and a method for producing the same. It relates to a dental composition comprising it.

[0002]

2. Description of the Related Art The following properties are required of composite restorations which are frequently used in the dental field in recent years. Mechanical strength that can withstand high occlusal pressure during mastication, durability under severe conditions, coefficient of thermal expansion similar to tooth, low polymerization shrinkage to prevent peeling from tooth during polymerization hardening, etc. Mechanical properties, color and transparency compatible with natural teeth, optical properties such as surface lubrication and glossiness observed during polishing, and non-toxic,
Biocompatibility such as insolubility and low water absorption is exemplified. In recent years, in particular, there has been a demand for a sustained release of fluorine, which enhances the tooth quality and suppresses secondary caries, and an X-ray contrast property, which can confirm the recurrence of dental caries after treatment and can be distinguished from enamel of the tooth. ing.

Conventionally, it is composed of a polymerizable monomer, a polymerization initiator, and a filler such as an inorganic substance, an organic substance, or an organic-inorganic composite compound, which can be polymerized for restoration, prosthesis, artificial dental root, and other uses of a tooth defect. Composite restorations are used.
Among these components, there have been many reports on fillers. This is because it is considered that the characteristics of the filler affect the characteristics of the composite restoration material since the proportion of the filler in the composite restoration material is large.

[0004] The filler used in the initial composite restoration material is α-quartz or various glasses having an average particle size of several μm to several hundred μm. It was mainstream. When these fillers are used, various properties such as moderate viscosity and operability, mechanical strength, low polymerization shrinkage, and thermal expansion coefficient close to that of teeth can be imparted to the composite restoration material. However, due to the large average particle size,
Polishing properties are not good, and there are drawbacks such as poor surface smoothness and surface gloss after polishing. In order to solve this problem, attempts have been made to make the average particle size as small as possible, but it is still insufficient. In order to overcome this drawback, ultrafine particles having an average particle diameter of 0.01 to 0.1 μm synthesized by a pyrolysis method or a gas phase reaction method, for example, spray pyrolysis silica or fumed silica were used as a filler. Composite restorations have been proposed and have been widely used under the general abbreviation MFR. This composite restoration material has good abrasiveness and excellent surface smoothness and surface gloss. However, when these ultrafine particles are dispersed in a polymerizable monomer,
Due to the large specific surface area, the consistency of the paste obtained is very high, so that the filling must be kept very low. For this reason, the mechanical properties of the composite restoration material, particularly the bending strength, are inferior. In addition, there are also problems such as a relatively large polymerization shrinkage when the paste is cured, and a very large thermal expansion coefficient of the cured product.

As other fillers, the particle size distribution synthesized from a solution reaction such as a sol-gel method starting from an organometallic compound is narrow and spherical, and the average particle diameter is from 0.1 μm to several μm.
m or silica or a silica composite oxide. These fillers are disclosed in JP-A-59-101409 and the like. Since this filler causes coagulation in the drying step, the surface treatment of the filler cannot be performed uniformly, and there is a problem in mechanical strength and durability such as material deterioration due to water absorption. Therefore, a hybrid composite restoration material combining ultrafine silica particles and a relatively large inorganic filler material has been proposed based on the idea of combining the advantages of the respective filler materials. For example, JP-A-57-82303, JP-T-57-500150, and JP-A-61-14810.
No. 9 and other publications. However, although these hybrid types can sufficiently improve the mechanical properties, there are problems such as the paste being sticky and the operability being poor, and the smoothness after finish polishing being insufficient compared with the MFR.

Recently, several fillers have been proposed that focus on optical properties such as abrasiveness and surface slipperiness.
For example, there are those commonly referred to as organic-inorganic composite fillers or composite fillers. These are obtained by mixing inorganic particles in advance with a polymerizable monomer, polymerizing once, and then pulverizing the polymer to obtain a composite filler. JP-A-54-1
JP 07187 discloses a composite filler using ultrafine silica as inorganic particles. However, due to the large specific surface area of the ultrafine silica, the proportion of the composite filler in the composite filler is reduced, and as a result, The composite restoration material containing the filler has disadvantages such as a low surface hardness and a large thermal expansion coefficient. Japanese Patent Publication No. 3-12043 discloses spherical inorganic silica having an average particle diameter of 0.1 to 1.0 μm and spherical and a composite inorganic oxide with another element capable of binding to silica. No. 143747 discloses an inorganic particle having a mean particle size of 0.01 to 0.1 μm, silicon dioxide and a composite oxide of a group II to group IV element of the periodic table, and JP-A-5-194135. Discloses a composite restoration material containing glass particles each having an average particle diameter of 0.1 to 5.0 μm as inorganic particles. These can solve the problems such as the surface hardness and the coefficient of thermal expansion by increasing the content of the inorganic component in the filler, but hardly improve the mechanical properties. Also,
Japanese Patent Publication No. 6-62887 discloses a composite filler having a double bond remaining on the filler surface by using a trifunctional or bifunctional polymerizable monomer as the composite filler.
Japanese Patent Publication No. 196430 discloses composite fillers containing aggregates obtained by aggregating and heat-treating inorganic particles having an average particle diameter of 1 μm or less. However, although these are aimed at improving mechanical properties, their effects are still insufficient. Therefore, a composite restoration material using a composite filler and another inorganic filler in a composite restoration material for the purpose of improving mechanical properties has been disclosed. Japanese Patent Publication No. 9-91170 discloses a composite restoration material containing glass powder, ultrafine silica and a composite filler, and Japanese Patent Application Laid-Open No. 9-194675 discloses a composite restoration material containing aggregated particles of a composite polymer and an inorganic oxide. However, these have disadvantages due to the use of the inorganic filler, and have never been satisfactory in all the properties required for the composite restoration material.

As described above, the composite filler has excellent optical properties such as surface lubricity and gloss after final polishing, but the effect of surface treatment on the composite filler is insufficient, and The wettability with the components deteriorated, and there was a major problem in mechanical properties or operability. The surface of the composite filler should be low in inorganic components and mostly organic. Also, when producing a composite filler even if inorganic components have appeared,
The inorganic particles have already been surface-treated using a silane coupling agent or the like. Therefore, the surface treatment effect on the composite filler particles is not recognized, and sufficient mechanical properties cannot be obtained. Also, if the surface treatment is not performed uniformly and efficiently,
This also affects the operability of the paste before curing of the composite restoration material and the durability of the composite restoration material after curing. Most of the conventional surface treatment of composite fillers has been limited to physical surface treatment agent adsorption. for that reason,
A minute gap is formed at the interface between the filler surface and the resin matrix, and water penetrates into this gap, thus causing a problem in durability and the like. As described above, the excellent abrasiveness conventionally recognized as a feature of the composite filler, particularly the surface lubricity and gloss after polishing are not impaired, and the surface treating agent works effectively, and is excellent. There was no organic composite filler capable of imparting mechanical properties and durability.

[0008]

The conventional organic-inorganic composite filler has few inorganic components on its surface, and most of the organic components are organic components. Poor wettability. Therefore, when it is contained in a dental composition, it cannot be uniformly dispersed, so that excellent mechanical strength, surface hardness and durability cannot be imparted to the dental composition. The object of the present invention is to provide crown materials, filling materials,
An organic-inorganic composite filler that can be used in dental compositions such as prosthetic materials and adhesive materials, and has particularly excellent polishing properties required as a filler, such as surface lubrication after polishing and gloss. An object of the present invention is to provide a polymer hybrid filler which has characteristics and can impart both excellent mechanical strength, surface hardness and durability, a method for producing the same, and a dental composition.

