JP4932210B2 - Dental composition - Google Patents

Description

  The present invention relates to a dental composition that can be particularly suitably used for dentistry. In detail, it is related with dental adhesive composition, such as dental cement and a dental bonding material.

  Caries are diseases in which teeth are decalcified by the acid produced by caries pathogens present in the oral cavity, and treatment is performed by cutting infected sites and filling / restoring dental materials. For these treatments, adhesive materials such as adhesive resin cement, bonding material, or glass ionomer cement are used.

  For adhesion to teeth, not only temporary adhesion strength but also durability in the oral cavity environment is regarded as important. For example, when a gap occurs at the interface between the tooth and the adhesive due to a decrease in the adhesive effect in the oral cavity environment, and microleakage occurs at the same time, irritating substances, bacteria, etc. enter the gap, and further, the caries are regenerated at the repaired part. The probability of occurrence increases and treatment often fails.

  On the other hand, in addition to the conventional dental adhesives described above, Non-Patent Document 1 and the like include an adhesive mainly composed of calcium phosphates of tetracalcium phosphate and dicalcium phosphate and converted into hydroxyapatite similar to that of living hard tissue. The use of wood is presented.

However, in the treatment for caries and the like, there is a concern that the application range is narrow due to the initial adhesive strength.
Furthermore, dental or biological adhesive compositions to which various calcium phosphates have been added have been proposed for the purpose of improving biocompatibility or mechanical strength. However, dental adhesives and these inorganic compounds are used in combination. It is also pointed out that this causes a significant decrease in adhesion performance.

  Patent Document 1 proposes a composition comprising calcium phosphate powder, polymethacrylate powder, and methacrylate monomer, and it is said that it is possible to obtain a cured product having particularly excellent physical properties. When bonding to a hard tissue, the bonding strength is low, which may cause microleakage.

For this reason, a dental composition that has an excellent adhesive effect and does not cause microleakage at the same time is desired.
Journal of Hard Tissue Biology; 4 (1): 1-7 JP 2001-231848 A

  An object of the present invention is to provide a novel dental composition, particularly a dental adhesive resin composition.

The present invention relates to (A) a polymerizable monomer having at least one acidic group in the molecule,
(B) a polymerizable monomer having at least one hydroxyl group in the molecule;
(C) a compound represented by the following formula (1) and / or (2),

(However, in Formula (1), R ¹ and R ² are each independently a hydrogen atom or an alkyl group which may have a functional group or a substituent, and R ³ is a hydrogen atom. An atom or a metal atom);

(In the formula (2), R ⁴ and R ⁵ are each independently a hydrogen atom or an alkyl group, and R ⁶ is a hydrogen atom, or a functional group or a substituent. Any of an alkyl group or an alkoxyl group which may have a group).
(D) a dental composition containing a filler containing tetracalcium phosphate (TTCP) and dicalcium phosphate (DCP);
The use amount of the acidic group-containing polymerizable monomer (A) constituting the dental composition is such that the acidic group-containing polymerizable monomer (A), the hydroxyl group-containing polymerizable monomer (B) and the formula ( Use of the acidic group-containing polymerizable monomer (B) in the range of 1 to 50% by weight in 100% by weight of the total amount of the compound (C) represented by 1) and / or (2) The amount of the compound (C) represented by the formula (1) and / or (2) is in the range of 0.01 to 30% by weight,
The amount of the calcium filler containing (D) tetracalcium phosphate (TTCP) and dicalcium phosphate (DCP) is the above acidic group-containing polymerizable monomer (A) and hydroxyl group-containing polymerizable monomer. Dental adhesive composition characterized by being in the range of 15 to 95 parts by weight with respect to 100 parts by weight of the total amount of the body (B) and the compound represented by formula (1) and / or (2) It is in the thing.

  The dental composition of the present invention can be used as a dental adhesive composition, and exhibits an excellent adhesive effect.

Hereinafter, the dental composition of the present invention will be described in detail. In the following description, unless otherwise indicated, “part” and “%” are based on weight.
The dental adhesive composition of the present invention comprises:
(A) a polymerizable monomer having at least one acidic group in the molecule;
(B) a polymerizable monomer having at least one hydroxyl group in the molecule;
(C) a compound represented by the following formula (1) and / or (2),

(However, in Formula (1), R ¹ and R ² are each independently a hydrogen atom or an alkyl group which may have a functional group or a substituent, and R ³ is a hydrogen atom. An atom or a metal atom);

(In the formula (2), R ⁴ and R ⁵ are each independently a hydrogen atom or an alkyl group, and R ⁶ is a hydrogen atom, or a functional group or a substituent. Any of an alkyl group or an alkoxyl group which may have a group).
(D) A dental adhesive composition containing a calcium filler containing tetracalcium phosphate (TTCP) and dicalcium phosphate (DCP).

  Thus, the dental composition of the present invention comprises an acidic group-containing polymerizable monomer (A), a hydroxyl group-containing polymerizable monomer (B), a specific reactive monomer (C), and phosphoric acid. It is a curable resin composition particularly suitable for dentistry containing a calcium filler (D) in which tetracalcium (TTCP) and dicalcium phosphate (DCP) are combined. That is, by using a calcium filler (D), which is a combination of a specific calcium-containing compound, tetracalcium phosphate (TTCP) and dicalcium phosphate (DCP), as a calcium filler of this composition, This has the effect of promoting the remineralization ability of the teeth.

