JP2000044421A - Dental adhesive composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a dental adhesive composition usable for preventing infection with bacteria by directly coating the surface of dentine with the composition so as to protect dentine and cutting off an external stimulation. SOLUTION: This composition comprises (A) 3-50 pts.wt. of a radical- polymerizable monomer containing an acidic group or an acidic base in the molecule, (B) 10-50 pts.wt. of a water-insoluble or a slightly water-soluble radical-polymerizable monomer having <5 wt.% water solubility, (C) 5-60 pts.wt. of a boron-containing polymerization initiator and (D) 5-60 pts.wt. of an aqueous solvent in 100 pts.wt. of the total of the components A-D.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

TECHNICAL FIELD The present invention relates to a dental adhesive composition which is advantageously used for restoring teeth and the like. More particularly, the present invention relates to a dental adhesive composition that can be used to prevent bacterial infection and block external stimuli by directly coating the tooth surface for the purpose of protecting the tooth. More specifically, since it can be directly applied to the tooth and has good adhesiveness, and has sufficient hardness, it can be applied as a coating material to the tooth, and the adhesiveness to the tooth can be improved. Insufficient zinc phosphate cement, carboxylate cement, glass ionomer cement, and the like can be further used on the coating material to apply the prosthetic restoration, and are also represented by composite resins, resin cements, and the like. The present invention relates to a dental adhesive composition that can also be used as an adhesive for bonding dental resin and dentin.

[0002]

2. Description of the Related Art In order to repair teeth lost due to cavities, fractures or wear, it is necessary to use a material that reliably adheres to the restoration and the tooth material. Uncertain adhesion can cause secondary caries by infiltration and propagation of bacteria to create gaps between restorations. Further, when the invading bacteria reach the pulp via the dentin tubules of the dentin, pulpitis may be caused.

[0003] In the case of dental restoration, the method of treatment differs depending on the condition of the teeth, the size of the defective part, and the like. For example, if the defect is relatively small and the teeth are in good hygiene,
Immediately after cutting and removing the carious portion, treatment can be completed at one visit by using a filler material such as a composite resin, a glass ionomer cement, or amalgam using an adhesive. However, treatment for a site where the defect is large or a large force is applied to the restoration cannot be performed in a single visit, and the patient must go to the hospital for several days. That is, in general,
The dentist first trims the patient's teeth appropriately (shaping the cavity) and creates a replica of the morphology using the impression material. Further, the tooth formed with the cavity is temporarily filled with a filler that does not adhere to the tooth, such as a temporary sealing material, and the initial treatment is completed. Metals and ceramics are cast or built based on the replica, and prostheses are manufactured over several days. The dentist visits the patient again after the prosthesis is completed, removes the temporary filling, and attaches the prosthesis to the tooth with cement.

[0004] In a treatment that can be performed in a single visit, there is little chance of infection because there is no contact of saliva or food on the ground surface. On the other hand, in the above-described conventional treatment in which a temporary sealing material is applied, the probability that bacteria adhere to the cut tooth surface or penetrate into the dentinal tubule is significantly increased. If the prosthesis is mounted without removing it, it may cause secondary caries or pulpitis. Furthermore, when a sharp jig or the like sharply touches the tooth material when removing the temporary sealing material, the tooth material may be damaged or severely damaged in some cases.

