JP4969800B2 - Dental materials, dental compositions, dental adhesives, remineralization accelerators, bioadhesives and caries detection materials - Google Patents

Description

  The present invention relates to a dental material, a dental composition, a dental adhesive, a remineralization promoting material, a biological adhesive, and a caries detection material. More specifically, the present invention relates to dental compositions such as dental bonding materials, dental resin cements, dental fillers, dental primer materials, dental adhesives or bioadhesives, and hard tissues such as teeth. Recalcification promoting material that can be applied and supplied with calcium components from the application site, and caries detection material that can detect caries when applied

  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. In the treatment of such caries, in cases where the dental pulp is exposed due to, for example, severe dental caries, the dental pulp removal therapy is usually selected. Thus, a tooth that has lost its pulp has a low mechanical strength, and there is an increased risk of breakage and the occurrence of purulent inflammation of the periodontal tissue, leading to an earlier time for extraction. Therefore, considering the life of the teeth, it is preferable to proceed to the next treatment without leaving excessive denting, leaving a low possibility of infection by cariogenic pathogens and leaving room for remineralization and hardening. . In this case, it is necessary to eradicate the remaining bacteria so that they do not grow, and it is necessary to compensate for the insufficient adhesive performance of the adhesive used when mounting the prosthesis, etc. A technique of applying an adhesive after using an inorganic compound such as calcium hydroxide in order to form a hard tissue has been adopted. However, such an inorganic compound has a long application period of several weeks to several months, and a new caries infection that occurs during that period, a gap occurs at the tooth-adhesive interface due to a decrease in the adhesive effect. So-called minute leakage is likely to occur. In addition, there is a concern that the adhesive performance may be significantly lowered by using the dental adhesive and these inorganic compounds at the same time.

  When microleakage occurs at the same time, irritating substances or bacteria enter through this gap, and the probability of caries reoccurrence at the repaired portion increases. For this reason, there is a demand for a dental composition or a dental adhesive that has an excellent adhesive effect and does not cause microleakage at the same time, and also has a remineralization ability with respect to surrounding teeth.

  Furthermore, the above-mentioned dental adhesives that have been conventionally used, for example, by adding a remineralization promoting material, can be imparted with a hard tissue forming action, that is, a property that promotes dentin remineralization. Since the problem can be solved and not only the treatment time is shortened but also the amount of tooth cutting or the loss of teeth can be reduced, a composition imparted with remineralization ability is desired.

  An object of this invention is to provide the dental material used for dentistry. More specifically, it has excellent adhesive curability when used as a dental caries and wear restoration, a dental caries preventive filler, etc., and calms symptoms such as external irritation and pain to the pulp after curing adhesion, An object of the present invention is to provide a dental material, a dental composition, a dental adhesive, and a bioadhesive capable of preventing and protecting the tooth quality.

  Another object of the present invention is to provide a remineralization promoting material. More specifically, an object of the present invention is to provide a remineralization promoting material that has a remineralization ability for hard tissues such as dentin and can be used for adhesion of oral tissues and the like.

  A further object of the present invention is to provide a caries detection material for detecting caries.

In the dental material of the present invention, the acidic group of the monomer (A) having a polymerizable group in the molecule and at least one acidic group selected from the group consisting of a carboxylic acid group and a phosphoric acid group is substantially formed by calcium. Fully neutralized monomeric calcium salt (S _A )
And / or polymer of a polymerizable monomer containing a monomer (A) having a polymerizable group in the molecule and at least one acidic group selected from the group consisting of a carboxylic acid group and a phosphoric acid group (P And the acidic group contains a polymer calcium salt (S _P ) substantially completely neutralized with calcium.

Moreover, the dental composition of this invention is comprised from (B)-(D) as described below.
(B) Monofunctional (meth) acrylate: 90 to 99 parts by weight (provided that the total of (B) and (C) is 100 parts by weight),
(C) Polymerizable monomer having at least one acidic group in the molecule: 1 to 10 parts by weight (provided that the total of (B) and (C) is 100 parts by weight),
(D) 0.5 to 300 parts by weight of a filler composed of the monomeric calcium salt (S _A ) and / or the polymer calcium salt (S _P ) (however, the total of (B) and (C) above is 100) Ratio to parts by weight).

Furthermore, the dental adhesive or the biological adhesive of the present invention is characterized by comprising the above-mentioned dental composition.
The remineralization promoting material of the present invention is characterized by comprising the above-mentioned dental composition.

  Furthermore, the caries detecting material of the present invention is characterized by comprising the above-mentioned dental composition.

By using the dental material of the present invention as a filler for a dental adhesive or a bioadhesive, an adhesive having excellent adhesive performance can be obtained without impairing operability.
In addition, the dental material and the dental composition of the present invention can be used as a remineralization promoting material to supply recalcification by supplying calcium to the surrounding hard tissue, for example, the tooth structure. The remineralization promoting material also has excellent adhesiveness.

  Furthermore, the dental composition can be used as a detection material for detecting caries.

  Hereinafter, the dental material, the dental composition, the dental adhesive, the remineralization promoting material, the living body adhesive, and the caries detection material of the present invention will be specifically described. Hereinafter, “part” and “%” indicate a weight basis unless otherwise indicated.

The dental material of the present invention has an effect of promoting remineralization around the affected area when used on a tooth or a living body.
Furthermore, the dental composition of the present invention is applied when performing a repair treatment of hard tissue represented by a tooth, and is polymerized at the application site, thereby providing a dental metal, a dental composite resin, and a dental hard resin. Or, it becomes an adhesive with a restoration material typified by bone cement and the like, and also has an effect of supplying a calcium component to the application site and promoting remineralization around the application site.

In the dental material of the present invention, the acidic group of the monomer (A) having a polymerizable group in the molecule and at least one acidic group selected from the group consisting of a carboxylic acid group and a phosphoric acid group is substantially formed by calcium. Monomeric calcium salt (S _A ) that is completely neutralized
Or a polymer (P) of a polymerizable monomer containing a monomer (A) having a polymerizable group and at least one acidic group selected from the group consisting of a carboxylic acid group and a phosphoric acid group in the molecule. A polymer calcium salt ( _SP ) in which the acidic group is substantially completely neutralized by calcium
Containing. The dental material of the present invention may contain both the monomeric calcium salt (S _A ) and the polymer calcium salt (S _P ), or may contain either one of them. Good.

The monomer calcium salt (S _A ) or polymer calcium salt (S _P ) contained in the dental composition of the present invention gradually releases calcium in a living body typified by the oral cavity. This encourages the surrounding tissue to remineralize.

The monomeric calcium salt (S _A ) used in the present invention has a polymerizable group in the molecule and at least 1
It is a polymerizable monomer in which the acidic group of the monomer (A) having two acidic groups is substantially completely neutralized with calcium.

In addition, the polymer calcium salt (S _P ) used in the present invention is a polymer monomer having a polymerizable group and at least one acidic group (A) in the molecule. It is a calcium salt of the union (P), and acidic groups present in this polymer are substantially completely neutralized by calcium.

Here, the acidic group is a carboxylic acid group and / or a phosphoric acid group.
In the present invention, “substantially completely neutralized” means that the gram equivalent of the acid of the acidic group which is the carboxylic acid group or phosphate group is substantially equal to the gram equivalent of calcium. It means being in a state. Here, gram equivalent means a value obtained by multiplying the number of moles by the valence of an acid (or base). That is, the number of moles of H ⁺ (or OH ⁻ ) that the acid (or base) can release to neutralization. In addition, when a weak acid such as a carboxylic acid group or a phosphoric acid group is neutralized with calcium, which is strongly basic, the pH value does not become 7 even when strictly neutralized strictly, and tends to be slightly inclined toward the alkali side. .

  In the present invention, the ratio of the calcium base gram equivalent due to the acid group calcium salt in the dental material or dental composition to the acid group acid gram equivalent (calcium base gram equivalent / acid gram equivalent) is preferably Is 0.5 to 2.0 [gram equivalent / gram equivalent], more preferably 0.7 to 1.5 [gram equivalent / gram equivalent], and still more preferably 0.8 to 1.2 [gram equivalent / gram equivalent]. ] Within the range. If the lower limit of the numerical range is not reached, the amount of calcium released will be reduced, and it may be substantially impossible to contribute to remineralization. The physical properties of the may decrease.