The polymerizable monomer containing at least one acidic group in the molecule as the component (A) to be blended in the dental composition of the present invention usually has an acidic group, one polymerizable group in the molecule, Is monofunctional. As the polymerizable group having an acidic group-containing polymerizable property, a radical polymerizable group is preferable. Examples of such a radical polymerizable group include a vinyl group, a vinyl cyanide group, an acryloyl group, a methacryloyl group, and an acrylamide group. And a methacrylamide group. Examples of the acidic group include a carboxyl group and its acid anhydride group, phosphoric acid group, thiophosphoric acid group, sulfonic acid group, and sulfinic acid group. Or what functions substantially as an acidic group like the acid anhydride group of a carboxyl group, such as being easily decomposed under practical conditions to become the acidic group, is regarded as an acidic group in the present invention.

As a specific example of the polymerizable compound having a carboxyl group in the molecule as the component (A) used in the present invention,
Α-unsaturated carboxylic acids such as (meth) acrylic acid (hereinafter referred to as the generic name of acrylic acid and methacrylic acid), maleic acid;
Vinyl aromatic ring compounds such as 4-vinylbenzoic acid;
11- (Meth) acryloyloxy-1,1-undecanedicarboxylic acid (hereinafter referred to as “(meth) acryloyl” as a generic term for acryloyl and methacryloyl), etc., between a (meth) acryloyloxy group and a carboxylic acid group A carboxylic acid compound in which a linear hydrocarbon group is present;
(Meth) acryloyloxyalkylnaphthalene (poly) carboxylic acids such as 6- (meth) acryloyloxyethylnaphthalene-1,2,6-tricarboxylic acid;
4- (meth) acryloyloxyalkyl trimellitic acid, 4- (meth) acryloyloxymethyl trimellitic acid, 4- (meth) acryloyloxyethyl trimellitic acid, 4- (meth) acryloyloxybutyl trimellitic acid, etc. ( (Meth) acryloyloxyalkyl trimellitic acid;
4- [2-hydroxy-3- (meth) acryloyloxy] butyl trimellitic acid and other compounds further containing a hydroxyl group;
Carboxybenzoyloxy such as 2,3-bis (3,4-dicarboxybenzoyloxy) propyl (meth) acrylate (hereinafter referred to as “(meth) acrylate” as a generic term for acrylate and methacrylate). A compound having:
N, O-di (meth) acryloyloxytyrosine, O- (meth) acryloyloxytyrosine, N- (meth) acryloyloxytyrosine, N- (meth) acryloyloxyphenylalanine, O- (meth) acryloyloxyphenylalanine, N, N- and / or O-substituted mono or di (meth) acryloyloxyamino acids such as O-di (meth) acryloyloxyphenylalanine;
N- (meth) acryloyl-4-aminobenzoic acid, N- (meth) acryloyl-5-aminobenzoic acid, 2- or 3- or 4- (meth) acryloyloxybenzoic acid, 4- or 5
-N- and / or O-mono or di (meth) acryloyl (amino or oxy) benzoic acid compounds such as (meth) acryloylaminosalicylic acid;
Addition product of 2-hydroxyethyl (meth) acrylate and pyromellitic dianhydride, 2-hydroxyethyl (meth) acrylate and maleic anhydride or 3,3 ', 4,4'-benzophenone tetracarboxylic acid An addition reaction product of a hydroxyalkyl (meth) acrylate and an unsaturated polycarboxylic acid anhydride such as an addition reaction product of an anhydride or 3,3 ′, 4,4′-biphenyltetracarboxylic dianhydride;
Compounds having polycarboxybenzoyloxy and (meth) acryloyloxy such as 2- (3,4-dicarboxybenzoyloxy) -1,3-di (meth) acryloyloxypropane;
An adduct of N-phenylglycine or N-tolylglycine and glycidyl (meth) acrylate;
4- [N- (2-hydroxy-3- (meth) acryloyloxypropyl) amino] phthalic acid, 3 or 4- [N-methyl-N- (2-hydroxy-3- (meth) acryloyloxypropyl) amino And N-alkyl-N- (hydroxy (meth) acryloyloxyalkyl) aminophthalic acid compounds such as phthalic acid. Among these, in the present invention, as the component (A), 11- (meta)
Acryloyloxy-1,1-undecanedicarboxylic acid and 4- (meth) acryloyloxyethyl trimellitic acid are preferably used.

  Further, as a polymerizable monomer having an acidic group used in the present invention, a group in which at least one hydroxyl group is bonded to a phosphorus atom and a functional group that can be easily converted into the group in water include, for example, phosphoric acid. Preferred examples include compounds having a group having one or two hydroxyl groups as ester groups.

Examples of the polymerizable monomer having such a group include 2- (meth) acryloyloxyethyl acid phosphate, 2- and / or 3- (meth) acryloyloxypropyl acid phosphate, 4- (meth) acryloyloxybutyl. Acid phosphate, 6- (
(Meth) acryloyloxyhexyl acid phosphate, 8- (meth) acryloyloxyoctyl acid phosphate, 10- (meth) acryloyloxydecyl acid phosphate, 12- (meth) acryloyl oxide decyl acid phosphate, etc. (meth) acryloyloxyalkyl acid phosphate ;
Acid phosphates having two or more (meth) acryloyloxyalkyl groups such as bis [2- (meth) acryloyloxyethyl] acid phosphate, bis [2- or 3- (meth) acryloyloxypropyl] acid phosphate;
2- (meth) acryloyloxyethylphenyl acid phosphate, 2- (meth) acryloyloxyethyl-p-methoxyphenyl acid phosphate and other (meth) acryloyloxyalkyl groups and aromatic rings such as phenylene groups, and oxygen atoms The acid phosphate etc. which have via a hetero atom can be mentioned. The compound which substituted the phosphate group in these compounds by the thiophosphate group can also be illustrated. Of these, 2- (meth) acryloyloxyethyl acid phosphate can be preferably used.