[0009]

Means for Solving the Problems The present inventors have made intensive studies to achieve the above object, and as a result, provided a polymer hybrid filler in which an organic component and an inorganic component were compounded at a molecular level. It came to be solved. That is, the present inventors provide the following inventions in the present application. The present invention provides (a) an oligomer and / or a polymer containing at least one silyl group in a molecule,
(B) General formula (I) in the presence or absence of a metal compound:

Embedded image (Where Z is R ¹ O— or OCN—, X is halogen, Y
Is OH—, R ¹ is an organic group having 8 or less carbon atoms, R ² is an organic group, a, b, and c are integers of 0 to 4, p is an integer of 0 to 3, and a + b + c + p = 4. The poly (organo) siloxane condensate obtained by hydrolyzing or partially hydrolyzing the (organo) silane compound and / or the low condensate of the (organo) silane compound alone or together with the metal oxide sol And a polymer hybrid filler characterized by comprising: further,
There is provided a polymer hybrid filler characterized by containing (c) a metal chelate compound in addition to the components (a) and (b). In the present invention, the component (a) has a content of 0.0
1 to 100.0 parts by weight, component (b) is 0.01 to 200 parts by weight
The polymer hybrid filler is provided in parts by weight. Further, the ratios (a) and (b)
The present invention provides the above polymer hybrid filler, which further comprises the component (c) in an amount of 0.001 to 30 parts by weight in addition to the component.

Further, the present invention provides: (1) a step of preparing a solution containing an oligomer and / or a polymer containing at least one silyl group in a molecule; and (2): in the presence or absence of a metal compound. The (organo) silane compound and / or the low condensate of the (organo) silane compound represented by the following general formula (I) are hydrolyzed or partially hydrolyzed together with the metal oxide sol alone or A) preparing a solution containing the condensed poly (organo) siloxane condensate; and (3) reacting the solutions prepared in steps (1) and (2) in the presence or absence of a metal chelate compound. Provided is a method for producing a polymer hybrid filler, comprising the step of producing a polymer hybrid filler. Further, (a) the above-mentioned polymer hybrid filler, (b)
Provided is a dental composition comprising a polymerizable monomer and (c) a polymerization initiator.

The polymer hybrid filler of the present invention has the following effects. In the polymer hybrid filler of the present invention, since an organic component and an inorganic component are complexed at a molecular level and can contain many inorganic components, a silane coupling agent or the like acts efficiently, and is uniformly dispersed in a resin matrix. Can be dispersed. When the polymer hybrid filler of the present invention is used as a filler in a dental composition, excellent mechanical properties, surface hardness and durability, as well as excellent abrasiveness, surface lubrication and gloss after polishing. Can be granted. Furthermore, by including a heavy metal element in the polymer hybrid filler, excellent X-ray contrast can be imparted.

[0012]

BEST MODE FOR CARRYING OUT THE INVENTION

Examples of the oligomer and / or polymer containing at least one silyl group in a molecule contained in the polymer hybrid filler of the present invention include a compound represented by the following general formula (II):

Embedded image (Where Z is R ¹ O— or OCN—, X is halogen, Y
Is OH-, R ¹ is an organic group having 8 or less carbon atoms, R ^{2 ′} is an organic group containing an unsaturated group, a, b and c are integers of 0 to 3, p
Is an integer of 1 to 3, and a + b + c + p = 4)
Oligomer obtained by homopolymerizing an organosilane compound having an unsaturated group and / or a low-condensate of an organosilane compound represented by the following formula, or by copolymerizing in the presence of another polymerizable monomer. And / or polymers. The number average molecular weight of these oligomers and / or polymers is 500 to 10
0000, more preferably 500-300.
00 range. These oligomers and / or polymers must contain at least one silyl group in the molecule, preferably in the range of 5 to 75.

The preparation of the oligomer or polymer can be carried out by a known polymerization method using a polymerization catalyst in an organic solvent, for example, any polymerization method such as solution polymerization, emulsion polymerization and suspension polymerization. As the organic solvent, benzene, toluene, hexane, isopropanol and the like can be used without any limitation. In addition, azobisisobutyronitrile (AIBN) as a polymerization catalyst,
Benzoyl peroxide, potassium persulfate, ammonium persulfate and the like can be used without any limitation. In the organosilane compound represented by the general formula (II),
R ² ′ represents an organic group containing an unsaturated group, and specific examples include a vinyl group, an acroyl group, a methacryloyl group, and a derivative group thereof. Z represents an R ¹ O group or OCN group capable of generating a silanol group by hydrolysis, X represents a halogen, Y represents an OH group, and R ¹ represents an organic group having 8 or less carbon atoms. , Ethyl, 2-chloroethyl, allyl, aminoethyl, propyl, isopentyl,
Examples include an alkyl group or an alkyl derivative group such as hexyl, 2-methoxyethyl, phenyl, m-nitrophenyl, and 2,4-dichlorophenyl, and preferably methyl or methyl in view of hydrolysis rate and carbon residue in the condensate. Ethyl, and halogen includes chlorine and bromine, and is preferably chlorine.

Specific examples of the organosilane compound having an unsaturated group represented by the general formula (II) include vinyltrimethoxysilane, vinyltriethoxysilane, vinyltri (β-methoxyethoxy) silane, and γ-methacryloxy. Examples thereof include propyltrimethoxysilane, allyltriethoxysilane, allyltrimethoxysilane, and vinylsilyltriisocyanate. In addition, low condensates of these organosilane compounds can also be used. These compounds can be used alone or in combination. Further, the organosilane compound having an unsaturated group represented by the general formula (II) and / or another polymerizable monomer that can be copolymerized with the low-condensation product of the organosilane compound is not particularly limited, and is not limited. Any compound having a saturated group can be used without any limitation. Specific examples include unsaturated aromatics such as styrene, α-methylstyrene, halogenated styrene, and divinylbenzene; unsaturated esters such as vinyl acetate and vinyl propionate; unsaturated nitriles such as acrylonitrile; butadiene; Compounds having an unsaturated group such as isoprene are exemplified. Preferably, it is a polymerizable monomer described below which is already known in the dental field. Among these polymerizable monomers, it is a preferred embodiment to copolymerize with a monofunctional polymerizable monomer. In addition, there is no problem even if another substituent, for example, an acidic group such as a carboxylic acid group or a phosphoric acid group is contained in the molecule of the polymerizable monomer. Among these, it is more preferable to use an oligomer and / or a polymer obtained by homopolymerizing γ-methacryloyloxypropyltrimethoxysilane or copolymerizing γ-methacryloyloxypropyltrimethoxysilane with methyl methacrylate.

The poly (organo) siloxane condensate contained in the polymer hybrid filler of the present invention has the general formula (I):

Embedded image (Where Z is R ¹ O— or OCN—, X is halogen, Y
Is OH—, R ¹ is an organic group having 8 or less carbon atoms, R ² is an organic group, a, b, and c are integers of 0 to 4, p is an integer of 0 to 3, and a + b + c + p = 4. )) Or a low-condensation product of the (organo) silane compound alone or in combination with the metal oxide sol by hydrolysis or partial hydrolysis to condense, or the compound represented by the general formula (I) ) And / or a low-condensation product of the (organo) silane compound alone or together with a metal oxide sol in the presence of a metal compound to undergo co-condensation by hydrolysis or partial hydrolysis. Can be obtained.

In the (organo) silane compound represented by the general formula (I), Z is an R ¹ O or OCN group capable of producing a silanol group by hydrolysis, X is a halogen, Y
Represents an OH group, R ¹ represents an organic group having 8 or less carbon atoms, and R ² represents an organic group. Specifically, R ¹ is an alkyl group or alkyl such as methyl, ethyl, 2-chloroethyl, allyl, aminoethyl, propyl, isopentyl, hexyl, 2-methoxyethyl, phenyl, m-nitrophenyl, 2,4-dichlorophenyl, etc. Derivative groups and the like can be mentioned, but from the viewpoint of hydrolysis rate and carbon residue in the (co) condensate, methyl or ethyl is preferable, and halogen includes chlorine and bromine, and preferably chlorine.