In the present invention, “caused” refers to a case where, for example, almost all calcium present in a dental material or dental composition originates from a calcium salt that is substantially completely neutralized. The gram equivalent of both the acidic group present in the raw material (for example, (D)) and the calcium present in the dental material or the whole composition (including other materials (including the composition matrix)) is substantially neutralized. The origin of calcium ions is not necessarily limited to the calcium salt.

Such a substantially completely neutralized calcium salt is produced by reacting the monomer (A) or polymer (P) with a calcium compound such as Ca (OH) ₂ in substantially the same gram equivalent. Can do. This neutralization reaction may be a reaction form in which the monomer (A) or the polymer (P) can react with the calcium compound, and is usually reacted in the presence of an aqueous medium such as water and reacted after the reaction. It is preferable to remove the solvent as appropriate by, for example, distillation, filtration, membrane separation or the like. Furthermore, it is preferable to wash the produced calcium salt with an aqueous solvent such as water or ethanol. When using such a washed calcium salt, the remaining solvent used for the washing is actively removed. It is preferable to use it. The content of the calcium salt contained in the product thus purified is preferably 40 to 100%, more preferably 60 to 100%, still more preferably 80 to 100%. The components other than the calcium salt contained in such a product are usually water or an aqueous solvent used as a reaction solvent during the reaction, and the content of such components other than the calcium salt is preferably It is 0-5%, More preferably, it is 0-4%, More preferably, it is 0-2%.

  If the calcium salt is prepared by appropriately managing the pH value, the loss of calcium is extremely small, and the charged amount can be regarded as the product composition (acid-base gram equivalent ratio). If necessary, the pH value of the removed solvent or washing solution or the pH value of the product may be measured and confirmed.

  In the present invention, a radical polymerizable group is preferably used as the polymerizable group present in the molecule of the monomer (A). Examples of these polymerizable groups include vinyl groups, vinyl cyanide groups, acryloyl groups. Groups, methacryloyl groups, acrylamide groups, methacrylamide groups and the like.

And in this invention, as an acidic group which exists in a molecule | numerator, a carboxyl group, its acid anhydride group, a phosphoric acid group, a thiophosphoric acid group etc. can be illustrated.
In the present invention, when the acidic group is a carboxyl group as the monomer (A) having a polymerizable group and at least one acidic group in the molecule, a monocarboxylic acid compound, dicarboxylic acid compound, tricarboxylic acid Acid compounds, tetracarboxylic acid compounds and polycarboxylic acid compounds can be used.

Therefore, in the present invention, examples of specific compounds that can be used as the monomer (A) having a polymerizable group and at least one acidic group in the molecule include (meth) acrylic acid (hereinafter referred to as “(meth) acrylic acid”). , Described as a generic term for acrylic acid and (meth) acrylic acid.), Α-unsaturated carboxylic acids such as maleic acid;
Carboxylic acids to which vinyl aromatic rings such as 4-vinylbenzoic acid are added;
Between a (meth) acryloyloxy group and a carboxylic acid group such as 11- (meth) acryloyloxy-1,1-undecanedicarboxylic acid (hereinafter referred to as (meth) acryloyl as a generic term for acryloyl and methacryloyl). A carboxylic acid in which a linear hydrocarbon group is present;
Carboxylic acids having an aromatic ring such as 1,4-di (meth) acryloyloxyethyl pyromellitic acid, 6- (meth) acryloyloxyethyl naphthalene-1,2,6-tricarboxylic acid;
4- (meth) acryloyloxyalkyl trimellitic acid such as 4- (meth) acryloyloxymethyl trimellitic acid, 4- (meth) acryloyloxyethyl trimellitic acid, 4- (meth) acryloyloxybutyl trimellitic acid, etc. ;
4- [2-hydroxy-3- (meth) acryloyloxy] butyl trimellitic acid and the like carboxylic acid having a hydrophilic group such as a hydroxyl group on the alkyl chain;
2,3-bis (3,4-dicarboxybenzoyloxy) propyl (meth) acrylate
A compound having carboxybenzoyloxy such as (to be described as a generic term for acrylate and methacrylate hereinafter);
N- and / or O-mono such as N, O-di (meth) acryloyloxytyrosine, O- (meth) acryloyloxytyrosine, N- (meth) acryloyloxytyrosine, N- (meth) acryloyloxyphenylalanine and the like Or di (meth) acryloyloxyamino acid;
N- (meth) acryloylaminobenzoic acid such as N- (meth) acryloyl-4-aminobenzoic acid, N- (meth) acryloyl-5-aminobenzoic acid and the like;
2- or 3- or 4- (meth) acryloyloxybenzoic acid, 4- or 5- (meth) acryloylaminosalicylic acid, addition product of 2-hydroxyethyl (meth) acrylate and pyromellitic dianhydride, 2- Addition of hydroxyethyl (meth) acrylate and maleic anhydride or 3,3 ', 4,4'-benzophenone tetracarboxylic dianhydride or 3,3', 4,4'-biphenyltetracarboxylic dianhydride Addition reaction product of hydroxyalkyl (meth) acrylate and unsaturated polycarboxylic acid anhydride such as reactants;
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-[(2-hydroxy-3- (meth) acryloyloxypropyl) amino] phthalic acid;
Examples include 3- or 4- [N-methyl-N- (2-hydroxy-3- (meth) acryloyloxypropyl) amino] phthalic acid.

  Among these, 11- (meth) acryloyloxy-1,1-undecanedicarboxylic acid and 4- (meth) acryloyloxyethyl trimellitic acid are preferably used in the present invention.

  In the present invention, as the monomer (A) having a polymerizable group and at least one acidic group in the molecule, when the acidic group is a phosphate group, at least one in the molecule. Examples of the group in which the hydroxyl group is bonded to the phosphorus atom and the functional group that can be easily converted to the group in water include a compound having a phosphate ester group having a group having one or two hydroxyl groups. .

Therefore, as an example of a specific compound that can be used as the monomer (A) having a polymerizable group in the molecule and a phosphate group as at least one acidic group in the present invention,
2- (meth) acryloyloxyethyl acid phosphate, 2- and 3- (meth) acryloyloxypropyl acid phosphate, 4- (meth) acryloyloxybutyl acid phosphate, 6- (meth) acryloyloxyhexyl acid phosphate, 8- ( (Meth) acryloyloxyalkyl acyl phosphate, such as (meth) acryloyloxyoctyl acid phosphate, 10- (meth) acryloyloxydecyl acid phosphate, 12- (meth) acryloyl oxide decyl acid phosphate;
(Meth) acryloyloxyalkyl groups such as bis [2- (meth) acryloyloxyethyl] acid phosphate, bis [2- or 3- (meth) acryloyloxypropyl] acid phosphate and the like are aromatic rings such as phenylene groups and further Is an acid phosphate having a heteroatom such as an oxygen atom;
(Examples include 2- (meth) acryloyloxyethylphenyl acid phosphate, 2- (meth) acryloyloxyethyl-p-methoxyphenyl acid phosphate, and other acid phosphates having two or more (meth) acryloyloxyalkyl groups). A compound in which the phosphate group in these compounds is replaced with a thiophosphate group can also be exemplified, among which 2- (meth) acryloyloxyethyl acid phosphate can be preferably used.

These monomeric calcium salts having an acidic group are generally poorly water-soluble, and these are used in polymerization alone or in combination of two or more.
Further, the calcium salt (S) may contain other components (T) other than the above in the form of mixing or copolymerization. The other component (T) is preferably a monomer or polymer having no acidic group, such as a monofunctional (meth) acrylate (B) described later or a polymer thereof. Or (C) a polymerizable monomer having at least one acidic group (excluding a carboxyl group and a phosphate group) in the molecule (described later), and an acidic group other than such a carboxylic acid group or a phosphate group It may be a polymerizable monomer having or a polymer thereof. The ratio of the other component (T) included is the component having no acidic group as described above (T _B
), The ratio of the calcium salt (S) to the total of 100 parts by weight of the component (T _B ) having no acidic group is usually 0.5 parts by weight or more, preferably 1 It is preferable to use at least 2 parts by weight, more preferably at least 2 parts by weight.

Moreover, when the dental material of this invention contains the component (Tc) which has the above acidic groups, with respect to a total of 100 weight part of the component (Tc) which has an acidic group, calcium salt ( The ratio of S) is usually 70 parts by weight or more, preferably 80 parts by weight or more, and further 90 parts by weight or more. In addition, it is preferable that the component (Tc) which has an acidic group is substantially completely neutralized with calcium.