Examples of polymerizable monomers having a sulfonic acid group or a functional group that can be easily converted into sulfonic acid group in water include 2-sulfoethyl (meth) acrylate, 2- or 1-sulfo-1- or 2-propyl (meth) ) Sulfoalkyl (meth) acrylates such as acrylate, 1- or 3-sulfo-2-butyl (meth) acrylate;
An atomic group containing a heteroatom such as halogen or oxygen in the alkyl part such as 3-bromo-2-sulfo-2-propyl (meth) acrylate and 3-methoxy-1-sulfo-2-propyl (meth) acrylate Having a compound;
1,1-dimethyl-2-sulfoethyl (meth) acrylamide, 2-methyl-2- (meth) acrylamide propanesulfonic acid and the like, which are acrylamide instead of the acrylate, etc .;
Furthermore, vinyl aryl sulfonic acids such as 4-styrene sulfonic acid and 4- (prop-1-en-2-yl) benzene sulfonic acid can be exemplified. Of these, 4-styrenesulfonic acid can be preferably used. These compounds can be used alone or in combination of two or more.

In the present invention, among the polymerizable monomers containing at least one of these acidic groups, 4
-(Meth) acryloxyethyl trimellitic acid and / or its acid anhydride are most preferred.

  In the dental composition of the present invention, the component (A) is preferably added in an amount of 1 to 50% by weight, preferably 100% by weight in total of the component (A), the component (B) described later, and the component (C). Is contained in an amount of 1 to 30% by weight. By using the polymerizable monomer (A) containing an acidic group in the molecule in such an amount, the dental composition is good for hard tissues typified by a dentin as an adherend. Show good adhesion.

  The component (B) in the dental composition of the present invention is a polymerizable monomer having at least one hydroxyl group in the molecule. These polymerizable monomers containing a hydroxyl group may further contain a functional group such as a carboxyl group, a phosphate group, a sulfonate group, an amino group, or a glycidyl group in the molecule.

As such compounds, for example, in the case of a monomer having a (meth) acryloyl group, 2-hydroxyethyl (meth) acrylate, 2- or 3-hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, 5- Monohydroxyalkyl (meth) acrylates such as high hydroxypentyl (meth) acrylate, 6-hydroxyhexyl (meth) acrylate, 10-hydroxydecyl (meth) acrylate;
Dihydroxyalkyl (meth) acrylates such as 1,2- or 1,3- and 2,3-dihydroxypropane (meth) acrylate;
Polyethylene glycol (meth) such as diethylene glycol mono (meth) acrylate, triethylene glycol mono (meth) acrylate, pentaethylene glycol mono (meth) acrylate, polyethylene glycol mono (meth) acrylate, dipropylene glycol mono (meth) acrylate Acrylates;
Hydroxyl-containing (meth) acrylamides such as methylol (meth) acrylamide, N- (2,3-dihydroxypropyl) (meth) acrylamide, N- (1,3-dihydroxypropyl) (meth) acrylamide;
Glycidyl (addition reaction product of 2-hydroxy-3-phenoxypropyl (meth) acrylate, 2-hydroxy-3-naphthoxypropyl (meth) acrylate, 1 mol of bisphenol A and 2 mol of glycidyl (meth) acrylate ( Mention may be made of addition products of (meth) acrylates with aliphatic or aromatic polyols (including phenol). These polymerizable monomers can be used alone or in combination. 2 of these
-Hydroxyethyl (meth) acrylate is most preferred.

In the dental adhesive composition of the present invention, the component (B) is 1 to 99.99 weights in a total of 100% by weight of the component (A), the component (B), and the component (C) described later. %, Preferably 3
It is contained in an amount in the range of ˜90% by weight.

  (C) in the dental composition of the present invention is represented by the following formula (1).

(In the above formula (1), R ¹ and R ² are each independently a hydrogen atom or an alkyl group which may have a functional group or a substituent, and R ³ is a hydrogen atom or a metal atom.
)
And / or the following formula (2)

(In the above formula (2), R ⁴ and R ⁵ are each independently a hydrogen atom or an alkyl group, and R ⁶ is a hydrogen atom or an alkyl group or an alkoxyl group which may have a functional group or a substituent. .)
And is used for the purpose of improving curability and improving adhesion performance to teeth.

Specific compounds included in the above formula (1) include N-phenylglycine, N-tolylglycine, N- (3- (meth) acryloxy-2-hydroxypropyl) -N-phenylglycine and / or these Mention may be made of salts. Among these, it is preferable to use N-phenylglycine and / or a salt thereof.

Specific compounds included in the formula (2) include N, N-dimethylaminobenzoic acid and its alkyl ester, N, N-diethylaminobenzoic acid and its alkyl ester, and N, N-dipropylamino. Benzoic acid and its alkyl ester, N-isopropylaminobenzoic acid and its alkyl ester, N-isopropyl-N-methylaminobenzoic acid and its alkyl ester, and the like, and the like, and the like. N, N-dimethylaminobenzaldehyde, N, N-diethylaminobenzaldehyde, aliphatic alkylaminobenzaldehydes represented by N, N-dipropylaminobenzaldehyde, N-isopropyl-N-methylaminobenzaldehyde, etc .; N, N-dimethylamino Acetylbenzene, N, N- Aliphatic alkylaminoacetylbenzenes and aliphatic alkylaminoacylbenzenes represented by ethylaminoacetylbenzene, N, N-dipropylaminoacetylbenzene, N-isopropylaminoacetylbenzene, N-isopropyl-N-methylaminoacetylbenzene and the like And so on.

These compounds can be used alone or in combination of two or more.
In the dental composition of the present invention, the component (C) is 0.01 to 30% by weight, preferably 0.8%, in the total of 100% by weight of the components (A), (B) and (C). Used in an amount in the range of 05-25% by weight.