Specific examples of the silane compound represented by p = 0 in the general formula (I) include tetramethoxysilane,
Tetraethoxysilane, tetrapropoxysilane, tetraallyloxysilane, tetrabutoxysilane, tetrakis (2-ethylhexyloxy) silane, trimethoxychlorosilane, triethoxychlorosilane, triisopropoxychlorosilane, trimethoxyhydroxysilane,
Diethoxydichlorosilane, tetraphenoxysilane,
Examples thereof include tetrachlorosilane, silicon hydroxide (silicon oxide hydrate), tetraisocyanate silane, ethoxysilane triisocyanate, and low-condensation products of these silane compounds. Of these, tetramethoxysilane or tetraethoxysilane is preferable. These compounds can be used alone or in combination.

Specific examples of the organosilane compound represented by p = 1 to 3 in the general formula (I) include methyltrimethoxysilane, ethyltrimethoxysilane, methoxytripropylsilane, propyltriethoxysilane, hexyl Trimethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, vinyltri (β-methoxyethoxy) silane, γ-methacryloyloxypropyltrimethoxysilane, γ-glycidoxypropylmethoxysilane, γ-mercaptopropyltrimethoxysilane, γ -Aminopropyltriethoxysilane, 3-aminopropyltriethoxysilane, methyltrichlorosilane, phenyltrichlorosilane, trimethylsilyl isocyanate, vinylsilyltriisocyanate, phenylsilyltriisocyanate And low-condensates of these organosilane compounds. Among these, methyltrimethoxysilane or γ-methacryloyloxypropyltrimethoxysilane is more preferred. These compounds can be used alone or in combination.

As the metal oxide sol, a hydrosol using water as a dispersion medium, an organosol or an aerosol using an organic solvent such as methanol, ethyl cellosolve, ethylene glycol and dimethylacetamide as a dispersion medium can be used without any limitation. Further, there is no limitation even if the metal oxide ultrafine particles are dispersed in various dispersion media using an appropriate disperser. Examples of the metal oxide that can be used as the sol or the fine particles include various metal oxides such as silica, alumina, antimony oxide, and zirconia, and mixtures thereof.

Among the above various compounds, the poly (organo) siloxane condensate contained in the polymer hybrid filler is an organosilane compound represented by the general formula (I) and a silane compound represented by the general formula (I) Alternatively, a combination of an organosilane compound represented by the general formula (I) and a metal oxide sol is preferable, and a combination of an organosilane compound and a metal oxide sol is more preferable. Specific examples include a combination of methyltrimethoxysilane and / or γ-methacryloyloxypropyltrimethoxysilane with silica sol and the like.

The metal compound which can coexist at the time of preparing the poly (organo) siloxane condensate is one which hydrolyzes or partially hydrolyzes alone and condenses to form a skeleton of the poly (organo) siloxane condensate. Alternatively, any of those which modify the skeleton of the poly (organo) siloxane condensate in the presence of another compound forming the skeleton of the poly (organo) siloxane condensate can be used without any particular limitation. Specific examples of such metal compounds include metal halides, metal nitrates, metal sulfates, metal ammonium salts, organometallic compounds, alkoxymetal compounds, and derivatives of these metal compounds. The metal compounds can be used alone or in combination of two or more. As metal elements constituting these metal compounds,
Each element of Group I to Group V of the periodic table can be mentioned. Also,
Among these metal compounds, a metal compound composed of a metal element of Groups III to V of the periodic table that can form a three-dimensional skeleton by hydrolysis and condensation alone is preferable. More preferably, it is a metal compound composed of Zr or Ti. By using a poly (organo) siloxane condensate in which a metal compound containing these metal elements coexists for the preparation of a polymer hybrid filler, a polymer hybrid filler having X-ray contrast performance can be obtained. Specific examples of a metal compound composed of Zr or Ti include titanium tetrachloride, titanyl sulfate, methyltrichlorotitanium, dimethyldichlorotitanium, tetramethoxytitanium, tetraethoxytitanium, tetraisopropoxytetan, tetraisobutoxytitanium, tetra (2 -Ethylhexyloxy) titanium, diethoxydibutoxytitanium, isopropoxytitanium trioctarate, diisopropoxytitanium diacrylate, tributoxytitanium stearate, zirconium tetrachloride, zirconium oxychloride, zirconium acetate, zirconium lactate, tetramethoxyzirconium , Tetraethoxyzirconium, tetraisopropoxyzirconium, tetrabutoxyzirconium and the like. In addition, derivatives of the above metal compounds can also be used. As derivatives of metal compounds,
For example, a part of a hydrolyzing group such as halogen, NO ₃ , SO ₄ , an alkoxy group and an acyloxy group may be partially replaced with a dicarboxylic acid group, an oxycarboxylic acid group, a β-diketone group, a β-ketoester group, a β-diester group, an alkanolamine. And a metal compound substituted with a group capable of forming a chelate compound such as a group. In addition, a low-condensation metal compound (oligomer or polymer) obtained by partially hydrolyzing and low-condensing a metal compound can also be used.

The hydrolysis or partial hydrolysis and (co) condensation of the above compounds are carried out under relatively slow stirring conditions. The stirring temperature is in the range of 10 ° C to 100 ° C, more preferably 25 ° C to 50 ° C. Poly (organo)
When an aqueous medium or the like is used in the step of preparing the siloxane condensate, there is no problem as long as the temperature is lower than the boiling point of the aqueous medium. The stirring time is usually in the range of several minutes to several tens of hours, more preferably 30 minutes to 24 hours,
It can be adjusted as appropriate depending on the type and amount of the compound to be condensed, the type of the solvent used and the ratio of the solvent to the whole, and the like. Stirring does not require a special method, and can be carried out by using equipment commonly used in the art. For example, stirring may be performed using a stirrer capable of stirring, such as a universal mixing stirrer or a planetary mixer.

In order to control the rate of hydrolysis or partial hydrolysis and (co) condensation, it is preferable to add a sol-gel catalyst such as an acid and an alkali, an organometallic compound, a metal alkoxide, or a metal chelate compound. is there. Specific examples of the catalyst include inorganic acids such as hydrochloric acid, acetic acid, nitric acid, formic acid, sulfuric acid, and phosphoric acid, and organic acids such as paratoluenesulfonic acid, benzoic acid, phthalic acid, and maleic acid;
Examples thereof include alkali catalysts such as potassium hydroxide, sodium hydroxide, and ammonia. As the aqueous medium, water alone or, if necessary, alcohols,
Those substituted with an aqueous solvent such as ketones such as acetone or ethers may be used. The form of the compound to be condensed in the step of preparing the poly (organo) siloxane condensate is not particularly limited, and may be a monomer, a low-condensate (oligomer) in which the monomer is partially hydrolyzed and low-condensed, and a mixture thereof. Either form can be used. There is no particular limitation on the method of adding the compound to be condensed to the solution, and the compounds to be added can be added separately or in advance, and can be added all at once or intermittently. However, in order to enhance the uniformity of the addition, a method of diluting with an organic solvent compatible with the compound to be added and an aqueous medium or the like, and adding the compound intermittently is preferable.