  The ratio of the calcium element (Ca) contained in the calcium salt (S) is preferably 0.05 to 26%, more preferably 0.1 to 22%, and still more preferably 0.2 to 19%. If the value is below the lower limit of the numerical range, the calcium releasing ability tends to be excessive, whereas if the value exceeds the upper limit, sufficient physical properties may not be exhibited.

In the dental material of the present invention, the calcium salt gradually releases calcium ions in a living body represented by the oral cavity and promotes remineralization of surrounding tissues. Further, this calcium salt (S _A ) is copolymerized with (B) and / or (C) described later to form a cured body, thereby not only becoming an adhesive for a restoration material, but also calcium around the application site. A source of supply.

Next, the dental composition of the present invention will be described.
The dental composition of the present invention comprises a monofunctional (meth) acrylate (B), a polymerizable monomer (C) having at least one acidic group in the molecule, and a filler (D). And in the dental composition of this invention, the filler (D) which consists of said monomer calcium salt (S _A ) and / or polymer calcium salt (S _P ) is used as a filler (D). It is preferable.

The monofunctional (meth) acrylate (B) constituting the dental composition of the present invention is usually a monomer having no acidic group, such as methyl (meth) acrylate, ethyl (meth). Alkyl (meth) acrylates such as acrylate, n-propyl (meth) acrylate, n-butyl (meth) acrylate;
Hydroxyalkyl (meth) acrylates such as 2-hydroxyethyl (meth) acrylate and 3-hydroxypropyl (meth) acrylate;
Alkyl poly (oxyalkanediyl) (meth) acrylates such as methylbis (oxy-2,1-ethanediyl) (meth) acrylate and methyltetra (oxy-2,1-ethanediyl) (meth) acrylate;
Acetoacetoxyethyl (meth) acrylate;
Cycloalkyl (meth) acrylates such as cyclobutyl (meth) acrylate and cyclohexyl (meth) acrylate;
Cyclic alkyl (meth) acrylates containing heteroatoms such as (tetrahydrofuran-2-yl) (meth) acrylate;
Fluoroalkyl esters of (meth) acrylic acid such as perfluorooctyl (meth) acrylate and hexafluoro (meth) acrylate;
Examples thereof include silane compounds having a (meth) acryloxyalkyl group such as 3- (trimethoxysilyl) propane (meth) acrylate. These monomers are used for polymerization alone or in combination of two or more.

  Further, in order to obtain a high adhesion to hard tissues such as teeth, a low molecular weight monomer, for example, a low molecular weight monomer having a molecular weight of 300 or less is useful for diffusing the monomer to the adhesion interface with the tooth, etc. Examples of the low molecular weight monomer include methyl methacrylate, ethyl methacrylate, propyl methacrylate, and ethylene glycol monomethyl ether (meth) acrylate. In the present invention, such a low molecular weight monomer can also be used as the monofunctional (meth) acrylate (B).

In particular, in the present invention, as the monofunctional (meth) acrylate (B), a methacrylate having a relatively low irritation to the human body is particularly preferably used.
The monofunctional (meth) acrylate (B) in the composition of the present invention is the total amount of the monofunctional (meth) acrylate (B) and the polymerizable monomer (C) having an acidic group forming the dental composition of the present invention. It is contained in 100 parts by weight in an amount in the range of 90 to 99 parts by weight, preferably in an amount in the range of 91 to 98 parts by weight, particularly preferably in an amount in the range of 92 to 97 parts by weight. This monofunctional (meth) acrylate (B) is a monomer serving as a basis for expressing the excellent properties of the recalcification accelerator of the present invention, and is used within the above range for the dental use of the present invention. Basic characteristics regarding the physical properties of the composition are established.

The polymerizable monomer (C) having at least one acidic group in the molecule constituting the dental composition of the present invention is a compound having an acidic group and an unsaturated double bond in the same molecule.
By incorporating a polymerizable monomer having at least one acidic group in the molecule (acidic group-containing polymerizable monomer) (C), the monomer component in the dental composition of the present invention High adhesion strength is expressed between the tooth and bone and other hard tissues.

  Examples of the acidic group-containing polymerizable monomer (C) that can be used in the present invention include a sulfonic acid group-containing polymerizable monomer, a carboxyl group-containing polymerizable monomer, and a phosphoric acid group-containing polymerizable monomer. The acidic group-containing polymerizable monomer is not neutralized by calcium.

  As the sulfonic acid-containing polymerizable monomer that can be used as the acidic group-containing monomer (C) in the present invention, in addition to the polymerizable monomer examples containing a sulfonic acid group, A polymerizable monomer having a functional group that can be easily converted can also be used.

Examples of such sulfonic acid group-containing polymerizable monomers include:
Sulfoalkyl (meth) acrylates such as 2-sulfoethyl (meth) acrylate, 2- or 1-sulfo-1- or 2-propyl (meth) acrylate, 1- or 3-sulfo-2-butyl (meth) acrylate, etc. ;
A part of the alkyl chain such as 3-bromo-2-sulfo-2-propyl (meth) acrylate, 3-methoxy-1-sulfo-2-propyl (meth) acrylate and the like may contain a halogen atom or an oxygen atom. A compound having an atomic group containing a heteroatom;
2-((meth) acrylamide) propane-2-sulfonic acid and other compounds that are acrylamide instead of the acrylate;
Furthermore, vinyl aryl sulfonic acids such as 4-styrene sulfonic acid, 4- (prop-1-en-2-yl) benzene sulfonic acid and the like can be mentioned.

These sulfonic acid group-containing polymerizable monomers can be used alone or in combination. Of these, 4-styrenesulfonic acid can be preferably used.
Examples of the carboxyl group-containing polymerizable monomer that can be used as the acidic group-containing polymerizable monomer (C) in the present invention include (meth) acrylic acid (hereinafter, a generic term for acrylic acid and (meth) acrylic acid). Described as above), α-unsaturated carboxylic acids such as maleic acid;
Carboxylic acids to which vinyl aromatic rings such as 4-vinylbenzoic acid are added;
11- (Meth) acryloyloxy-1,1-undecanedicarboxylic acid (hereinafter referred to as (meth) acryloyl as a generic term for acryloyl and methacryloyl) and the like between a (meth) acryloyloxy group and a carboxylic acid group A carboxylic acid in which a linear hydrocarbon group is present;
Carboxylic acids having an aromatic ring such as 1,4-di (meth) acryloyloxyethyl pyromellitic acid, 6- (meth) acryloyloxyethyl naphthalene-1,2,6-tricarboxylic acid;
4- (meth) acryloyloxyalkyl trimellitic acid such as 4- (meth) acryloyloxymethyl trimellitic acid, 4- (meth) acryloyloxyethyl trimellitic acid, 4- (meth) acryloyloxybutyl trimellitic acid, etc. ;
A carboxylic acid having a hydrophilic group such as a hydroxyl group on an alkyl chain such as 4- [2-hydroxy-3- (meth) acryloyloxy] butyl trimellitic acid;
A compound having carboxybenzoyloxy such as 2,3-bis (3,4-dicarboxybenzoyloxy) propyl (meth) acrylate (hereinafter referred to as a generic name of acrylate and methacrylate) and the like;
N- and / or O-mono such as N, O-di (meth) acryloyloxytyrosine, O- (meth) acryloyloxytyrosine, N- (meth) acryloyloxytyrosine, N- (meth) acryloyloxyphenylalanine and the like Or di (meth) acryloyloxyamino acid;
2- or 3- or 4- (meth) acryloyloxybenzoic acid, 4- or 5- (meth) acryloylaminosalicylic acid, N- (meth) acryloyl-4-aminobenzoic acid, N- (meth) acryloyl-5 A (meth) acryloyl compound of benzoic acid having a functional substituent such as aminobenzoic 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 dianhydride 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-[(2-hydroxy-3- (meth) acryloyloxypropyl) amino] phthalic acid;
3 or 4- [N-methyl-N- (2-hydroxy-3- (meth) acryloyloxypropyl) amino] phthalic acid.