In the dental composition of the present invention, tetracalcium phosphate (Ca ₄ (PO ₄ ) ₂ O) (hereinafter referred to as TTCP) and dicalcium phosphate (CaHPO) are used as the calcium filler as component (D). ₄ ) (hereinafter referred to as DCP). By using the above combination of TTCP and DCP as a calcium filler, after applying the dental composition, both are converted into hydroxyapatite similar to dental hard tissue in the presence of moisture in the oral cavity, Stronger adhesive strength is developed. In addition, these are preferably anhydrides, and the composition weight ratio is also calculated on the assumption thereof. Incidentally, DCP is also known as dicalcium phosphate, calcium hydrogen phosphate, dicalcium hydrogen phosphate, dicalcium hydrogen phosphate, or calcium monohydrogen phosphate, all of which are the same CaHPO _4.
It is.

  The blending molar ratio of TTCP and DCP (TTCP / DCP) is usually in the range of 0.33 to 3.5, preferably in the range of 2.3 to 3, particularly preferably in the range of 2.3 to 2.7. . When deviating from this range, the conversion to hydroxyapatite is not sufficiently performed, and not only the purpose is not achieved, but also the molecules that did not participate in the conversion to hydroxyapatite react with the acidic group in component (A), Adhesiveness with a tooth is remarkably inferior, and it may be a cause of lowering mechanical properties of the cured composition.

  The particle size of TTCP is usually in the range of 0.5-30 μm, more preferably 1-25 μm, more preferably 10-20 μm, and the particle size of DCP is usually 0.001-30 μm, more preferably 0.05. -20 μm, more preferably in the range of 0.1-15 μm. When the value is below the lower limit of the numerical range, the curing time becomes extremely small and the operation becomes difficult. When the value exceeds the upper limit, the curing time becomes long and the operability is inferior and the adhesive performance is liable to deteriorate.

Furthermore, the existence form of TTCP and DCP is not particularly limited, and both may be substantially formed particles mixed in the above blending range, and the overall blending ratio is substantially The TTCP particles and the DCP particles may be mixed, or particles having different blending ratios may be mixed so as to be within the above range.

  In the dental composition of the present invention, the component (D) is usually 15 to 95 parts by weight, preferably 20 parts per 100 parts by weight of the total of the components (A), (B) and (C). It is mix | blended in the quantity within the range of -90 weight part.

  If it is less than 15 parts by weight below this range, the effect of improving the adhesive performance due to the formation of hydroxyapatite after application is not observed, and if it exceeds this range and exceeds 95 parts by weight, it is before the conversion to hydroxyapatite after application. This is because, in this case, the bonding performance may be lowered by reacting with (A).

  In the present invention, (E) a polymerization initiator can be added to the dental composition as desired. As the polymerization initiator (E), organic peroxides, inorganic peroxides, alkylboranes, partial oxides of alkylboranes, α-diketone compounds, acylphosphine oxides, organic sulfinic acids, organic sulfinates, inorganic Sulfur compounds and barbituric acids can be mentioned. These can be used alone or in combination of two or more.

Examples of the organic peroxide include diacetyl peroxide, dipropyl peroxide, dibutyl peroxide, dicaproyl peroxide, dilauryl peroxide, benzoyl peroxide (BPO), p, p′-dichlorobenzoyl peroxide ( ClBPO
), P, p′-dimethoxybenzoyl peroxide, p, p′-dimethylbenzoyl peroxide and p, p′-dinitrodibenzoyl peroxide. Of these, benzoyl peroxide is most preferred.

  Examples of inorganic peroxides include ammonium persulfate, potassium persulfate, potassium chlorate, potassium bromate, and potassium perphosphate. Examples of the redox metal compound include nitrates, chlorides, and acetylacetates of transition metals such as copper, iron, and cobalt.

Alkylborane compounds include triethylboron, tri (n-propyl) boron, triisopropylboron, tri (n-butyl) boron, tri (s-butyl) boron, triisobutylboron, tripentylboron, trihexylboron, Trialkyl borons such as octyl boron, tridecyl boron, tridodecyl boron, tricyclopentyl boron, tricyclohexyl boron, butyl dicyclohexyl borane;
Alkoxyalkylborons such as butoxydibutylboron;
Dialkylboranes such as diisoamylborane, 9-borabicyclo [3.3.1] nonane;
Examples thereof include aryl borate compounds such as sodium tetraphenylboron, tetraphenylboron triethanolamine salt, tetraphenylboron dimethyl-p-toluidine salt, and tetraphenylboron dimethylaminoethylbenzoate.

Examples of the partial oxide of alkylborane include partially oxidized tributyl boron.
Examples of α-diketones include benzoins such as benzoin, benzoin methyl ether, benzoin ethyl ether, and benzoin isopropyl ether; benzyl, 4,4′-dichlorobenzyl, diacetyl, α-cyclohexanedione, d, l-camphorquinone,
Examples thereof include camphorquinone-10-sulfonic acid and camphorquinone-10-carboxylic acid.

Examples of acylphosphine oxides include 2,4,6-trimethylbenzoyldiphenylphosphine oxide.
Organic sulfinic acids include aromatic sulfinic acids such as benzenesulfinic acid, o-toluenesulfinic acid, p-toluenesulfinic acid, ethylbenzenesulfinic acid, decylbenzenesulfinic acid, dodecylbenzenesulfinic acid, chlorobenzenesulfinic acid, and naphthalenesulfinic acid. Or the salt can be mentioned.

The inorganic sulfur compound is preferably a reducing inorganic sulfur compound used as a redox polymerization initiator that can be used when polymerizing a radical polymerizable monomer in a medium such as water or an aqueous solvent, such as sulfurous acid or bisulfite. And metasulphite, metabisulfite, pyrosulfite, thiosulfuric acid, 1 dithionic acid, 1,2 thionic acid, hyposulfite, hydrosulfurous acid and salts thereof.