[0005] So far, as a composition that adheres to the tooth substance,
Japanese Patent Publication No. 7-64699, Japanese Patent Publication No. 7-59487, Japanese Patent Publication No. 6-99528, Japanese Patent No. 25435.
No. 16 and Japanese Patent Application Laid-Open No. 7-97306 have been proposed. Japanese Patent Publication No. 9-110913 has been proposed as a boron-containing polymerization initiator that can be used for the proposal. However, these are mainly adhesives such as composite resins, and are adhesive compositions suitable for treatments that can be treated at a single visit, and when used as coating materials, it is necessary to control the thickness of the film. It was difficult, and the hardness of the cured product was insufficient. That is, since a relatively hydrophobic curable composition is formed in order to improve adhesiveness and adhesive durability, it is necessary for a user to form a thin film on a tooth surface containing a large amount of moisture. However, the composition applied to the tooth surface must be spread with a brush or sponge or the like, and the thickness must be adjusted by squeezing air or the like, and it has been difficult to form a uniform thickness with good reproducibility. In addition, the composition spread thinly was strongly affected by oxygen in the air, the radical polymerizability was reduced, and as a result of insufficient curing, the surface hardness and the adhesiveness were sometimes reduced. .
Furthermore, the pretreatment (etching) such as phosphoric acid, citric acid, and EDTA which may contain a metal salt is required for the dentin to be adhered. JP-B-6-2792 as a curable composition that can be directly adhered to the cut tooth without any pretreatment
No. 26 has been proposed. Although this proposal is characterized by using a high molecular polymer containing an acidic group, a composition containing the component generally has a high viscosity and tends to have a thick coating layer. For this reason, it may not be possible to use it for applications where the thickness is inconvenient.

[0006]

SUMMARY OF THE INVENTION An object of the present invention is to provide a dental adhesive composition which can solve the above-mentioned difficulties in film formation, insufficient film strength and insufficient adhesiveness, and which can be directly applied to tooth surfaces. Is to provide. In order to achieve the object of the present invention, (1) a thin film can be formed with a uniform thickness, and (2) it adheres well even when applied directly to the tooth material,
Another object of the present invention is to provide a dental adhesive composition which can satisfy the required property that the cured product on the film is hard.

In order to achieve the object of the present invention, more specifically, (1) To form a thin and uniform film,
The solvent can be volatilized after the radical polymerizable monomer dissolved in the organic solvent is applied to the tooth surface, and (2) the acid is contained in one molecule so that it can be applied directly to the tooth surface to achieve good adhesion. Provided is a dental adhesive composition using a radically polymerizable monomer having low solubility in water so that a radical polymer having a group can be sufficiently dissociated and (3) a hard film can be formed. Is to do. Another object of the present invention is to provide a curable composition having excellent storage stability in use. That is, it is an object of the present invention to provide a composition in which phase separation of a liquid does not occur for a long period of time and performance is not impaired even when stored for a long time. Still other objects and advantages of the present invention will become apparent from the following description.

[0008]

According to the present invention, the above objects and advantages of the present invention are as follows: (A) 1 to 50 parts by weight of a radical polymerizable monomer having an acidic group or a salt thereof in a molecule;
(B) 1 to 70 parts by weight of a radical polymerizable monomer, (C) 1 to 60 parts by weight of a boron-containing polymerization initiator, and (D) water 1
７０70 parts by weight, and the total of the components (A) to (D) is 100 parts by weight. The dental adhesive composition of the present invention further comprises:
(E) 1 to 100 parts by weight of a water-miscible organic solvent and / or (F) 0.001 to 5 parts by weight of a photopolymerization initiator, and (G) 0.1 to 25 parts by weight of a filler It can also be contained in parts. Further, the composition of the present invention can provide a cured product having a Brinell hardness of 7 or more.

In the dental adhesive composition of the present invention, the radically polymerizable monomer is a compound having at least one kind of radically polymerizable group in the molecule. Compounds having an acryloyl group, styryl group, vinyl group, allyl group, and the like, that is, unsaturated hydrocarbons can be mentioned.

In the present invention, the component (A) is a radical polymerizable monomer having an acidic group or an acidic base in one molecule. Examples of the acidic group include a carboxylic acid group, a carboxylic acid anhydride group, a phosphoric acid group, and a sulfonic acid group.