Of these, 11- (meth) acryloyloxy-1,1-undecanedicarboxylic acid and 4- (meth) acryloyloxyethyl trimellitic acid are preferably used.
Examples of the phosphoric acid group-containing polymerizable monomer that can be used as the acidic group-containing polymerizable monomer (C) in the present invention include a group in which at least one hydroxyl group is bonded to a phosphorus atom and the group easily in water. A polymerizable monomer having a functional group that can be converted into a group can be used. Here, as a functional group that can be easily converted into the group in water, for example, a phosphate ester group having one or two hydroxyl groups can be preferably exemplified.

Examples of such phosphate group-containing polymerizable monomers include:
2- (meth) acryloyloxyethyl acid phosphate, 2- and 3- (meth) acryloyloxypropyl acid phosphate, 4- (meth) acryloyloxybutyl acid phosphate, 6- (meth) acryloyloxyhexyl acid phosphate, 8- ( (Meth) acryloyloxyalkyl acyl phosphate, such as (meth) acryloyloxyoctyl acid phosphate, 10- (meth) acryloyloxydecyl acid phosphate, 12- (meth) acryloyl oxide decyl 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 and the like;
Aromatic rings such as 2- (meth) acryloyloxyethylphenyl acid phosphate, 2- (meth) acryloyloxyethyl-p-methoxyphenyl acid phosphate, etc., and phenylene groups, and oxygen atoms And acid phosphates having a heteroatom such as Moreover, as a phosphate group containing polymerizable monomer used by this invention, the compound which replaced the phosphate group in the above compounds with the thiophosphate group can also be illustrated. Among these, 2- (meth) acryloyloxyethyl acid phosphate can be preferably used in the present invention.

  When such an acidic group-containing polymerizable monomer (C) is used, the acidic group present in the acidic group-containing polymerizable monomer (C) is used in a form that is not neutralized by calcium or the like. The In particular, in the present invention, it is preferable to use a sulfonic acid group-containing polymerizable monomer as the acidic group-containing polymerizable monomer (C).

  In the dental composition of the present invention, the polymerizable monomer (C) containing an acidic group in the molecule comprises a monofunctional (meth) acrylate (B) and an acidic group constituting the dental composition of the present invention. In a total amount of 100 parts by weight of the polymerizable monomer (C) having an amount of 1 to 10 parts by weight, preferably 2 to 9 parts by weight, particularly preferably 3 to 8 parts by weight. Can be used in amounts within the range. By using the polymerizable monomer (C) containing an acidic group in the molecule in such an amount, the dental adhesive composition of the present invention is a hard material represented by a dentine as an adherend. Good adhesion to tissue is exhibited.

The total amount of the monofunctional (meth) acrylate (B) and the polymerizable monomer (C) having at least one acidic group in the molecule in the dental composition of the present invention is the same as that of the dental composition of the present invention. The amount is usually 13 to 99.5 parts by weight, preferably 16 to 99 parts by weight, and more preferably 20 to 98.5 parts by weight with respect to 100 parts by weight. When these are less than 13 parts by weight below the lower limit, the operability of the composition is remarkably inferior, and microleakage is a concern. If the upper limit of 99.5 parts by weight is exceeded, there is a concern that the remineralization promoting effect will be reduced.

The filler (D) contained in the dental composition of the present invention has a single group having a polymerizable group and at least one acidic group selected from the group consisting of a carboxylic acid group and a phosphoric acid group in the molecule. Monomeric calcium salt (S _A ) in which the acidic group of the monomer (A) is substantially completely neutralized by calcium
And / or polymer of a polymerizable monomer containing a monomer (A) having a polymerizable group in the molecule and at least one acidic group selected from the group consisting of a carboxylic acid group and a phosphoric acid group (P And a dental material comprising a polymeric calcium salt (S _P ) in which the acidic groups are substantially completely neutralized with calcium.

In the present invention, both can be used alone or in combination as the filler (D).
In the dental composition of the present invention, the filler (D) is a total of 100 of the monofunctional (meth) acrylate (B) and the polymerizable monomer (C) having at least one acidic group in the molecule. The amount is usually 0.5 to 300 parts by weight, preferably 1 to 210 parts by weight, and more preferably 2 to 150 parts by weight with respect to parts by weight.

Incidentally, when using the acidic group is a carboxylic acid group the polymer calcium salt (S _P), the polymer calcium salt (S _P) is a cured product of the dental composition of the present invention by a copolymer preferably the mechanical properties are improved, also, the polymer calcium salt in acidic group is to use the polymer calcium salt is phosphoric acid group (S _P) (S _P) is the present invention by keeping the homopolymer Since the mechanical property of the hardened | cured material of this dental composition improves, it is preferable.

  When the dental composition of the present invention is used as a remineralization promoting material, in order to reduce the film thickness formed by the remineralization promoting material and further improve the restoration effect, The average particle diameter is preferably in the range of 0.001 to 30 μm, and more preferably in the range of 0.01 to 25 μm.

  In addition, although said example has mainly shown the aspect which used calcium salt (S) as a filler, unless it obstruct | occludes the effect of invention, using suitable surfactant etc., calcium salt (S ) And monofunctional (meth) acrylate (B) or the like are emulsified and mixed to form an emulsion, and the filler (C) can be used as an emulsion of monofunctional (meth) acrylate (B) or the like.

  In the dental composition of the present invention, in addition to the filler (D) as described above, a filler (D ′) usually used for dentistry can be used. The filler (D ′) used here is not particularly limited as long as it is a filler normally used for dentistry, and a known organic filler, inorganic filler, or inorganic-organic composite filler is used. be able to.

  As an example of the organic filler which is the filler (D ′) in the present invention, substantially non-crosslinked (meth) acrylate polymer particles containing 70% or more of (meth) acrylate component units are preferably used.

As an example of the monomer constituting this (meth) acrylate component unit,
Mention may be made of (meth) acrylate monomers such as methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, cyclohexyl (meth) acrylate and benzyl (meth) acrylate. Examples of monomers other than such (meth) acrylate monomers include vinyl acetate, vinyl pyrrolidone, maleic anhydride, maleic acid, and vinyl benzoic acid. These can be used alone or in combination.

  Moreover, the (meth) acrylate polymer of this invention can copolymerize a small amount of crosslinking | crosslinked monomers as needed. Examples of the crosslinkable monomer include polyfunctional monomers such as ethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, and butadiene.

The weight average molecular weight of the (meth) acrylate polymer particles suitably used as the filler (D ′) in the present invention is preferably in the range of 50,000 to 300,000.
In the present invention, these organic fillers can be used alone or in combination.

Examples of the inorganic filler used as the filler (D ′) component in the present invention include metal oxide powders such as zirconium oxide, bismuth oxide, titanium oxide, zinc oxide and aluminum oxide particles, calcium carbonate, Metal salt powder such as bismuth carbonate, calcium phosphate, zirconium phosphate and barium sulfate, silica glass, aluminum-containing glass, barium-containing glass, strontium-containing glass and zirconium silicate glass and other glass fillers, silver sustained-release filler, fluorine gradual Examples thereof include releasable fillers. These inorganic fillers can be used alone or in combination.

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 the filler (D ′) that can be used in the present invention include inorganic and organic composite fillers containing the above inorganic filler and / or organic filler. As the inorganic / organic composite filler, it is possible to use a TMPT filler or the like pulverized after mixing and polymerizing trimethylolpropane methacrylate and silica filler.

These organic fillers, inorganic fillers, and inorganic-organic composite fillers can be used alone or in combination.
In the dental composition of the present invention, as the filler (D ′), in order to reduce the film thickness of the dental composition and further improve the restoration effect, the average particle diameter is 0.001 to 0.001. 30μ
It is preferable to use particles in the range of m, and it is particularly preferable to use particles in the range of 0.01 to 25 μm.

In the dental composition of the present invention, the filler (D ′) has at least one acidic group in the monofunctional (meth) acrylate (B) and molecules forming the dental composition of the present invention. Usually in the range of 0.4 to 300 parts by weight, preferably 0.5 to 250 parts by weight, more preferably 0.7 to 210 parts by weight with respect to 100 parts by weight of the total amount of the polymerizable monomers (C). Can be used in any amount.

In the embodiment using (D) as a filler, the calcium content contained in the total amount of component (B), component (C), component (D) and (D ′) is usually 0.005 to 0.005. It is preferable to adjust the amounts of the component (D) and the component (D ′) so as to be 10%, preferably 0.01 to 9%, more preferably 0.02 to 8%. If the value falls below the lower limit of the numerical range, the calcium releasing ability becomes too small to exert the effects of the invention, and if the value exceeds the upper limit, the physical properties of the cured body are inferior and the performance cannot be exhibited at the same time. There is.