In addition, in order to improve the polymerization initiation effect of the polymerization initiator, a reducing compound other than the above can be used in combination as desired. For example, N, N-dimethylaniline, N, N-dimethyl-p-toluidine, N, N-diethyl-p-toluidine, N, N-diethanol-p-toluidine, N, N-dimethyl-p-t-butyl Examples include aniline, N, N-dimethylanisidine, N, N-dimethyl-p-chloroaniline, N, N-dimethylaminoethyl (meth) acrylate, N, N-diethylaminoethyl (meth) acrylate, and the like. Can be used alone or in combination of two or more.

The component (E) in the composition of the present invention is the sum of the component (A), the component (B), the component (C), the component (E) and the component (F) blended as desired (however, the following ( F) component is included even when it is 0.) In 100% by weight, usually 0.01 to 50% by weight, preferably
It is blended in an amount in the range of 0.05 to 40% by weight, more preferably 0.1 to 20% by weight.

If desired, (F) polyfunctional (meth) acrylate can be used in the dental composition of the present invention.
As such polyfunctional (meth) acrylate (F),
Poly (oxyalkylene) di (meth) acrylates such as ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate;
Glycerol di (meth) acrylate;
Di (meth) acrylates of butanetriol, such as trimethylolpropane;
Di (meth) acrylate or tri (meth) acrylate of butanetetraol such as meso-erythritol, di (meth) acrylate of pentanetriol;
Di (meth) acrylate or tri (meth) acrylate of pentanetetraol such as tetramethylolmethane;
Polyfunctional (meth) acrylate having 1-2 hydroxyl groups of xylitol and its isomers;
Di (meth) acrylate of hexanetriol;
Di (meth) acrylate or tri (meth) acrylate of hexanetetraol;
Polyfunctional (meth) acrylate having 1 to 2 hydroxyl groups of hexanepentaol;
Polyfunctional (meth) acrylate having 1 to 2 hydroxyl groups of hexanehexaol;
Or following formula (3)

[In the formula (3), R ⁷ is a divalent aromatic or cycloalkyl residue which has at least one aromatic ring and may have an oxygen atom or a sulfur atom in the molecule, preferably Chemical formula (4)

And R ⁸ and R ⁹ independently of each other represent a hydrogen atom or a methyl group, and n and m represent a positive integer.] Can do. These polyfunctional (meth) acrylates preferably have 2 to 3 functional groups, and more preferably bifunctional ones. When the number of functional groups is large, the degree of cross-linking of the cured product of the composition increases depending on the amount added, the flexibility of the cured product of the composition is impaired, and the adhesiveness to the tooth or dental metal tends to be reduced. is there.

  In the dental composition of the present invention, the component (F) is 100% by weight of the total weight of (A), (B), (C), (E) and (F) (provided that the component (E) is 0) In some cases, it is usually contained in an amount of 5 to 70% by weight, more preferably 10 to 65% by weight, and still more preferably 15 to 60% by weight.

When the addition amount of the polyfunctional (meth) acrylate compound (F) is small, the effect of promoting the curing rate tends to be small, and when the addition amount of the component (F) is large, the curing time becomes too short. There is no room for appropriate treatment, the water absorption of the cured composition is increased, and the durability of adhesion to hard tissues such as metal, tooth, or bone tends to decrease. Moreover, there exists a tendency for the bridge | crosslinking degree of a composition hardening body to become high, and for the softness | flexibility of a composition hardening body to be impaired.

  If desired, at least one filler (G) selected from the group consisting of (G) an organic filler, an inorganic filler, and an organic-inorganic composite filler can be added to the dental composition of the present invention.

  Examples of the organic filler include poly (alkyl (meth) acrylate), polyolefin, polyvinyl acetate, polyethylene glycol, polypropylene glycol and the like.

  Examples of monomers constituting poly (alkyl (meth) acrylate) include methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, cyclohexyl (meth) acrylate, and benzyl (meth). Mention may be made of (meth) acrylate monomers such as acrylates. In addition, a small amount of a crosslinkable monomer can be copolymerized with poly (alkyl (meth) acrylate) as necessary. Examples of the crosslinkable monomer include polyfunctional monomers such as ethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, and butadiene.

Examples of the monomer constituting the polyolefin include ethylene and propylene. In addition, the polyolefin may be copolymerized with components such as ethylidene norbornene, 1,4-hexadiene, dicyclopentadiene, if necessary.

  Examples of inorganic fillers include metal oxide powders such as zirconium oxide, bismuth oxide, titanium oxide, zinc oxide and aluminum oxide particles; metal salt powders such as calcium carbonate, bismuth carbonate, zirconium phosphate and barium sulfate; Examples thereof include glass fillers such as silica glass, aluminum-containing glass, barium-containing glass, strontium-containing glass, and zirconium silicate glass; silver-releasing filler, fluorine-releasing filler, and the like.

In order to obtain a strong bond between the inorganic filler and the resin, it is preferable to use an inorganic filler that has been subjected to a surface treatment such as silane treatment or polymer coating.
Furthermore, examples of fillers that can be used in the present invention include inorganic-organic composite fillers. As the inorganic-organic composite filler, for example, TMPT filler (trimethylolpropane methacrylate and silica filler mixed and polymerized and then pulverized) can be used.

These organic fillers, inorganic fillers, and inorganic-organic composite fillers can be used alone or in combination.
As the component (G) that is a filler in the dental composition of the present invention, the average particle size is 0.05.
Contains 40 to 80% by weight of 10 to 10 μm zirconium oxide filler, 10 to 30% by weight of spherical silica filler having an average particle diameter of 1 to 10 μm, and 10 to 30% by weight of organic composite filler having an average particle diameter of 1 to 30 μm A filler is preferred. Further, the zirconium oxide used here is a filler having an average particle diameter of 5 to 30 μm, particularly 1 to 30 μm, which is coated with a polymer that can be dissolved in the component (B), for example, PMMA or polyvinyl acetate (PVAc). Is preferred.