For example, examples of the monofunctional polymerizable monomer having a carboxylic acid group or an anhydride group in one molecule include monocarboxylic acid, dicarboxylic acid, tricarboxylic acid, tetracarboxylic acid, and polycarboxylic acid or anhydride thereof. Can be mentioned. Here, examples of the compound that can be used include a carboxylic acid and / or an anhydride thereof (a2) described in JP-B-6-62688. In particular, for example, (meth) acrylic acid, maleic acid, p
-Vinylbenzoic acid, 11- (meth) acryloyloxy-1,1-undecanedicarboxylic acid (MAC-10),
1,4-di (meth) acryloyloxyethylpyromellitic acid, 6- (meth) acryloyloxyethylnaphthalene-1,2,6-tricarboxylic acid, 4- (meth) acryloyloxymethyltrimellitic acid and anhydrides thereof,
4- (meth) acryloyloxyethyl trimellitic acid and its anhydride, 4- (meth) acryloyloxybutyl trimellitic acid and its anhydride, 4- [2-hydroxy-3- (meth) acryloyloxy] butyl trimellitate Acids and anhydrides, 2,3-bis (3,4-dicarboxybenzoyloxy) propyl (meth) acrylate, 2 or 3 or 4- (meth) acryloyloxybenzoic acid, N, O-di (meth) acryloyl Oxytyrosine, O- (meth) acryloyloxytyrosine,
N- (meth) acryloyloxy tyrosine, N- (meth) acryloyloxyphenylalanine, N- (meth) acryloyl p-aminobenzoic acid, N- (meth) acryloyl O-aminobenzoic acid, N-phenylglycine or N-tolyl Adduct of glycine 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, (meth) acryloylaminosalicylic acid, (meth)
Acryloyloxysalicylic acid can be mentioned.
Of these, 11-methacryloyloxy-1,1-undecanedicarboxylic acid (MAC-10) and 4-methacryloyloxyethyl trimellitic acid (4-MET) or its anhydride (4-META) are preferably used. As the polyfunctional polymerizable monomer that can be used as the component (A), the polymerizable monomer having at least two carboxyl groups in one molecule includes dicarboxylic acid, tricarboxylic acid and tetracarboxylic acid or derivatives thereof. Can be mentioned. For example, an addition product (PMDM) of 2-hydroxyethyl (meth) acrylate and pyromellitic dianhydride, 2 mol of 2-hydroxyethyl (meth) acrylate and 1 mol of maleic anhydride or 3,
An addition reaction product obtained by reacting 3 ′, 4,4′-benzophenonetetracarboxylic dianhydride (BTDA) or 3,3 ′, 4,4′-biphenyltetracarboxylic dianhydride;
2- (3,4-dicarboxybenzoyloxy) 1,3-
Di (meth) acryloyloxypropane and the like can be mentioned.

Examples of the polymerizable monomer having at least one phosphate group in one molecule 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) acryloyloxyoctyl acid phosphate, 10- (meth) acryloyloxydecyl Acid phosphate, 12- (meth) acryloyl oxide decyl acid phosphate, bis {2- (meth) acryloyloxyethyl} acid phosphate, bis {2 or 3- (meth) acryloyloxypropyl} acid phosphate, 2- (meth) acryloyl Oxyethyl phenyl acid phosphate, 2
-(Meth) acryloyloxyethyl p-methoxyphenyl acid phosphate and the like. The phosphate group in these compounds can be replaced by a thiophosphate group. Examples of the polymerizable monomer having a thiophosphoric acid group include JP-A-54-21438 and JP-A-59-42438.
140276 and JP-A-59-142268 can be used. Specific examples include the following compounds, which may be the tautomers shown in [].

[0013]

Embedded image

Of these, 2- (meth) acryloyloxyethyl phenyl acid phosphate, 10- (meth)
Acryloyloxydecyl acid phosphate is preferably used. These polymerizable monomers having a phosphate group can be used alone or in combination.

A polymerizable monomer having a sulfonic acid group in one molecule. As such a polymerizable monomer, for example, 2-
Sulfoethyl (meth) acrylate, 2 or 1-sulfo-1 or 2-propyl (meth) acrylate, 1 or 3-sulfo-2-butyl (meth) acrylate, 3
-Bromo-2-sulfo-2-propyl (meth) acrylate, 3-methoxy-1-sulfo-2-propyl (meth) acrylate, 1,1-dimethyl-2-sulfoethyl (meth) acrylamide, and the like. .
Among them, 2-methyl-2- (meth) acrylamidopropanesulfonic acid is preferably used.

In the component (A), part or all of the acidic groups are 1
It can also be used as a salt such as a monovalent or polyvalent metal salt or ammonium salt. In this case, it is usually preferable that the component (A) functions as an acid when contacted with another acidic compound. All of the above components (A) can be used alone or in combination.