The solution containing the poly (organo) siloxane condensate prepared above and the solution containing the silyl group-containing oligomer and / or polymer are mixed, and the mixture is stirred under heating to carry out a graft reaction. ,
A so-called polymer hybrid precursor solution can be obtained. A polymer hybrid precursor solution can also be obtained by coexisting a metal chelate compound in a mixed solution for the purpose of improving the uniformity of the graft reaction. The metal chelate compound used for the graft reaction can be used without any limitation. Among these metal chelate compounds, metal chelate compounds such as aluminum, titanium and zirconium are preferred. Specific examples thereof include aluminum chelate compounds such as aluminum ethyl acetoacetate diisopropylate, aluminum tris (ethyl acetoacetate), aluminum tris (acetoacetate), and aluminum bisethyl acetoacetate monoacetate. Aluminum tris (ethyl acetoacetate) is preferred. Examples of titanium chelate compounds include diisopropoxybis (acetylacetonato) titanium, isopropoxy (2-ethyl-1,3-hexanediolato) titanium, di-n-butoxybis (triethanolaminate) titanium, and tetraacetylacetonate Titanium and hydroxybis (lactato) titanium are listed, and titanium tetraacetylacetonate is particularly preferred. Examples of zirconium chelate compounds include zirconium tri-n-butoxyethyl acetate, zirconium di-n-butoxybis (ethylacetoacetate), zirconium n-butoxytris (ethylacetoacetate), zirconium tetrakis (n-propylacetoacetate), and tetrakis (ethyl). (Acetoacetate) zirconium and the like, and particularly preferred is tri-n-butoxyethyl acetate zirconium. These compounds can be used alone or in combination.

The graft reaction in the above reaction system is carried out under a relatively low speed stirring condition. The stirring temperature is from 0 ° C to 150
° C, more preferably from 10 ° C to 80 ° C. The stirring time is usually in the range of several minutes to several tens of hours, more preferably 30 minutes to 24 hours. Stirring does not require a special method, and can be carried out by using equipment commonly used in the art. In order to enhance the uniformity of the graft reaction, a solvent compatible with the two prepared solutions can be used without any limitation. Particularly preferably, it can be appropriately selected from alcohols, ketones and ethers. Specific examples of these solvents include ethyl alcohol, n-propyl alcohol,
Isopropyl alcohol, n-butyl alcohol, t-
Examples include alcohols such as butyl alcohol and isobutyl alcohol, ethers such as tetrahydrofuran and dioxane, and ketones such as acetone. These solvents may be used alone or in combination of two or more. Preferably, ethyl alcohol, n-propyl alcohol, and isopropyl alcohol are suitably used.

Next, the solvent is separated from the polymer hybrid precursor solution thus obtained. The method of separation can be a conventional method, and can be separated and purified by centrifugation, reprecipitation, ultrafiltration and the like. Also, from the solution using a drying method such as heating, vacuum and freezing,
The solvent can be removed for separation. After separation, the polymer hybrid precursor is heat-treated to obtain a polymer hybrid solidified product. This heat treatment aims at strengthening the inorganic phase contained in the polymer hybrid precursor, and any heat source device such as a box-type hot air dryer (stationary method) or a rotary kiln (rotary method) and a drying method can be used. It can be carried out. When a box-shaped hot air dryer is used, the removal of the solvent and the strengthening of the inorganic phase can be performed simultaneously. The heat treatment needs to be performed at a low temperature so as not to strain the inorganic phase structure. The heat treatment temperature can be appropriately selected so as not to adversely affect the organic components contained in the polymer hybrid precursor, such as carbonization. Heat treatment temperature from 10 ° C to 200
° C, more preferably in the range of 40 to 150 ° C. If the temperature is lower than this range, the solvent removal is insufficient, and if the temperature is higher than this range, the solvent may evaporate rapidly, causing a defect or a crack to occur in the inorganic phase. . The heat treatment time can be appropriately selected because it depends on the capacity of the equipment used and the like. Therefore,
In the next step, the solidified polymer hybrid is pulverized to obtain the polymer hybrid filler of the present invention. The method of pulverizing the solidified polymer hybrid is not particularly limited, but can be performed by a method generally employed in the art. For example, a container driving medium mill such as a ball mill and a vibration mill, a high-speed rotation mill such as a hammer mill and a turbo mill, and a medium stirring mill such as a sand grinder and an attritor can be used, and can be appropriately selected according to a required average particle diameter. The average particle size of the polymer hybrid filler is not particularly limited, but is preferably in the range of 0.1 to 100.0 μm, and more preferably in the range of 5.0 to 50.0 μm. The shape of the polymer hybrid filler is spherical, plate-like,
Any shape such as a crushed shape and a scale shape may be used, and there is no particular limitation.

The polymer hybrid filler of the present invention comprises: (a) an oligomer and / or a polymer containing at least one silyl group in a molecule;
Parts by weight, and (b) a (organo) silane compound and / or a low-condensate of an (organo) silane compound represented by the general formula (I) in the presence or absence of a metal compound, alone or in combination with a metal In the coexistence with an oxide sol, the poly (organo) siloxane condensate hydrolyzed or partially hydrolyzed and (co) condensed can be obtained by a graft reaction at a mixing ratio of 0.01 to 200 parts by weight. . When a metal chelate compound is contained as the component (c) in the polymer hybrid filler in order to enhance the uniformity of the graft reaction, it can be contained in the range of 0.001 to 30 parts by weight. The component (a) contained in the polymer hybrid filler is in the range of 0.01 to 100.0 parts by weight, and when the content of the component (a) increases, the mechanical properties of the polymer hybrid filler, particularly It is not preferable because problems occur in strength, coefficient of thermal expansion, surface hardness and the like. The component (b) contained in the polymer hybrid filler is in the range of 0.01 to 200.0 parts by weight, and when the content of the component (b) increases, the mechanical properties of the polymer hybrid filler improve. However, on the contrary, it tends to be brittle, and the wettability with the organic component constituting the dental composition is deteriorated, which is not preferable. The content of the component (b) is a sum of the content in terms of SiO ₂ and / or the content in terms of metal oxide of an element other than the Si element. When a metal chelate compound is contained as the component (c) in the polymer hybrid filler in order to enhance the uniformity of the graft reaction, it can be contained in the range of 0.001 to 30 parts by weight.

The polymer hybrid filler of the present invention thus obtained is a filler in which an organic component and an inorganic component are compounded at a molecular level, and may contain a higher level of an inorganic component than conventional organic composite fillers. it can. The amount of inorganic components contained in the polymer hybrid filler is TG-D
It can be confirmed by TA analysis or the ash method.
In addition, in the conventional organic composite filler, the inorganic component is unevenly dispersed inside the filler. However, the polymer hybrid filler of the present invention has an organic component and an inorganic component compounded at a molecular level inside the filler. To be
Evenly dispersed. This dispersion state can be confirmed with a transmission electron microscope (TEM). Further, in order to highly fill the polymer hybrid filler in a dental composition, the general formula (I):

Embedded image (Where Z is R ¹ O— or OCN—, X is halogen, Y
Is OH—, R ¹ is an organic group having 8 or less carbon atoms, R ² is an organic group, p is an integer of 1 to 3, a, b, and c are all 0 to
It is effective to further treat the surface of the polymer hybrid filler with an organosilane compound represented by an integer of 3 and a + b + c + p = 4). As a result, high filling of the polymer hybrid filler becomes possible, and various properties required as a dental composition can be satisfied.

Specific examples of the organosilane compound represented by the general formula (I) include methyltrimethoxysilane, ethyltrimethoxysilane, methoxytripropylsilane, propyltriethoxysilane, hexyltrimethoxysilane, vinyltrimethoxysilane. Silane, vinyltriethoxysilane, vinyltri (β-methoxyethoxy)
Silane, γ-methacryloyloxypropyltrimethoxysilane, γ-glycidoxypropyltrimethoxysilane, γ-mercaptopropyltrimethoxysilane, γ-
Examples include aminopropyltriethoxysilane, 3-aminopropyltriethoxysilane, methyltrichlorosilane, phenyltrichlorosilane, and the like. Among these organosilane compounds, vinyltrimethoxysilane, a compound known as a silane coupling agent in the dental field,
Vinyltriethoxysilane, vinyltrichlorosilane,
Vinyl (β-methoxyethoxy) silane, γ-methacryloyloxypropyltrimethoxysilane, γ-glycidoxypropyltrimethoxysilane, γ-mercaptopropyltrimethoxysilane, γ-aminopropyltrimethoxysilane, and the like. More preferably, it is γ-methacryloyloxypropyltrimethoxysilane.
These organosilane compounds can be used alone or in combination of two or more. The reason that these organosilane compounds enhance the affinity with the resin component is that the polymer hybrid filler contains many inorganic components, so that the organosilane compound can be efficiently and uniformly formed on the surface. This is because it was processed.