In the dental composition of the present invention, the amount of component (G) used is (A), (B), (C), (D), (E), (F) and (G). 100% by weight of total ingredients (
However, the case where at least one of the component (E) and the component (F) is 0 is also included. )inside,
Usually, it can be contained in an amount of 15 to 85% by weight, more preferably 20 to 80% by weight, and still more preferably 25 to 75% by weight.

  If desired, the (H) dye and / or pigment may be added to the dental composition of the present invention. Examples of such dyes and / or pigments include Phloxine BK, Acid Red, Fast Acid Magenta, Phloxine B, Fast Green FCF, Rhodamine B, Basic Fuchsin, Acid Fuchsin, Eosin, Ethithrosin, Safranine, Rose Bengal, Bemel, Gentian Purple, Examples include copper chlorophyll soda, lacaic acid, sodium fluorescein, cochineal, perilla, talc, and titanium white. These dyes and / or pigments can be used alone or in combination of two or more.

  If desired, a compound capable of releasing fluoride ions in water may be added to the dental composition of the present invention as component (I). As the component (I), any component that releases soluble effective fluorine ions into the composition can be used. For example, disodium fluorophosphate, tin fluoride, sodium fluoride , Potassium fluoride, sodium silicon fluoride, fluoroaluminosilicate glass, ammonium fluoride, etc. can be used, among which sodium fluoride, calcium fluoride, sodium monofluorophosphate, stannous fluoride are used. preferable. The blending amount is appropriately set in consideration of the use amount and application frequency of the dental composition of the present invention, the acid resistance, the effectiveness of remineralization and the influence on the human body. By blending the component (I), the effect of improving the acid resistance of the hard tissue can be expected. In the present invention, the component (I) is preferably in the range of 0.0001 to 5% by weight, more preferably 0.001 to 2% by weight, particularly 0.01 to 1% by weight as the fluorine ion concentration in the composition. It is preferable to use it in an amount. If it is less than 0.0001% by weight, which is below this range, the acid resistance effect and remineralization effect of the desired tooth will not be sufficiently exhibited, and if it exceeds 5% by weight, there is a concern for harm to the living body.

  If desired, a polymerization inhibitor (J) may be added to the dental composition of the present invention for the purpose of storage stability. As the component (J) which is a polymerization inhibitor, conventionally known components can be used, and examples thereof include 4-methylphenol and 2,6-di-t-butylcresol.

  In the composition of the present invention, a compound having properties of two or more categories as one component (for example, components (A), (B), (C), (F), etc. ) May be used.

The concept of the method for calculating the composition ratio of each component in such a case will be described in detail in the following assumed model case. For example, assume a system consisting of those having the properties of categories C (x) and C (y) (referred to as S (x) and S (y), respectively). And S (xy) having the property C (xy) having the property (y). In this case, the total weight W (xy) of S (xy) is halved and counted as the total weight W (x) of S (x) and the total weight W (y) of S (y). The weight ratios R (x) and R (y) for each category are calculated. That is,
R (x) = {W (x) + W (xy) / 2} / {W (x) + W (y) + W (xy)} × 100
R (y) = {W (y) + W (xy) / 2} / {W (x) + W (y) + W (xy)} × 100
As the calculation. In addition to the case where there is such a double dependency C (xy), the same calculation (W (xyz) / 3) can be performed when there is a triple dependency or more. In other words, each n-weight dependent weight is divided by n and distributed.

Even when there are two or more categories of properties, the total weight ratio (R (x) + R (y)) exceeds 1 (100% by weight). Absent. The total (R (x) + R (y)) is selected from the above numerical ranges so that the weight parts of the respective components do not exceed 100 parts by weight.

  If desired, a solvent can be added to the dental composition of the present invention. Examples of the solvent include water, and examples of the organic solvent include alcohols such as ethanol and propanol; ketones such as acetone. In addition, although the water used here can use distilled water, ion-exchange water, Japanese Pharmacopoeia purified water, etc., physiological saline etc. can also be used instead of water. In particular, in the present invention, it is preferable to use Japanese Pharmacopoeia purified water. These solvents can be used alone or in combination of two or more.

  As a form of use of the dental composition of the present invention, a method in which the components (A) to (J) are mixed in advance and applied to a tooth tissue or the like can be exemplified. If the mixture of these components changes in form and performance over a long period of time and may impair the effects of the present invention, each component may be stored alone or divided in any combination and mixed before use. Composition.

  In the present invention, `` configured '' is not limited to being all mixed in this composition from the beginning, and if necessary, each component is appropriately sealed and stored, It includes mixing at the time of use. That is, the present invention includes a dental composition that is mixed and used at the ratio by weight when used.

In addition, as a concrete preservation | save form of a dental composition, there exist the following forms, for example.
(1) At least two components selected from the group consisting of an acidic group-containing polymerizable monomer (A), a hydroxyl group-containing polymerizable monomer (B) and a polyfunctional (meth) acrylate compound (F) are mixed. Preservation form.

  (2) Selected from the group consisting of compound (C) represented by formula (1) or (2), calcium filler (D), polymerization initiator (E), filler (G) and fluorine-releasing compound (I) A storage form in which at least two components are mixed.

(3) The acidic group-containing polymerizable monomer (A), the hydroxyl group-containing polymerizable monomer (B) and / or the polyfunctional (meth) acrylate compound (F) is converted into a polymerization initiator (E), formula (1) Or (2)
The compound (C), the calcium filler (D), the filler (G) and / or the fluorine-releasing compound (I) represented by the formula (I) are packaged separately from each other.

(4) The polymerization initiator (E) and / or the compound (C) represented by the formula (1) or (2) is a calcium filler (D), filler (G) and / or fluorine releasing compound (I).
And the preservation form that is packaged isolated from each other.