In particular, when the dental composition of the present invention is used as a remineralization promoting material, it is preferable to use the filler (D ′) in an amount within the above range.
Furthermore, the dental composition of the present invention has the above monofunctional (meth) acrylate compound (B), acidic group-containing polymerizable monomer (C), filler for improving physical properties and adjusting the curing time. (D) In addition to the normal filler (D ′), a polyfunctional radical polymerizable monomer (E) can be added if necessary.

As an example of the polyfunctional radical polymerizable monomer (E) used in the present invention,
Di (meth) acrylate of butanetriol such as glycerol di (meth) acrylate, 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;
A polyfunctional (meth) acrylate having 1 to 2 hydroxyl groups of hexanehexaol or a polyfunctional (meth) acrylate represented by the following chemical formula (1) can be exemplified.

In the above formula (1), R ¹ is a divalent aromatic residue having at least one aromatic ring or cyclic alkyl group and optionally having an oxygen atom or a sulfur atom in the molecule, preferably Any one selected from the following chemical formula (2) is shown, R ² and R ³ are hydrogen atoms or methyl groups, and n and m are positive integers.

  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 polyfunctional radical polymerizable monomer (E) is a monofunctional (meth) acrylate (B), a polymerizable monomer having an acidic group (C), and a polyfunctional radical polymerizable. In a total of 100 parts by weight of the monomer (E), it can be contained in an amount in the range of 1 to 35 parts by weight, preferably in an amount in the range of 1 to 20 parts by weight, most preferably 2 to 2 parts by weight. It can be contained in an amount within the range of 9 parts by weight. When the amount of the polyfunctional radical polymerizable monomer (E) is small, the effect of accelerating the curing rate is small, and when the amount of the polyfunctional radical polymerizable monomer (E) is large, the curing time is too short to treat. There is no room to properly apply the composition, 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. In particular, when the dental composition of the present invention is used as a remineralization accelerator, it is preferable to use the polyfunctional radical polymerizable monomer (E) in an amount within the above range.

An organoboron compound (F) can be blended with the dental composition of the present invention.
This organoboron compound (F) acts as a polymerization initiator for the polymer monomer contained in the dental composition of the present invention.

Examples of organoboron compounds (F) that can be used in the present invention include triethylboron, tri (n-propyl) boron, triisopropylboron, tri (n-butyl) boron, tri (s-butyl) boron, Tri (cyclo) alkyl boron such as triisobutyl boron, tripentyl boron, trihexyl boron, trioctyl boron, tridecyl boron, tridodecyl boron, tricyclopentyl boron, tricyclohexyl boron, butyl dicyclohexyl borane;
Alkoxyalkylboranes such as butoxydibutylboron; dialkylboranes such as diisoamylborane, 9-borabicyclo [3.3.1] nonane;
Aryl borate compounds such as tetraphenyl boron sodium, tetraphenyl boron triethanolamine salt, tetraphenyl boron dimethyl-p-toluidine salt, tetraphenyl boron dimethylaminoethyl benzoate;
Examples thereof include partially oxidized trialkylboron such as partially oxidized tributylboron. Among these, it is preferable to use tributyl boron or partially oxidized tributyl boron, and the most preferable organic boron compound is partially oxidized tributyl boron.

  The organoboron compound (F) blended in the dental composition of the present invention comprises the monofunctional (meth) acrylate (B) that forms the dental composition of the present invention, and a polymerizable monomer (C) having an acidic group. ) Is usually 0.5 to 10 parts by weight, preferably 1 to 10 parts by weight. In order to suitably balance the pot life and the curing time, the organoboron compound (F) is used in an amount within the above range.

In the dental composition of the present invention, an organic peroxide, an inorganic peroxide, or a redox metal compound can be blended as an auxiliary of the curing agent as necessary. 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. Mention may be made of '-dimethoxybenzoyl peroxide, p, p'-dimethylbenzoyl peroxide and p, p'-dinitrodibenzoyl peroxide. Examples of inorganic peroxides include ammonium persulfate, potassium persulfate, potassium chlorate, potassium bromate, and potassium perphosphate. Examples of the redox metal compound include nitrates of transition metals such as copper, iron and cobalt, carboxy salts such as chloride and acetylacetate. Among these, benzoyl peroxide (BPO), p, p′-dichlorobenzoyl peroxide (ClBPO), and acetylacetocopper are preferable.

  The amount of the organic peroxide, inorganic peroxide, or redox metal compound used as an auxiliary of the curing agent in the dental composition of the present invention is 0.1 of the amount of the organic boron compound (F) used. ~ 2 times the amount.

When the dental composition of the present invention is used as a remineralization accelerator, a photopolymerization initiator (G) may be blended unless the object of the present invention is impaired.
As the photopolymerization initiator (G) used in the present invention, those capable of initiating polymerization of a polymerizable monomer by irradiation with visible light are preferably used. For example, benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin Benzoins such as isopropyl ether; benzyl, 4,4′-dichlorobenzyl, diacetyl, α-cyclohexanedione, d, l-camphorquinone (CQ), camphorquinone-10-sulfonic acid, camphorquinone-10-carvone Α-diketones such as acids; diphenyl monoketones such as benzophenone, methyl benzoylbenzoate, hydroxybenzophenone; thioxanthones such as 2,4-diethylthioxanthone, 2-isopropylthioxanthone; 6-G It can be exemplified photosensitizers such as acylphosphine oxides, such as methyl benzoyl diphenyl phosphine oxide. These photopolymerization initiators can be used alone or in combination.

When the dental composition of the present invention is used as a remineralization accelerator, when a photopolymerization initiator is used, as the photopolymerization initiator, benzyl, 4,4′-dichlorobenzyl, diacetyl, α-diketones and acylphosphine oxides such as α-cyclohexanedione, d, l-camphorquinone (CQ), camphorquinone-10-sulfonic acid, camphorquinone-10-carboxylic acid and the like are preferably used. Among these, d, l-camphorquinone, camphorquinone-10-carboxylic acid, 2,4,6-trimethylbenzoyldiphenylphosphine oxide is particularly preferable.

  When a photopolymerization initiator is used in the present invention, the photopolymerization initiator is preferably used in an amount in the range of 0.1 to 10 parts by weight, when the amount of the organic boron compound (F) used is 100 parts by weight. Is used in an amount in the range of 0.2 to 5 parts by weight.

In order to improve the polymerization initiating effect of the photopolymerization initiator, a reducing compound that does not adversely affect the catalytic effect of the organic boron compound can be used in combination. For example, N, N-dimethylaniline, N, N-dimethyl-p-toluidine, N, N-diethyl-p-toluidine, N, N-diethanol-p-toluidine, N, N-dimethyl-pt-butyl Aniline, N, N-dimethylanisidine, N, N-dimethyl-p-chloroaniline, N, N-dimethylaminoethyl (meth) acrylate, N, N-diethylaminoethyl (meth) acrylate, N, N-dimethylamino Benzoic acid and alkyl esters thereof and salts thereof, N, N-diethylaminobenzoic acid and alkyl esters thereof and salts thereof, N, N-dimethylaminobenzaldehyde, N-phenylglycine and salts thereof, N-tolylglycine and salts thereof N, N- (3-methacryloyloxy-2-hydroxypropyl) pheny It can include organic reducing compound such as glycine and salts thereof.

The compounding amount of the reducing compound is usually in the range of 0.5 to 3.0 times the amount of photopolymerization initiator used.
A substance (H) capable of supplying fluorine ions in water may be added to the dental composition of the present invention. As the substance (H) capable of supplying fluorine ions in water, any substance 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., among which sodium fluoride, calcium fluoride, sodium monofluorophosphate, The use of stannous fluoride is preferred. 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 using the substance (H) capable of supplying fluorine ions in water, an effect of improving the acid resistance of the hard tissue can be expected. In the present invention, the component (H) is preferably in the range of 0.0001 to 5%, more preferably 0.001 to 2%, and particularly preferably 0.01 to 1% as the fluorine ion concentration in the composition. If it is less than 0.0001%, 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%, there is a concern about harm to the living body.