Another embodiment of the present invention is a dental composition comprising the above-described polymer hybrid filler of the present invention.
In particular, (a) the polymer hybrid filler of the present invention,
A dental composition comprising (b) a polymerizable monomer and (c) a polymerization initiator. The polymer hybrid filler of the present invention can be uniformly dispersed in a non-aggregated state in a resin matrix containing an organic polymer material as a main component. Furthermore, the cured product of the dental composition containing the polymer hybrid filler of the present invention as a filler has excellent abrasiveness, particularly excellent surface lubricity and gloss after polishing, and excellent mechanical properties and durability. It has the characteristic of exhibiting physical properties. This excellent property is due to the fact that the organic component and the inorganic component contained in the polymer hybrid filler are complexed at the molecular level.

The polymerizable monomers that can be used in the dental composition together with the polymer hybrid filler of the present invention include known monofunctional and polyfunctional monomers generally used as dental compositions. It can be used from polymerizable monomers. A typical example that is generally preferably used is a polymerizable monomer having an acryloyl group and / or a methacryloyl group. In the present invention, both the acryloyl group-containing polymerizable monomer and the methacryloyl group-containing polymerizable monomer are represented by (meth) acrylate or (meth) acryloyl.

A specific example is as follows. Monofunctional monomers such as methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate,
Hexyl (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, glycidyl (meth) acrylate,
Lauryl (meth) acrylate, cyclohexyl (meth) acrylate, benzyl (meth) acrylate, allyl (meth) acrylate, 2-ethoxyethyl (meth) acrylate, methoxypolyethylene glycol (meth) acrylate, glycerol (meth) acrylate, isobonyl (meth) ) Acrylate compounds such as acrylates, silane compounds such as γ- (meth) acryloyloxypropyltrimethoxysilane, γ- (meth) acryloyloxypropyltriethoxysilane, 2- (N, N-dimethylamino) ) Ethyl (meth) acrylate, N-methylol (meth) acrylamide,
Nitrogen-containing compounds such as diacetone (meth) acrylamide, aromatic bifunctional monomer: 2,2-bis (4- (meth)
Acryloyloxyphenyl) propane, 2,2-bis (4- (3- (meth) acryloyloxy-2-hydroxypropoxy) phenyl) propane, 2,2-bis (4- (meth) acryloyloxyethoxyphenyl)
Propane, 2,2-bis (4- (meth) acryloyloxydiethoxyphenyl) propane, 2,2-bis (4
-(Meth) acryloyloxytetraethoxyphenyl) propane, 2,2-bis (4- (meth) acryloyloxypentaethoxyphenyl) propane, 2,2-
Bis (4- (meth) acryloyloxydipropoxyphenyl) propane, 2 (4- (meth) acryloyloxyethoxyphenyl) -2 (4- (meth) acryloyloxydiethoxyphenyl) propane, 2 (4- (meth) Acryloyloxydiethoxyphenyl) -2 (4
-(Meth) acryloyloxytriethoxyphenyl)
Propane, 2 (4- (meth) acryloyloxydipropoxyphenyl) -2 (4- (meth) acryloyloxytriethoxyphenyl) propane, 2,2-bis (4
-(Meth) acryloyloxydipropoxyphenyl)
Aliphatic difunctional monomers such as propane and 2,2-bis (4- (meth) acryloyloxyisopropoxyphenyl) propane: 2-hydroxy-3-acryloyloxypropyl methacrylate, neopentyl glycol dihydroxypivalate (Meth) acrylate, ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, butylene glycol di (meth) acrylate, polyethylene glycol di (meth) acrylate, neopentyl glycol di ( (Meth) acrylate, propylene glycol di (meth) acrylate, 1,3-butanediol di (meth)
Acrylate, 1,4-butanediol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, glycerol di (meth) acrylate, etc. Trifunctional monomer: trimethylolpropane tri (meth)
Acrylate, trimethylolethane tri (meth) acrylate, trimethylol methane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, etc. Tetrafunctional monomer: pentaerythritol tetra (meth)
Specific examples of acrylates, ditrimethylolpropanetetra (meth) acrylate, and the like, and urethane-based polymerizable monomers; 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate; 3-chloro-2 A polymerizable monomer having a hydroxyl group such as hydroxypropyl (meth) acrylate, methylcyclohexane diisocyanate, methylene bis (4-cyclohexyl isocyanate), hexamethylene diisocyanate, trimethylhexamethylene diisocyanate, isophorone diisocyanate, diisocyanate methyl methylbenzene, 4, Having a difunctional or trifunctional or higher urethane bond derived from an adduct with a diisocyanate compound such as 4-diphenylmethane diisocyanate Distearate (meth) acrylate. In addition to the (meth) acrylate-based polymerizable monomer, other polymerizable monomers depending on the purpose of the dental composition, for example, a monomer, oligomer or oligomer having at least one polymerizable group in the molecule. There is no limitation even if a polymer is used. In addition, there is no problem even if a substituent such as an acidic group or a fluoro group is present in the same molecule.

In the present invention, the polymerizable monomer includes not only a single component but also a mixture of a plurality of polymerizable monomers. When the viscosity of the polymerizable monomer is extremely high at room temperature or when the polymerizable monomer is solid, it is preferable to use the polymerizable monomer as a mixture of a low-viscosity polymerizable monomer and a combination polymerizable monomer. This combination is not limited to two types,
Three or more types may be used. Further, since a polymer composed of only a monofunctional polymerizable monomer does not have a crosslinked structure, the mechanical strength of the polymer generally tends to be inferior. Therefore, when a polymerizable monomer is used, it is preferable to use it together with a polyfunctional polymerizable monomer. The most preferable combination of the polymerizable monomers is a method in which an aromatic compound of a bifunctional polymerizable monomer is used as a main component and combined with an aliphatic compound of a bifunctional polymerizable monomer.

When a dental composition containing the polymer hybrid filler of the present invention is provided with tooth or base metal adhesion, a phosphate group,
It is effective to use a polymerizable monomer containing an acid group such as a carboxylic acid group and a sulfonic acid group in the molecule. In order to impart noble metal adhesion, it is also effective for the present invention to use a polymerizable monomer containing a sulfur atom in the molecule. Specific examples of the polymerizable monomer having an adhesive ability to these are as follows. Carboxylic acid group-containing polymerizable monomer: (meth) acrylic acid,
1,4-di (meth) acryloyloxyethyl pyromellitic acid, 6- (meth) acryloyloxynaphthalene-
1,2,6-tricarboxylic acid, N- (meth) acryloyl-p-aminobenzoic acid, N- (meth) acryloyl-5
-Aminosalicylic acid, 4- (meth) acryloyloxyethyl trimellitic acid and its anhydride, 4- (meth)
Acryloyloxybutyl trimellitic acid and its anhydride, 2- (meth) acryloyloxybenzoic acid, β-
(Meth) acryloyloxyethyl hydrogen succinate, β- (meth) acryloyloxyethyl hydrogen maleate, 11- (meth) acryloyloxy-1,1-undecanedicarboxylic acid, p-vinylbenzoic acid and the like.