The reason for adopting the storage mode as described above is as follows.
The acidic group-containing polymerizable monomer (A), the hydroxyl group-containing polymerizable monomer (B), and the polyfunctional (meth) acrylate compound (F) are all in a liquid state at room temperature or compatible with each other. Since there are many things which are easy to do, there is little possibility that it will isolate | separate even if it mixes beforehand, and it is preferable in many cases that the effort which mixes by the time of use by mixing beforehand is saved. The compound (C) represented by the formula (1) or (2), the polymerization initiator (E), the calcium filler (E), the filler (G), and the fluorine releasing compound (I) are all powders. In many cases, it is easily prepared in a particulate form, and is therefore often suitable for powder mixing.

A mixture of polymerizable monomers (that is, an acidic group-containing polymerizable monomer (A), a hydroxyl group-containing polymerizable monomer (B), a polyfunctional (meth) acrylate compound (F)) and a formula ( By separating the compound (C), calcium filler (D), polymerization initiator (E), filler (G) or fluorine-releasing compound (I) represented by 1) or (2), a polymerization initiator ( The progress of the polymerization reaction of the polymerizable monomer during storage due to E) can be prevented. In addition, by dividing and packaging in this way, there is no risk of performance change due to neutralization or ion exchange of the acidic group of the monomer by the calcium filler (D), which is often basic, Furthermore, there is an advantage that there is no possibility of trouble occurring due to non-uniform and agglomeration of the calcium filler (D), filler (G), or fluorine releasing compound (I) that is difficult to dissolve in the monomer liquid. .

In the case of a mixture of tetracalcium phosphate (TTCP) and dicalcium phosphate (DCP), the reaction to convert to hydroxyapatite proceeds in the presence of water, but in a dry state, in the absence of crystal water, or non-aqueous In the solvent system, the reaction that these are converted into hydroxyapatite does not substantially proceed. Therefore, in such a state, even if both of them coexist and are mixed, they can be used favorably as a dental composition.
〔Example〕
Hereinafter, the present invention will be described in more detail with reference to examples, but the present invention is not limited to the examples.
(Explanation of abbreviations)
The abbreviations described in the examples described below represent the components shown below. TTCP: Tetracalcium phosphate (Ca ₄ (PO ₄ ) ₂ O)
DCP: dicalcium phosphate (CaHPO ₄ )
HEMA: 2-hydroxyethyl methacrylate 4-MET: 4-methacryloxyethyl trimellitic acid P-2M: bis (2-methacryloxyethyl) acid phosphate 3G: triethylene glycol dimethacrylate 2.6-E : 2,2-bis (4-methacryloyloxypoly (ethoxy) phenyl) propane A-9300: N, N, N-tris (2-acryloxyethyl) isocyanurate Bis-GMA: 2,2-bis [4 -(2-Hydroxy-3-methacryloyloxypropoxy) phenyl] propane CQ: d, l-camphorquinone NPGNa: N-phenylglycine sodium EDAB: ethyl 4- (N, N-diethylamino) benzoate (preparation of calcium filler) )
TTCP and DCP were each pulverized with a planetary ball mill and classified with a # 280 sieve. Classified TTCP 36.7 g (0.1 mol) and DCP 13.6 g (0.1 mol) were mixed well again with a planetary ball mill to obtain a calcium filler. When the average particle size of the obtained calcium filler was measured with a laser diffraction / scattering particle size distribution analyzer (LA-910, Horiba, Ltd.), the average particle size was 1 μm and the maximum particle size was 10 μm. The TTCP / DCP blending molar ratio of the obtained calcium filler is 1.0.
(Measurement of dentin bond strength)
The front forehead of the bovine is polished with # 180 emery paper under water pouring, the flat surface of the dentin for adhesion is cut out, washed and dried, and then the mold with a diameter of 4.8 mm and a thickness of 1 mm is fixed to the surface of the dentin with double-sided tape. The adhesion area was defined. About 0.09 g of a liquid material obtained by mixing a predetermined composition and 0.9 g of a powder material obtained by mixing a predetermined composition with a planetary ball mill are kneaded on a kneaded paper, filled in a mold, and the filled surface is made of polyester. The film was covered with a transparent film, and irradiated with light for 30 seconds with a dental visible light irradiator (trade name: Translux CL2, manufactured by Kultzer). Subsequently, the polyester film is removed, and the cured product is bonded to a PMMA rod having a diameter of 6 mm and a height of 20 mm with a dental adhesive (trade name: Superbond C & B, manufactured by Sun Medical Co., Ltd.) for 30 minutes. After leaving still at room temperature, it was immersed in 37 degreeC water for 24 hours. Tensile bond strength with crosshead speed of 1mm /
It was measured in min and the adhesive strength was evaluated. Thereby, the basic characteristics of the adhesive can be evaluated.
(Evaluation of marginal sealing)
The anterior teeth of the bovine mandible were polished with # 180 emery paper under water injection, the flat dentin surface was shaved, and a cavity with a diameter of about 3 mm and a depth of 2 mm was formed under water injection using a dental air turbine. The cavity surface was treated with dentin surface treatment material green (dental surface treatment agent for dentin mainly composed of citric acid and ferric chloride, manufactured by Sun Medical Co., Ltd.) for 10 seconds, washed with water and dried. . 0.09 g of a monomer solution having a predetermined composition and 0.9 g of a powder material having a predetermined composition are kneaded on a kneaded paper, filled into the cavity, and the filled surface is coated with cellophane (registered trademark), and then saturated at 37 ° C. Left overnight in humidity. After standing, the filled surface was polished with # 600 emery paper under water injection to make a smooth surface, and then the tooth filled in a 0.3% basic fuchsin aqueous solution was immersed for 3 minutes. After the tooth taken out from the aqueous fuchsin solution was washed with distilled water, the filling surface was further polished with water injection with # 100 emery paper, and it was observed with a microscope whether fuchsin had entered the tooth surface from the polished surface. Furthermore, the filling tooth was cut parallel to the cutting direction of the cavity, and it was similarly observed using a microscope whether fuchsin penetrated from the cavity surface toward the inside of the tooth. In both cases, the case where fuchsin did not enter was evaluated as ◯, and the case where fuchsin was intruded was evaluated as x.