  When the dental composition of the present invention is used as a remineralization accelerator, a solvent or a dispersion medium can be used as desired. The solvent or dispersion medium that can be used here is not particularly limited as long as it has no possibility of harm in vivo, and examples of such a solvent or dispersion medium include ethanol, acetone, Water etc. can be mentioned. These solvents or dispersion media can be used alone or in combination of two or more.

  When the dental composition of the present invention is used as a remineralization accelerator, a thickener can be used as desired. Examples of the thickener used here include polyethylene glycol, polypropylene glycol, carboxymethyl cellulose and the like in addition to the fillers mentioned as the polyfunctional radical polymerizable monomer (E). These thickeners can be used alone or in combination of two or more.

  If desired, the dental composition of the present invention can be used in combination with a dye and / or a pigment. Examples of dyes and / or pigments that can be used here include Phloxine BK, Acid Red, Fast Acid Magenta, Phloxine B, Fast Green FCF, Rhodamine B, basic fuchsin, acidic fuchsin, eosin, ethysulosin, safranin, Examples include rose bengal, bemel, gentian purple, copper chlorophyll soda, lacqueric acid, sodium fluorescein, cochineal and perilla, talc, titanium white and the like. These dyes and / or pigments can be used alone or in combination of two or more.

The dental composition of the present invention comprises
(1) The filler (D) composed of the calcium salt (S) is suspended in an appropriate solvent or dispersion medium to form a primer or liner composition, which is directly applied to the application site using a brush or the like, and is solvent-coated with an air gun. Or a method of evaporating the dispersion medium,
(2) Filler (D) made of the above calcium salt (S), suitable monofunctional (meth) acrylate (B), acidic group-containing polymerizable monomer (C), polyfunctional (meth) acrylate (E) A combination of the polymerizable monomers listed in the above to obtain a primer or liner composition, which is applied directly to the application site, the excess polymerizable monomer is evaporated by an air gun, and the application site is modified,
(3) Monofunctional (meth) acrylate (B), acidic group-containing polymerizable monomer (C), filler (D) made of calcium salt, polyfunctional (meth) acrylate (E), organoboron compound ( F) is combined and mixed to prepare a curable dental composition, and this dental composition is applied directly to the application site and cured, or used as an adhesive. be able to.

  The dental composition of the present invention can be used as a remineralization promoting material as described above, and as a dental adhesive, for adhesion of dental metals, dentures, dental fillings, or for living organisms. As an adhesive, it can also be used for bonding bones and the like.

Further, the dental composition of the present invention can be used as a caries detection material by being blended in a caries detection liquid described in, for example, JP-A-56-967000.
That is, the caries detection material of the present invention is prepared by dissolving or dispersing a dye typified by acid red, basic fuchsin, or fluorescein in water, a solvent typified by polyethylene glycol or a dispersion medium, and a filler ( It consists of a solution in which D) is dissolved or a dispersed dispersion.

  Apply this solution or dispersion to the suspected caries infection site, remove the excess composition with water, stain the caries infected area, and visually detect the caries area by observing the stained state. Can do. Furthermore, according to the caries detection material of the present invention, remineralization of the application portion can be promoted.

EXAMPLES Hereinafter, although the Example of this invention is shown and this invention is demonstrated further in detail, this invention is not limited by these Examples.
[Production Example 1 of calcium salt]
4.19 g (0.01 mol) of 4-methacryloxyethyl trimellitic acid (hereinafter referred to as 4-MET) and 64 g of ethanol are charged into a reactor equipped with a stirrer, a condenser, a thermometer, and a dropping funnel. The mixture was stirred while cooling the internal temperature to 10 ° C.

To this solution, an aqueous solution in which 0.74 g (0.01 mol) of calcium hydroxide was dissolved in 400 g of distilled water was added dropwise over 30 minutes while maintaining the internal temperature at 10 ° C. or lower, and further aged for 30 minutes at room temperature. The obtained reaction mass was concentrated, filtered, washed with ethanol, and dried to obtain 3.34 g of a colorless powder.

  As a result of NMR analysis and elemental analysis, the obtained colorless powder was confirmed to be a calcium salt of 4-MET. The obtained calcium salt of 4-MET was further pulverized with a planetary ball mill and classified with a # 280 sieve to obtain a dental material usable as a filler.

The acid-base gram equivalent ratio (calcium base gram equivalent / acid gram equivalent) of the obtained product was 1.0 [gram equivalent / gram equivalent].
[Production Example 2 of calcium salt]
In a reactor equipped with a stirrer, a condenser, a thermometer, and a dropping funnel, 21.0 g (0.1 mol) of 2-methacryloxyethyl acid phosphate and 250 g of ethanol
And stirred while cooling the internal temperature to 5 ° C. An aqueous solution in which 7.41 g (0.1 mol) of calcium hydroxide was dissolved in 700 g of distilled water was added dropwise over 90 minutes while maintaining the internal temperature at 10 ° C. or lower, and further aged while maintaining the temperature for 2 hours.

The obtained reaction mass was concentrated, filtered, washed with ethanol, and dried to obtain 21.9 g of a colorless powder.
As a result of NMR analysis and elemental analysis, the obtained colorless powder was confirmed to be a calcium salt of 2-methacryloxyethyl acid phosphate.

The obtained calcium salt of 2-methacryloxyethyl acid phosphate was further pulverized with a planetary ball mill and classified with a # 280 sieve to obtain a dental material usable as a filler.
The acid-base gram equivalent ratio (calcium base gram equivalent / acid gram equivalent) of the obtained product was 1.0 [gram equivalent / gram equivalent].
[Production Example 3 of calcium salt]
A reactor equipped with a stirrer, condenser, thermometer, nitrogen inlet, and dropping funnel was charged with 40 g of distilled water and 0.4 g of potassium persulfate, and after bubbling with nitrogen for 15 minutes, the internal temperature was raised to 75 ° C. did.

To this reactor, 76 g of methyl methacrylate and 4 g of 4-MET (0.012 mol)
Then, 0.4 g of an emulsified solution consisting of 0.6 g of sodium dodecyl sulfate and 76 g of distilled water was added and slowly stirred.

After 30 minutes, the remainder of the emulsified solution was dropped from the dropping funnel over 3 hours, and polymerization was continued for another 4 hours while maintaining the temperature.
Next, the internal temperature was cooled to room temperature, and a solution prepared by dissolving 0.92 g (0.012 mol) of calcium hydroxide in 500 g of distilled water was added dropwise over 1 hour and aged for 3 hours.

The obtained reaction mass was washed and dried with 1000 ml of distilled water while passing through an ultrafiltration membrane (manufactured by Sanko Junyaku Co., Ltd .; ultramolecular weight 10,000) to obtain 77 g of colorless powder.
As a result of NMR analysis, IR analysis, and elemental analysis, the obtained colorless powder was confirmed to be a calcium salt of a methacrylate polymer.

The calcium salt of the methacrylate polymer was further pulverized with a planetary ball mill and classified with a # 280 sieve to obtain a dental material that could be used as a filler.
The acid-base gram equivalent ratio (calcium base gram equivalent / acid gram equivalent) of the obtained product was 1.0 [gram equivalent / gram equivalent].
[Production Example 4 of calcium salt]
A reactor equipped with a stirrer, a condenser, a thermometer, a nitrogen inlet, and a dropping funnel was charged with 30 g of acetone, 0.08 g of N, N-azobisisobutyronitrile, and 15 g (0.047 mol) of 4-MET. After nitrogen bubbling for 15 minutes, the internal temperature was raised to 50 ° C. for polymerization, and polymerization was continued for 8 hours while maintaining the temperature.

Next, the internal temperature was cooled to room temperature, and a solution prepared by dissolving 3.45 g (0.047 mol) of calcium hydroxide in 500 g of distilled water was added dropwise over 1 hour, followed by aging for 3 hours.
The obtained reaction mass was discharged into a large excess of methanol, filtered, washed with acetone and dried to obtain 17 g of colorless powder.

As a result of NMR analysis, IR analysis, and elemental analysis, this inorganic powder was confirmed to be a calcium salt of 4-MET polymer.
The calcium salt of the 4-MET polymer thus obtained was further pulverized with a planetary ball mill and classified with a # 280 sieve to obtain a dental material usable as a filler.