The component (B) of the present invention is a radical polymerizable monomer, and specifically includes, for example, methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, and (meth) acrylic acid. Aliphatic esters of (meth) acrylic acid such as butyl acrylate, neopentyl glycol di (meth) acrylate, and trimethylolpropane tri (meth) acrylate; 2-hydroxyethyl (meth) acrylate, 2 or 3-propyl (meth) A) acrylate, glycerol mono (meth) acrylate, diethylene glycol mono (meth) acrylate, triethylene glycol mono (meth) acrylate, pentaethylene glycol mono (meth) acrylate, polyethylene glycol mono (meth) acrylate, 2-hydroxy-
Hydroxyl-containing (meth) acrylates such as 3-phenoxypropyl (meth) acrylate, an adduct of 1 mol of bisphenol A and 2 mol of glycidyl (meth) acrylate; hydroxyl-containing (meth) such as methylol (meth) acrylamide Acrylamides: ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, triethylene glycol di (meth)
Polyethylene glycol di (meth) acrylates such as acrylate, pentaethylene glycol di (meth) acrylate, nonaethylene glycol di (meth) acrylate, and tetradecaethylene glycol di (meth) acrylate; propylene glycol di (meth) acrylate, dipropylene Polypropylene glycol di (meth) acrylates such as glycol di (meth) acrylate, tripropylene glycol di (meth) acrylate, nonapropylene glycol di (meth) acrylate; the above-mentioned polyethylene glycol di (meth) acrylate and polypropylene glycol di (meth) ) Acrylates in which one (meth) acryloyl group is substituted with a methyl group or an ethyl group, etc.
Acrylates; urethane bonds such as 2- (meth) acryloyloxyethyl isocyanate or 2,2,4-trimethylhexamethylene diisocyanate or an adduct of 1,3,5-trimethylhexamethylene diisocyanate with 2-hydroxyethyl (meth) acrylate (Meth) acrylates having the formula: 2,2-bis (4- (meth) acryloyloxypolyethoxyphenyl) propane, which is obtained by further condensing (meth) acrylic acid with a product obtained by adding oxyethylene to bisphenol A; Can be mentioned. These polymerizable monomers can be used alone or in combination. Among the component (B) of the present invention, a radical polymerizable monomer having a solubility in water of less than 5% is particularly preferable among the above-mentioned radical polymerizable monomers.

Specific examples of the component (B) include aromatic vinyl compounds such as styrene and divinylbenzene: vinyl esters such as vinyl acetate; methyl (meth) acrylate, ethyl (meth) acrylate, Meta)
Propyl acrylate, butyl (meth) acrylate, pentyl (meth) acrylate, hexyl (meth) acrylate, neopentyl glycol di (meth) acrylate,
Aliphatic esters of (meth) acrylic acid such as trimethylolpropane tri (meth) acrylate; aromatic esters such as phenyl (meth) acrylate;

[0019]

Embedded image Wherein R ¹ is H or CH ₃ and R ² is a phenyl or naphthyl group;

For example, 2-hydroxy-3-phenoxypropyl (meth) acrylate (HPP)
M) Adduct of 1 mol of bisphenol A and 2 mol of glycidyl methacrylate (Bis-GMA), 1 mol of addition polymer of bisphenol A glycidyl ether and 2 mol
Mole of (meth) acrylic acid condensate (VR90), 1 mole of ethylene oxide adduct of bisphenol A and 2 moles of (meth) acrylic acid condensate (m + n ≧ 2; m + n = 2.6 (Abbreviated as 2.6E)
Aromatic (meth) acrylates such as; 2- (meth)
Acryloyloxyethyl isocyanate, 1 mole of 2,2,4- (or 2,4,4-) trimethyl-1,6-
Adduct of hexamethylene diisocyanate and 2 moles of 2-hydroxyethyl (meth) acrylate (UDMA)
Urethane bond-containing (meth) acrylate represented by;
1,6-hexamethylene dimethacrylate (1,6-H
X), aliphatic esters of (meth) acrylic acid such as neopentyl glycol di (meth) acrylate, trimethylolpropane tri (meth) acrylate; ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, triethylene Glycol di (meth) acrylates (chain number n = 9 or less); propylene glycol di (meth) acrylate, dipropylene glycol di (meth) acrylate, tripropylene glycol di (meth) acrylate, nonapropylene glycol di (meth) acrylate Polypropylene glycol di (meth) acrylates (the number of chains n = 1)
2) and the like, and these polymerizable monomers can be used alone or in combination. Among them, solid or 100
A polymerizable monomer having a viscosity of cP or more is preferable. For example, HPPM, Bis-GMA, VR90, 2.6E and UDMA are preferably used. Use of such a solid or a polymerizable monomer having a viscosity of 100 cP or more ensures adhesion to the coating surface when the composition of the present invention is applied, plays a role of preventing sagging, and has an adhesive property and a surface hardness. Is stably expressed. Substantially solid or viscous polymerizable monomers can be combined with monomers having lower viscosities or solvents can be used to adjust the viscosity of the composition of the present invention.