4-MET 20g, HEMA 39.5g, Bis-GMA 20g, 2.6-E 15g, 3G 5g, CQ 0.5g was mixed well, and the liquid material was obtained.
On the other hand, a powder material composed of 97 g of the above calcium filler and 3 g of NPGNa was obtained.

  As a result of performing the above-mentioned dentin adhesive strength test and marginal sealability test using both, the result of the dentin adhesive strength test was 9 MPa, and the result of the marginal sealability test was “◯”.

4-MET 10g, P-2M 2g, HEMA 40g, A-9300 20g, 3G 10g, CQ 0.5g was mixed well, and the liquid material was obtained.
On the other hand, a powder material comprising 50 g of the above calcium filler, 30 g of zirconium oxide having an average particle diameter of 1 μm, 19 g of spherical silica filler having an average particle diameter of 3 μm, and 1 g of NPGNa was obtained.

  As a result of performing the above-mentioned dentin adhesive strength test and marginal sealability test using both, the result of the dentin adhesive strength test was 12 MPa, and the result of the marginal sealability test was “◯”.

4-MET 20g, HEMA 39.5g, Bis-GMA 20g, 2.6-E 15g, 3G 5g, CQ 0.5g was mixed well, and the liquid material was obtained.
On the other hand, a powder material composed of 97 g of the above calcium filler and 3 g of EDEB was obtained.

  As a result of performing the above-mentioned dentin adhesive strength test and marginal sealability test using both, the result of the dentin adhesive strength test was 8 MPa, and the result of the marginal sealability test was “◯”.

4-MET 10g, P-2M 2g, HEMA 40g, A-9300 20g, 3G 10g, CQ 0.5g was mixed well, and the liquid material was obtained.
On the other hand, a powder material comprising 50 g of the above calcium filler, 30 g of zirconium oxide having an average particle diameter of 1 μm, 19 g of spherical silica filler having an average particle diameter of 3 μm, and 1 g of EDAB was obtained.

As a result of performing the above-mentioned dentin adhesive strength test and marginal sealability test using both, the result of the dentin adhesive strength test was 9 MPa, and the result of the marginal sealability test was “◯”.

Claims (10)

(A) a polymerizable monomer having at least one acidic group in the molecule;
(B) a polymerizable monomer having at least one hydroxyl group in the molecule;
(C) a compound represented by the following formula (1 ) ,

(However, in Formula (1), R ¹ and R ² are each independently a hydrogen atom or an alkyl group which may have a functional group or a substituent, and R ³ is a gold atom. Genus atom )),
(D) A calcium filler containing tetracalcium phosphate (TTCP) and dicalcium phosphate (DCP) in a blending molar ratio (TTCP / DCP) in the range of 0.33 to 3.5. A dental composition,
The use amount of the acidic group-containing polymerizable monomer (A) constituting the dental composition is such that the acidic group-containing polymerizable monomer (A), the hydroxyl group-containing polymerizable monomer (B) and the formula ( 1 ) The amount of the hydroxyl group-containing polymerizable monomer (B) used is 1 to 99.99 in the range of 1 to 50% by weight in 100% by weight of the total amount used with the compound (C) represented by 1 ). in the range of weight%, a dental composition usage, characterized in near Rukoto the range of 0.01 to 30% by weight of the compound of formula (1) (C). The dental composition includes the acidic group-containing polymerizable monomer (A), the hydroxyl group-containing polymerizable monomer (B), the compound (C) represented by the formula (1 ), and the calcium filler (D) . In addition, it further contains (E) a polymerization initiator, and the amount of the polymerization initiator (E) constituting the dental composition is such that the acidic group-containing polymerizable monomer (A) and the hydroxyl group-containing polymerizable are used. In 100% by weight of the total amount of the monomer (B), the compound (C) represented by the formula (1 ), the polymerization initiator (E), and the polyfunctional (meth) acrylate compound (F) blended as required. The dental adhesive composition according to claim 1, wherein the composition is in the range of 0.01 to 50% by weight.   The dental composition according to claim 1, wherein the dental composition further comprises (F) a polyfunctional (meth) acrylate compound.   The dental composition according to claim 1, wherein the dental composition further comprises (G) at least one filler selected from the group consisting of an organic filler, an inorganic filler, and an organic-inorganic composite filler. .   The dental composition according to claim 1, wherein the dental composition further comprises (H) a pigment.   The dental composition according to claim 1, wherein the dental composition further comprises (I) a compound that releases fluoride ions in water.   2. The polymerizable monomer having at least one hydroxyl group in the molecule (B) is 4- (meth) acryloxyethyl trimellitic acid and / or an acid anhydride thereof. Dental composition.   The (E) polymerization initiator is an organic peroxide, an inorganic peroxide, an alkylborane, a partial oxide of an alkylborane, an α-diketone compound, an acylphosphine oxide, an organic sulfinic acid, an organic sulfinate, an inorganic The dental composition according to claim 2, wherein the dental composition is at least one polymerization initiator selected from the group consisting of a sulfur compound and barbituric acid. A liquid material containing the monomer (A), the monomer (B) and the polymerization initiator (E);
  The dental composition of Claim 1 obtained by mixing the said compound (C) and the powder material containing a calcium filler (D).   The dental composition according to any one of claims 1 to 9, wherein the dental composition is a dental adhesive composition.