Phosphoric acid group-containing monomer: 2- (meth) acryloyloxyethyl dihydrogen phosphate,
3- (meth) acryloyloxypropyl dihydrogen phosphate, 10- (meth) acryloyloxydecyl dihydrogen phosphate, bis (2-
(Meth) acryloyloxyethyl) hydrogen phosphate, 2- (meth) acryloyloxyethyl phenyl hydrogen phosphate and the like. Sulfonic acid group-containing monomer: 2- (meth) acrylamide-2-methylpropanesulfonic acid, 4- (meth) acryloyloxybenzenesulfonic acid, 3- (meth) acryloyloxypropanesulfonic acid and the like. Polymerizable monomer containing a sulfur atom: (meth) acrylate having a triazine thiol group, (meth) acrylate having a mercapto group, (meth) acrylate having a polysulfide group, (meth) having a thiophosphate group
Examples include acrylate, (meth) acrylate having a disulfide cyclic group, (meth) acrylate having a mercaptodithiazole group, (meth) acrylate having a thiouracil group, and (meth) acrylate having a thiirane group. There is no problem even if these polymerizable monomers are used alone or in combination of two or more.

The polymerization initiator that can be used in the dental composition together with the polymer hybrid filler of the present invention is not particularly limited, and a known radical generator can be used without any limitation. Polymerization initiators generally initiate polymerization by mixing immediately before use (chemical polymerization initiator),
It is roughly classified into those that initiate polymerization by heating or heating (thermal polymerization initiator) and those that initiate polymerization by light irradiation (photopolymerization initiator). Examples of the chemical polymerization initiator include a redox-type polymerization initiation system composed of an organic peroxide / amine compound or an organic peroxide / amine compound / sulfinate, an organic peroxide / amine compound / borate compound, and oxygen and water. Examples thereof include organometallic polymerization initiator systems which initiate polymerization by reacting. Further, sulfinic acid salts and borate compounds can be initiated by reaction with a polymerizable monomer having an acidic group. Specific examples of the organic peroxide include benzoyl peroxide, parachlorobenzoyl peroxide, 2,4-dichlorobenzoyl peroxide, acetyl peroxide, lauroyl peroxide, tertiary butyl peroxide, cumene hydroperoxide, Examples thereof include 2,5-dimethylhexane, 2,5-dihydroperoxide, methyl ethyl ketone peroxide, and tertiary butyl peroxybenzoate. The amine compound is preferably a secondary or tertiary amine in which an amine group is bonded to an aryl group.
N, N-dimethyl-toluidine, N, N-dimethylaniline, N-β-hydroxyethyl-aniline, N, N-di (β-hydroxyethyl) -aniline, pN, N-di (β-hydroxyethyl ) -Toluidine, N-methyl-
Aniline, p-N-methyl-toluidine and the like can be mentioned.

Specific examples of the sulfinates include sodium benzenesulfinate, lithium benzenesulfinate, sodium p-toluenesulfinate and the like. As the borate compound,
Trialkylphenylboron, trialkyl (p-fluorophenyl) boron (alkyl group is n-butyl group, n-
Octyl group, n-dodecyl group, etc.), lithium salt, potassium salt, magnesium salt, tetrabutylammonium salt, tetramethylammonium salt and the like. In addition, as the organometallic polymerization initiator,
Organic boron compounds such as triphenylborane, tributylborane, and tributylborane partial oxide are exemplified. As the thermal polymerization initiator by heating or heating, azo compounds such as azobisisobutyronitrile, methyl azobisisobutyrate and azobiscyanovaleric acid are preferably used in addition to the above-mentioned organic peroxides.

On the other hand, examples of the photopolymerization initiator include those composed of a photosensitizer, and a photosensitizer / photopolymerization accelerator.
Specific examples of the photosensitizer include benzyl,
Camphorquinone, α-naphthyl, acetonaphthene,
p, p′-dimethoxybenzyl, p, p′-dichlorobenzylacetyl, pentanedione, 1,2-phenanthrenequinone, 1,4-phenanthrenequinone, 3,4-phenanthrenequinone, 9,10-phenanthrenequinone,
Α-diketones such as naphthoquinone, benzoin alkyl ethers such as benzoin, benzoin methyl ether and benzoin ethyl ether, thioxanthone, 2-chlorothioxanthone, 2-methylthioxanthone, 2-
Thioxanthones such as isopropylthioxanthone, 2-methoxythioxanthone, 2-hydroxythioxanthone, 2,4-diethylthioxanthone, and 2,4-diisopropylthioxanthone; benzophenones such as benzophenone, p-chlorobenzophenone and p-methoxybenzophenone; Acylphosphine oxides such as 2,6-trimethylbenzoyldiphenylphosphine oxide and bis (2,6-dimethoxybenzoyl) -2,4,4-trimethylpentylphosphine oxide; 2-benzyl-dimethylamino-1- (4 -Morpholinophenyl) -butanone-1,2-benzyl-
Diethylamino-1- (4-morpholinophenyl)-
Α-aminoacetophenones such as propanone-1, ketals such as benzyldimethylketal, benzyldiethylketal, and benzyl (2-methoxyethylketal); bis (cyclopentadienyl) -bis [2,6-difluoro-3- (1-pyrrolyl) phenyl] -titanium,
Bis (cyclopentadienyl) -bis (pentanefluorophenyl) -titanium, bis (cyclopentadienyl)
And titanocenes such as -bis (2,3,5,6-tetrafluoro-4-disiloxyphenyl) -titanium.

Specific examples of the photopolymerization accelerator include N, N-dimethylaniline, N, N-diethylaniline, N, N-di-n-butylaniline, N, N-dibenzylaniline, p- N, N-dimethyl-toluidine, m-
N, N-dimethyl-toluidine, p-N, N-diethyl-
Toluidine, p-bromo-N, N-dimethylaniline,
m-chloro-N, N-dimethylaniline, p-dimethylaminobenzaldehyde, p-dimethylaminoacetophenone, p-dimethylaminobenzoic acid, p
-Dimethylaminobenzoic acid ethyl ester, p-dimethylaminobenzoic acid amino ester, N, N-dimethylanthranilic acid methyl ester, N, N-dihydroxyethylaniline,
p-N, N-dihydroxyethyl-toluidine, p-dimethylaminophenyl alcohol, p-dimethylaminostyrene, N, N-dimethyl-3,5-xylidine, 4-
Dimethylaminopyridine, N, N-dimethyl-α-naphthylamine, N, N-dimethyl-β-naphthylamine,
Tributylamine, tripropylamine, triethylamine, N-methyldiethanolamine, N-ethyldiethanolamine, N, N-dimethylhexylamine, N,
N-dimethyldodecylamine, N, N-dimethylstearylamine, N, N-dimethylaminoethyl methacrylate, N, N-diethylaminoethyl methacrylate,
Tertiary amines such as 2,2 '-(n-butylimino) diethanol; secondary amines such as N-phenylglycine; 5-butylbarbituric acid; 1-benzyl-5-phenylbarbituric acid; Tin compounds such as barbituric acids, dibutyltin diacetate, dibutyltin dilaurate, dioctyltin dilaurate, dioctyltin diversate, dioctyltin bis (isooctyl mercaptoacetate) salt, and tetramethyl-1,3-diacetoxydistannoxane , Lauryl aldehyde,
Aldehyde compounds such as terephthalaldehyde, dodecyl mercaptan, 2-mercaptobenzoxazole,
Examples thereof include sulfur-containing compounds such as 1-decanethiol and thiosalicylic acid. Further, in order to improve the photopolymerization accelerating ability, in addition to the photopolymerization accelerator, citric acid, malic acid,
Addition of oxycarboxylic acids such as tartaric acid, glycolic acid, gluconic acid, α-oxyisobutyric acid, 2-hydroxypropanoic acid, 3-hydroxypropanoic acid, 3-hydroxybutanoic acid, 4-hydroxybutanoic acid, dimethylolpropionic acid is effective It is a target.