The acid-base gram equivalent ratio (calcium base gram equivalent / acid gram equivalent) of the obtained product was 1.0 [gram equivalent / gram equivalent].
[Production Example 5 of calcium salt]
To a reactor equipped with a stirrer, a condenser, a thermometer, a nitrogen inlet, and a dropping funnel, ethanol 60 g, methyl methacrylate 19 g, (2-methacryloxyethyl) acid phosphate 1 g (4.8 mmol), 2, After adding 0.1 g of 2′-azobisisobutyronitrile and bubbling with nitrogen for 15 minutes, the temperature was raised to 70 ° C. while stirring and polymerization was carried out while maintaining the temperature for 5 hours.

  Next, the internal temperature was cooled to room temperature, and a slurry composed of 0.35 g (4.8 mmol) of calcium hydroxide, 150 g of distilled water, and 150 g of acetone was added dropwise over 1 hour, followed by aging for 2 hours.

The obtained reaction mass was filtered, washed with ethanol, and dried to obtain 10.3 g of a colorless powder.
As a result of NMR analysis, IR analysis, and elemental analysis, this colorless powder was confirmed to be a calcium salt of a methacrylate polymer.

The calcium salt of the methacrylate polymer was further pulverized with a planetary ball mill and classified with a # 280 sieve to obtain a dental material that could be used as a filler.
The acid-base gram equivalent ratio (calcium base gram equivalent / acid gram equivalent) of the obtained product was 1.0 [gram equivalent / gram equivalent].
[Production Example 6 of calcium salt]
To a reaction apparatus equipped with a stirrer, a condenser, a thermometer, a nitrogen inlet, and a dropping funnel, 84 g of ethanol, 21 g (0.1 mol) of (2-methacryloxyethyl) acid phosphate, 2,2′-azobis After charging 0.1 g of isobutyronitrile and bubbling with nitrogen for 15 minutes, the temperature was raised to 70 ° C. while stirring and polymerization was carried out while maintaining the temperature for 5 hours.

Next, the internal temperature was cooled to room temperature, and a slurry in which 7.4 g (0.1 mol) of calcium hydroxide was dispersed in 600 g of distilled water was added dropwise over 1 hour, followed by aging for 2 hours.
The obtained reaction mass was filtered, washed with ethanol and dried to obtain 27.1 g of colorless powder.

The obtained colorless powder was confirmed to be a calcium salt of (2-methacryloxyethyl) acid phosphate polymer as a result of NMR analysis, IR analysis, and elemental analysis.
The calcium salt of the 2-methacryloxyethyl phosphate polymer was further pulverized with a planetary ball mill and classified with a # 280 sieve to obtain a dental material usable as a filler.

The acid-base gram equivalent ratio of the obtained product (calcium base gram equivalent / acid gram equivalent)) was 1.0 [gram equivalent / gram equivalent].
[General method of remineralization induction test]
Solvents for the remineralization induction test were 10 mmol / l Hepes adjusted to pH 7.4 with potassium hydroxide, 2.24 mmol / l calcium chloride, 1.34 mmol / l potassium dihydrogen phosphate,
An aqueous solution to which 50 mmol / l potassium chloride and 0.02% sodium azide had been added was used after being sterilized by filtration with a 0.22 μm filter immediately before use.

Further, the degree of saturation of hydroxyapatite of this calcifying solvent by the Davies modified Debye-Huechkel equation is 3.85 × 10 ⁷ , and this solvent has no spontaneous crystal deposition at 37 ° C. for at least 7 days. It was confirmed.

  Add 3 ml of the above-mentioned calcified solvent previously heated to 37 ° C. to a polystyrene tube (manufactured by Falcon) sterilized by γ-ray, and further prepare a test sample 20%, Hepes 10 mmol / l, potassium chloride 150 mmol / l. 2 μl of the prepared aqueous solution (pH 7.4) was added and incubated at 37 ° C. and 125 rpm for 2 hours in a constant temperature shaking water bath.

The tube was collected and filtered with calcification solvent and test sample filtration using a 0.45 μm filter, and the filter was washed with 0.03% ammonium hydroxide aqueous solution and the calcified sample on the filter was allowed to air dry. . The obtained sample was dissolved in a solution consisting of 3 ml of hydrochloric acid having a concentration of 0.3% and 3 ml of lanthanum oxide having a concentration of 0.25%, and the calcium concentration in the sample was determined using an atomic absorption spectrometer (Model 5100 manufactured by Perkin Elmer). It was measured. Further, the obtained calcified sample was vapor-deposited according to a conventional method, observed with a scanning electron microscope (manufactured by Shimadzu Corporation; SS550), and further an X-ray diffractometer (manufactured by Rigaku Corporation; Rint2000) was used. The obtained calcified sample was identified. Thereby, the calcium amount as a hydroxyapatite produced | generated in the calcification solvent, ie, a remineralization induction ability, can be evaluated.
[Calcium release test]
Pepsin solubilized type I collagen hydrochloric acid solution (manufactured by Nitta Gelatin Co., Ltd., cell matrix) was sufficiently dialyzed with distilled water, and the resulting collagen gel was lyophilized to obtain a collagen sponge.

A polyethylene container was charged with 6.6 ml of 50 mM Tris-HCl (pH value 7.4), 20 mg of the collagen sponge obtained as described above was further added, and the mixture was stirred for 2 hours to obtain a suspension.

The polyethylene container containing the above suspension was covered with a dialysis membrane (manufactured by Sanko Junyaku Co., Ltd.) having an excluded molecular weight of 10,000.
This was stirred at 20 ° C. at 4 ° C. while stirring in contact with 15 ml of a suspension of 50 mM Tris-HCl (pH 7.4) to which the calcium salt obtained in the above production example was added at a rate of 1%. Dialyzed for days.

Next, the Tris-HCl added with calcium salt was exchanged with deionized water, and further 5 ° C. at 4 ° C.
Dialysis was performed for a day, and the inside of the polyethylene container was freeze-dried to obtain a calcified collagen gel.

After adding 6 ml of concentrated nitric acid to 10 mg of the resulting calcified collagen gel and boiling for 3 hours, 0.6 ml of 60% perchloric acid was added and heated to 150 ° C. to decompose the organic components.
Further, the solution was concentrated to the point before dryness, and 1% hydrochloric acid was added to make 10 ml. The amount of calcium and phosphorus contained in the calcified collagen gel was measured with an induction plasma light emitting device (Seiko Instruments Co., Ltd.). .

From the result, it can be evaluated whether the mineralization ability of collagen is promoted by the test sample.
[Measurement of dentin bond strength]
The front forehead of the bovine is polished with # 600 emery paper under water injection, and the flat surface of the dentin for adhesion is cut off, and the dentin surface is treated with a dentin surface treatment material green (dentin consisting mainly of citric acid and ferric chloride) A surface treatment agent for dental use (manufactured by Sun Medical Co., Ltd.), washed with water and dried, and then an adhesive area of 4.8 mm in diameter was defined with double-sided tape.

  About 0.09 g of a monomer liquid having a predetermined composition is put on a mixing dish, and about 0.007 g of superbond catalyst (corresponding to partially oxidized tributyl boron: (F) component, manufactured by Sun Medical Co., Ltd.) (100 parts by weight of monomer liquid) 7.8 parts by weight) was added dropwise, mixed with 0.08 g of the powder shown below with an adhesive brush, applied to the adhesive tooth surface, and then pressed and planted with a PMMA adhesive rod.

The sample adhered after 1 hour was immersed in distilled water at 37 ° C., and after 24 hours, the tensile adhesive strength was evaluated.
From this result, it is possible to evaluate the basic characteristics when the remineralization promoting material of the present invention is used as an adhesive application, or when it is used as a biological primer or liner for an adhesive.
(Evaluation of edge 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. .
A monomer solution having a composition of 95 g of methyl methacrylate (corresponding to the above component (B)) and 5 g of 4-methacryloxyethyl trimellitic anhydride (corresponding to the above component (C)) was added to the mixing dish at about 0. 09g, superbond catalyst (partially tributyl boron oxide, equivalent to component (E) above, manufactured by Sun Medical Co., Ltd.), about 0.007g (7.8 parts by weight with respect to 100 parts by weight of monomer liquid) was dropped. The mixture was mixed with 0.08 g of powder to be described later with an adhesive brush, filled into the cavity, and the filled surface was covered with cellophane, and then left overnight at 37 ° C. and saturated humidity.

  After leaving, the filling surface was polished with water injection with # 600 emery paper to make a smooth surface, and then the tooth filled with the composition in the cavity as described above in a 0.3% basic fuchsin aqueous solution for 3 minutes Soaked.

  After removing the tooth from the fuchsin aqueous solution and washing it with distilled water, the filling surface of the tooth is further polished by pouring water with # 100 emery paper, and a microscope is used to check whether fuchsin has penetrated in the direction from the polished surface to the tooth. And observed.

Furthermore, the filling tooth was cut parallel to the cutting direction of the cavity, and whether or not fuchsin penetrated from the cavity surface toward the inside of the tooth was observed using a microscope as described above. In both cases, the case where fuchsin did not enter was evaluated as ◯, and the case where fuchsin was intruded was evaluated as x.
[Dyeing discrimination test for caries detection materials]
100 g of distilled water, 5 g of the dye shown in the examples and 1 g of the calcium salt obtained in the above production example were added and suspended to prepare a caries detecting material of the present invention.

50μl of various caries detection materials that were well agitated immediately before use were applied to the cut surface of human carious dentin that was conveniently removed using this, and the application site was washed with distilled water after 10 seconds. Was observed more clearly, and judged according to the criteria described below.

In addition, the caries detection material using fluorescein sodium as a pigment is irradiated with light using a commercially available dental visible light irradiator to observe whether the caries part and the healthy dentin part are dyed more clearly. The determination was made according to the criteria described below.
++: Vividly dyed +: Dyed ±: Slightly dyed-: Almost not dyed [Examples 1 to 6]
Using the calcium salt powders obtained in Production Examples 1 to 6, the remineralization induction test and the calcium release ability test were respectively performed.

The results are shown in Table 1.
[Comparative Example 1]
Into the flask, 10 ml of sodium carbonate having a concentration of 0.5 mol / l, 2 ml of agarose beads (DEAE-Sepharose 4B, manufactured by Amersham Pharmacia Biotech) and 1 ml of dibilsulfone are stirred and stirred for 2 hours at room temperature. After activating, phosvitin 30 mg which is a phosphoprotein having a calcifying action is added to this, and phosvitin is cross-linked on the surface of the agarose beads by continuing stirring for 2 hours, and 0.5 ml of 2-mercaptoethanol is added. The reaction was stopped.

The obtained agarose beads were washed with a sufficient amount of distilled water and then washed with a concentration of 0.5 mol / l sodium hydroxide and 50 mmol / l Tris-HCl (pH 7.4) in this order, and phosvitin was added at 2.56 × 10 6. 2 ml of phosvitin-conjugated agarose beads containing ^-4 % were obtained.

In Examples 1 to 6, the remineralization induction test described above was performed in the same manner except that the phosvitin-conjugated beads obtained as described above were used instead of the calcium salt.
The results are shown in Table 1.
[Comparative Example 2]
In the same manner as in Example 1 except that Superbond powder material clear (trade name; polymethyl methacrylate, manufactured by Sun Medical Co., Ltd.) was used instead of calcium salt, the above-described remineralization induction test and calcium release ability were used. Each test was conducted.

The results are shown in Table 1.
[Examples 7 to 20]
Calcium salt powder obtained in Production Example 1 and Super Bond powder material clear (trade name; polymethyl methacrylate, manufactured by Sun Medical Co., Ltd.) are taken at a predetermined ratio, and these are mixed using a planetary ball mill. Using the powder obtained by classification with a 280 sieve, the above-described measurement of dentin bond strength and the evaluation of marginal sealing were performed.

The results are shown in Table 1.
[Comparative Examples 3 to 7]
Calcium hydroxide is pulverized in advance using a planetary ball mill, and the pulverized calcium hydroxide and Superbond powder material clear (trade name; polymethyl methacrylate, manufactured by Sun Medical Co., Ltd.) are taken at a predetermined ratio. These were mixed with a planetary ball mill and classified with a # 280 sieve to measure the dentin bond strength and evaluate the marginal sealing performance.

The results are shown in Table 1.
[Examples 21 to 26]
In the above-described dye discrimination test, acid red was used as a pigment, and the product obtained in Production Examples 1 to 6 of the calcium salt was used as a calcium salt.

The results are shown in Table 3.
[Examples 27 to 32]
In the above-described dye discrimination test, basic fuchsin was used as a pigment, and the products obtained in the above calcium salt production examples 1 to 6 were used as calcium salts.

The results are shown in Table 3.
[Examples 33 to 38]
In the above-described dye discrimination test, fluorescein sodium was used as a pigment, and the products obtained in the above calcium salt production examples 1 to 6 were used as calcium salts.

The results are shown in Table 3.
[Comparative Example 8]
In the above-described dye discrimination test, acid red was used as a pigment, and a dyeing solution was prepared and tested without adding a calcium salt.

The results are shown in Table 3.
[Comparative Example 9]]
In the above-described dye discrimination test, basic fuchsin was blended as a pigment, and a dyeing solution was prepared and tested without blending a calcium salt.

The results are shown in Table 3.
[Comparative Example 10]]
In the above-described staining discrimination test, sodium fluorescein was blended as a pigment, and a staining solution was prepared and tested without blending a calcium salt.

  The results are shown in Table 3.

From Table 1, it was shown that the calcium salt of the present invention has a remineralization promoting ability equal to or higher than phosvitin which is a positive control.
Table 2 shows that the dental composition containing the calcium salt of the present invention is useful as a dental adhesive and does not impair the adhesive performance.

Furthermore, from Table 3, the caries detection material containing the calcium salt of the present invention does not impair the original performance, and, together with Table 1, has the possibility of promoting remineralization at the application site. It has been shown.

Claims (11)

The following (B) ~ Dental composition you characterized by being comprised of (D);
(B) Monofunctional (meth) acrylate: 90 to 99 parts by weight (provided that the total of (B) and (C) is 100 parts by weight),
(C) Polymerizable monomer having at least one acidic group in the molecule: 1 to 10 parts by weight (provided that the total of (B) and (C) is 100 parts by weight),
(D) The acidic group of the monomer (A) having a polymerizable group and at least one acidic group selected from the group consisting of a carboxylic acid group and a phosphoric acid group in the molecule is completely neutralized by calcium. Monomer calcium salt (S _A )
And / or
A polymer (P) of a polymerizable monomer containing a monomer (A) having a polymerizable group and at least one acidic group selected from the group consisting of a carboxylic acid group and a phosphoric acid group in the molecule. , A filler comprising a polymer calcium salt (S _P ) in which the acidic group is completely neutralized with calcium ; 0.5 to 300 parts (provided that the ratio of (B) and (C) is 100 parts by weight in total) a is is),
The component (B) is methyl methacrylate,
The component (C) is 4-methacryloxyethyl trimellitic acid and / or its anhydride,
The calcium salt (S1) of the monomer (A1) wherein the component (D) is selected from at least one of the group consisting of 4- (meth) acryloxyethyl trimellitic acid and 2- (meth) acryloxyethyl acid phosphate _A1 ) and / or a calcium salt (S _P1 ) of a polymer (P1) having a repeating unit derived from the monomer (A1), and having an average particle diameter in the range of 0.001 to 30 μm It is a material. The dental composition further comprises (E) polyfunctional (meth) acrylate; 1 to 35 parts by weight (provided that the ratio of (B), (C), and (E) is 100 parts by weight in total). The dental composition according to claim 1, comprising : a dental composition according to claim 1. The dental composition according to claim 1 or 2 , wherein the dental composition further comprises (F) an organoboron compound. The dental composition according to any one of claims 1 to 3 , wherein the dental composition further comprises (G) a photopolymerization initiator. The dental composition according to any one of claims 1 to 4 , wherein the dental composition further comprises (H) a compound capable of supplying fluoride ions in water. (F) The organoboron compound contained in the dental composition is at least one boron compound selected from the group consisting of trialkylboron, alkoxyalkylboron, dialkylborane and partially oxidized trialkylboron. The dental composition according to any one of claims 3 to 5 , wherein the dental composition is characterized in that The dental composition according to claim 6 , wherein at least one of the alkyl groups constituting the organoboron compound is a butyl group. A dental adhesive comprising the dental composition according to any one of claims 1 to 7 . Remineralization promoting material characterized by comprising from dental composition according to one of claims paragraphs 1 through 7 wherein. Biomedical adhesive material characterized by consisting of dental composition according to one of claims paragraphs 1 through 7 wherein. It caries detection material characterized by consisting of dental composition according to one of claims paragraphs 1 through 7 wherein.