These polymerization initiators can be used alone or in combination of two or more. Further, they can be used in combination regardless of the polymerization form or the type of polymerization initiator. The amount of the polymerization initiator to be added may be appropriately selected according to the intended use. Generally, 0.1 to polymerizable monomer
It may be selected from the range of 10 to 10 parts by weight. Among the polymerization initiators described above, it is a preferred embodiment to use a photopolymerization initiator that generates a radical by light irradiation, and is most preferable in that the dental composition can be polymerized in a state where air is little mixed. It is preferably used. Among the photopolymerization initiators, a combination of an α-diketone and a tertiary amine is more preferable, and an aromatic amine having an amino group such as camphorquinone and ethyl pN, N-dimethylaminobenzoate directly bonded to a benzene ring is more preferable. Alternatively, a combination of an aliphatic amine having a double bond in a molecule such as N, N-dimethylaminoethyl methacrylate is most preferable. In addition, depending on the intended use, coumarin-based, cyanine-based, thiazine-based sensitizing dyes, halomethyl group-substituted -s-triazine derivative, diphenyliodonium salt compound or the like by irradiation of Brönsted acid or Lewis acid. The resulting photoacid generator, quaternary ammonium halides, transition metal compounds and the like can also be used as appropriate.

As a dental composition, a second filler can be compounded in addition to the polymer hybrid filler of the present invention. As the second filler, those known as dental fillers, for example, quartz, amorphous silica, clay,
Aluminum oxide, talc, mica, kaolin, glass,
Inorganic substances such as barium sulfate, zirconium oxide, titanium oxide, silicon nitride, aluminum nitride, titanium nitride, silicon carbide, boron carbide, calcium carbide, hydroxyapatite, calcium phosphate; polymethyl methacrylate, polyethyl methacrylate, polyvinyl chloride, polystyrene, polyester And organic substances such as polymers or oligomers such as nylon; and organic-inorganic composites. There is no problem even if the second filler is used alone or in combination of two or more. In addition, it is more preferable that the second filler is generally surface-treated with a titanate coupling agent, an aluminate coupling agent, or a silane coupling agent which is commonly used. The mixing ratio of the second filler can be appropriately selected as needed, and may be selected, for example, from a range of 1 to 90 parts by weight.

Further, in the dental composition, an ultraviolet absorbent such as 2-hydroxy-4-methylbenzophenone, a polymerization of hydroquinone, hydroquinone monomethyl ether, 2,5-ditert-butyl-4-methylphenol and the like are included. Inhibitors, discoloration inhibitors, antibacterial materials, coloring pigments,
Other conventionally known components such as additives can be optionally added as needed. Packaging form of the dental composition of the present invention,
There is no particular limitation, and any one of a one-pack packaging form and a two-pack packaging form or any other form is possible depending on the type of polymerization initiator or purpose of use, and can be appropriately selected according to the application.

[0044]

EXAMPLES Hereinafter, the present invention will be described in more detail and specifically with reference to Examples, but the present invention is not limited thereto. The performance evaluation method of the dental composition employed in the following examples is as follows. (1) Bending test and durability test Evaluation purpose: To evaluate the bending strength of a dental composition test specimen and the bending strength after long-term immersion in water. Evaluation method: After filling the prepared dental composition into a stainless steel mold, placing a cover glass on both sides and pressing it with a glass kneading plate, using a photopolymerization irradiator (Denter-Color XS: manufactured by Kluzzer) One side: Light irradiation was performed for 3 minutes to cure. After curing, the cured product was taken out of the mold, and the back surface was similarly irradiated with light for 3 minutes (6 minutes on both sides) to cure. The cured product is carborundum paper # 20
00 and finish polished, and polished the specimen (25 × 2 ×
2 mm: rectangular parallelepiped). The specimen was heated at 37 ° C for 24 hours.
After immersion in water for a period of time and three months, a bending test was performed. The bending test was performed using an Instron universal testing machine (Instron 5567, manufactured by Instron), and the distance between the fulcrums was 20.
mm, a crosshead speed of 1 mm / min, and a load cell of 1 KN. In addition, the test was performed with five test pieces and the average value was adopted.

(2) Hardness test evaluation purpose: To evaluate the hardness of a dental composition test specimen. Evaluation method: After filling the prepared dental composition into a glass mold, placing a cover glass on both sides and pressing it with a glass plate, using a photopolymerization irradiator (Denter-Color XS: manufactured by Kluzzer). One side: Light irradiation was performed for 3 minutes to cure. After curing, the cured product was taken out of the mold, and the back surface was similarly irradiated with light for 3 minutes (6 minutes on both sides) to cure. The cured product is carborundum paper # 2000
And finish polishing using a test piece (25 × 2 × 2 m
m: rectangular parallelepiped). The test piece was immersed in water at 37 ° C. for 24 hours and then subjected to a Rockwell hardness test. The hardness test was performed using a superficial type Rockwell hardness tester (manufactured by Akashi) with a steel ball of 1/8 inch and a load of 30 kgf.
(249 N) (30 W) under a load time of 30 seconds. In addition, the test was performed with five test pieces, two points were measured for each test piece, and the average value was evaluated.

Reference Example 1 [Preparation of Silyl Group-Containing Polymer Solution 1] 100.0 parts of benzene was placed in a reactor equipped with a stirrer and a condenser.
Further, 100.0 parts of γ-methacryloyloxypropyltrimethoxysilane (hereinafter abbreviated as γ-MPTS) (0.
4 mol) and 2.7 parts of azobisisobutyronitrile (hereinafter abbreviated as AIBN), and the mixture was stirred at 80 ° C. for 3 hours to prepare a silyl group-containing polymer solution 1 having a solid concentration of 50%. The polymer was analyzed by gel permeation chromatography (hereinafter abbreviated as GPC), and as a result, it was estimated that the polymer had a number average molecular weight of 11,000 in terms of polystyrene and contained an average of 44 silyl groups per polymer molecule.

Reference Example 2 [Preparation of Silyl Group-Containing Polymer Solution 2] 140.0 parts of benzene was charged into a reactor equipped with a stirrer and a condenser.
Further, methyl methacrylate (hereinafter abbreviated as MMA) 40
Part (0.4 mol), 100.0 parts of γ-MPTS (0.
4 mol) and 4.0 parts of AIBN, and stirred at 80 ° C. for 5 hours to prepare a silyl group-containing polymer solution 2 having a solid content of 50%. As a result of GPC analysis of this polymer, it was estimated that the polymer had a number average molecular weight of 12,000 in terms of polystyrene, and contained an average of 26 silyl groups per polymer molecule.

Reference Example 3 [Preparation of Poly (organo) siloxane Condensate Solution 3] In a reactor equipped with a stirrer and a condenser, 145.8 parts (0.7 mol) of tetraethoxysilane (hereinafter abbreviated as ES) were placed.
1), 24.8 parts (0.1 mol) of γ-MPTS, methyl triethoxysilane (hereinafter abbreviated as MTES) 35.7
Parts (0.2 mol), ion-exchanged water 30.6 parts (1.7
mol) and 0.3 part of a 0.1N hydrochloric acid solution, and
And stir for 3 hours at a solid concentration of 32% poly (organo)
A siloxane condensate solution 3 was prepared. As a result of GPC analysis of this poly (organo) siloxane condensate, it had a number average molecular weight of 3,300 in terms of polystyrene.

Reference Examples 4 and 5 [Preparation of poly (organo) siloxane condensate solutions 4 and 5] Poly (organo) siloxane condensate solutions 4 and 5 were prepared in the same manner as in Reference Example 3 with the mixed compositions shown in Table 1. did.

Reference Example 6 [Preparation of poly (organo) siloxane condensate solution 6] MTES 10 was placed in a reactor equipped with a stirrer and a condenser.
0.0 part (0.48 mol), 24.8 parts (0.1 mol) of γ-MPTS, 200.0 parts of methanolic silica sol (hereinafter abbreviated as silica sol: silica content 30%),
25.0 parts (1.9 mol) of ion-exchanged water were added, and 60
The mixture was stirred at 3 ° C. for 3 hours to prepare a poly (organo) siloxane condensate solution 6.

Reference Examples 7 to 9 [Preparation of poly (organo) siloxane condensate solutions 7 to 9] Poly (organo) siloxane condensate solutions 7 to 9 were prepared in the same manner as in Reference Example 6 with the mixed compositions shown in Table 1. did.

Example 1 Production of Polymer Hybrid Filler 1 In a reactor equipped with a stirrer and a condenser, 237.3 parts of the poly (organo) siloxane condensate solution 3 prepared in Reference Example 3, ethyl alcohol 45 .4 parts and 22.9 parts of the silyl group-containing polymer solution 1 prepared in Reference Example 1, and tris (ethylacetoacetate) aluminum (hereinafter referred to as T
EAAL: Kawaken Fine Chemical Co.) plus 2
The mixture was stirred at 0 ° C. for 30 minutes, and further stirred at 50 ° C. for 2 hours to complete the graft reaction. After completion of the reaction, the solvent was removed,
A polymer hybrid solid was obtained. After heat-treating the solidified polymer hybrid at 105 ° C. for 3 hours,
The mixture was pulverized with a ball mill and sieved with a sieve of 325 meshes to obtain polymer hybrid filler 1.

Examples 2 to 7 [Production of Polymer Hybrid Fillers 2 to 7] Reference Example 1
Or 2, using the silyl group-containing polymer solution 1 or 2 prepared in 2 and the poly (organo) siloxane condensate solutions 4 to 7 prepared in Reference Examples 4 to 7 as in Example 1; At polymer hybrid filler 2
~ 7 were produced.

Example 8 [Preparation of Dental Composition] Each of the components was kneaded at the mixing ratio shown below, followed by defoaming under reduced pressure to prepare Dental Compositions 1 to 7. These dental compositions 1 to 7
, And a bending test, a durability test and a hardness test were performed, and the results are shown in Table 3. Dimethacryloyloxyethyl-2,2,4-trimethyl 13 parts Hexamethylene-1,6-dicarbamate (hereinafter abbreviated as UDMA: manufactured by Shin-Nakamura Chemical) Triethylene glycol dimethacrylate 10 parts (hereinafter abbreviated as TEGDMA: Shin-Nakamura) Chemical product) Pentamethacryloyloxyethoxymonofluorocyclotri 10 parts Phosphazene (synthetic product) Camphorquinone 0.3 parts Dibenzyl 1.5 parts 2-methacryloyloxyethyl-p-dimethylaminobenzoate 1.4 parts Polymer hybrid filler 1 7 67.0 parts

Comparative Example 1 As Comparative Example 1, the same test was carried out using a commercially available visible light-curable composite resin Heliomollar Radiopaque (Vivadent: Lot 22542; for premolars) containing an organic composite filler. 3 is shown.

[0056]

[Table 1]

[0057]

[Table 2]

[0058]

[Table 3]

[0059]

EFFECTS OF THE INVENTION In a dental composition, by blending the polymer hybrid filler of the present invention as a filler, excellent mechanical strength and surface properties as well as excellent polishing properties, surface lubrication and glossiness are obtained. Hardness and durability can be imparted.

 ──────────────────────────────────────────────────続 き Continued on the front page F term (reference) 4C089 AA02 AA06 BC02 BC06 BC08 BC11 BC13 BE11 4J002 BG07W BQ00W CP03X CP05X CP09X DE096 DE126 DE146 DJ016 FD016

Claims (9)

[Claims] (1) an oligomer and / or a polymer containing at least one silyl group in a molecule, and (b) a general formula (I): (Where Z is R ¹ O— or OCN—, X is halogen, Y
Is OH—, R ¹ is an organic group having 8 or less carbon atoms, R ² is an organic group, a, b, and c are integers of 0 to 4, p is an integer of 0 to 3, and a + b + c + p = 4. ), The (organo) silane compound and / or the low-condensate of the (organo) silane compound is hydrolyzed or partially hydrolyzed in the presence or absence of a metal oxide sol, and the condensed poly ( An organo) siloxane condensate and a polymer hybrid filler. (A) an oligomer and / or a polymer containing at least one silyl group in a molecule; and (b) a general formula (I): (Where Z is R ¹ O— or OCN—, X is halogen, Y
Is OH—, R ¹ is an organic group having 8 or less carbon atoms, R ² is an organic group, a, b, and c are integers of 0 to 4, p is an integer of 0 to 3, and a + b + c + p = 4. ), The (organo) silane compound and / or the low-condensate of the (organo) silane compound is hydrolyzed or partially hydrolyzed in the presence or absence of a metal oxide sol, and the condensed poly ( 2. The polymer hybrid filler according to claim 1, comprising an (organo) siloxane condensate and (c) a metal chelate compound. 3. The polymer hybrid filler according to claim 1, wherein component (a) is contained in a proportion of 0.01 to 100.0 parts by weight and component (b) is contained in a proportion of 0.01 to 200 parts by weight. 4. Component (a) in an amount of 0.01 to 100.0 parts by weight, component (b) in an amount of 0.01 to 200 parts by weight, and component (c) in an amount of 0.001 to 30 parts by weight. 3. The polymer hybrid filler of claim 2, wherein (5) The component (a) has a general formula (II): (Where Z is R ¹ O— or OCN—, X is halogen, Y
Is OH-, R ¹ is an organic group having 8 or less carbon atoms, R ^{2 ′} is an organic group containing an unsaturated group, a, b and c are integers of 0 to 3, p
Is an integer of 1 to 3, and a + b + c + p = 4)
Or an oligomer and / or polymer obtained by homopolymerizing a low-condensation product of an organosilane compound and / or an organosilane compound represented by the formula (1), or copolymerizing in the presence of another polymerizable monomer. Claim 1
5. The polymer hybrid filler according to any one of items 4 to 4. 6. The composition according to claim 1, wherein the component (b) is a (organo) silane compound represented by the general formula (I) and / or (organo)
The low-condensate of a silane compound alone or a metal oxide sol and a co-condensate hydrolyzed or partially hydrolyzed in the presence of a metal compound. 2. The polymer hybrid filler according to item 1. (1): a step of preparing a solution containing an oligomer and / or a polymer containing at least one silyl group in a molecule, (2): a general formula in the absence or presence of a metal compound The (organo) silane compound and / or the low-condensation product of the (organo) silane compound represented by (I) are (co) condensed by hydrolysis or partial hydrolysis together with the metal oxide sol. Preparing a solution containing the poly (organo) siloxane condensate, and (3) reacting the solutions prepared in steps (1) and (2) to produce a polymer hybrid filler. 7. The method for producing a polymer hybrid filler according to any one of 1, 3, 5, and 6. (1): a step of preparing a solution containing an oligomer and / or a polymer containing at least one silyl group in a molecule, (2): a general formula in the absence or presence of a metal compound The (organo) silane compound and / or the low-condensation product of the (organo) silane compound represented by (I) are (co) condensed by hydrolysis or partial hydrolysis together with the metal oxide sol. Preparing a solution containing the poly (organo) siloxane condensate, and (3) reacting the solutions prepared in steps (1) and (2) in the presence of a metal chelate compound to produce a polymer hybrid filler. The method for producing a polymer hybrid filler according to any one of claims 2, 4, 5, and 6, comprising a step of producing a polymer hybrid filler. 9. A polymer hybrid of one of the polymer hybrid fillers obtained by the method for producing a polymer hybrid filler according to claim 1 and the polymer hybrid filler according to claim 7 or claim 8. A dental composition comprising a filler, (b) a polymerizable monomer, and (c) a polymerization initiator.