A radically polymerizable monomer having a solubility in water of less than 5% by weight is defined as 5% by weight of the polymerizable monomer in distilled water.
The mixture was stirred at 37 ° C. for 30 minutes, allowed to stand at the same temperature for 10 minutes, and then visually observed, when oil droplets were separated, or when clear water was used. The phase means a polymerizable monomer when phase separation is observed between the phase and the cloudy phase.Other than that, for example, for a polymerizable monomer that is kept uniformly transparent or cloudy for at least 10 minutes, The solubility in water was defined as 5% by weight or more. It is particularly preferable that the mixture of the components (A) and (B) in the composition ratio used in the composition of the present invention is less than 5% by weight when tested by the above-mentioned solubility measurement method.

The component (C) of the present invention is a boron-containing polymerization initiator. As such a polymerization initiator, an organic boron compound or a composition containing the same can be generally mentioned. As an organic boron compound, for example,
Triethyl boron, tripropyl boron, triisopropyl boron, tributyl boron, tri-sec-butyl boron, triisobutyl boron, tripentyl boron,
Trialkylboranes such as trihexyl boron, trioctyl boron, tridecyl boron, tridodecyl boron, tricyclopentyl boron, tricyclohexyl boron; alkoxyalkyl borons such as butoxydibutyl boron; butyl dicyclohexyl borane, diisoamyl borane, 9 And dialkylboranes such as -borabicyclo [3.3.1] nonane. These compounds may be partially oxidized. further,
These compounds can be used in combination.
Of these, tributylboron or partially oxidized tributylboron is preferably used. As the partially oxidized tributylboron, for example, those obtained by adding 0.3 to 0.9 mol of oxygen to 1 mol of tributylboron are preferably used.

In addition to the organoboron compound, a composition containing an aprotic solvent and / or a liquid or solid organic oligomer or polymer inert to the organoboron compound may be used as the component (C). it can.

The component (D) of the present invention is water. The water in the present invention originally has the property of accelerating the decomposition of the boron-containing initiator which is the component (C) and inactivating it. Also,
Excessive water can reduce adhesion, decrease coating hardness, and impair the durability of those properties. Further, when the component (B) having a solubility in water of less than 5% is used,
Even when used in combination with the component (E), phase separation may occur at a low temperature or storage stability may be impaired. Therefore, the amount of water in the composition of the present invention must be used within an appropriate range that does not impair the effects of the present invention. The amount of water in the curable composition of the present invention affects tooth adhesion, hardness of the coating on the tooth surface, and storage stability of the component mixture other than the boron-containing polymerization initiator. When the amount of water in the curable composition increases,
There is a tendency for the adhesive strength to the cut tooth material not pre-treated to be high. On the other hand, when the amount of water is small, the solution of the component mixture other than the boron-containing polymerization initiator can be kept uniform, and the adhesive performance can be stably exhibited over time. Therefore, the amount of water in the curable composition of the present invention is used in consideration of the above-mentioned balance of performance. Examples of water that can be used here include distilled water, ion-exchanged water, purified water, and physiological saline. Particularly, distilled water, purified water and ion-exchanged water are preferably used. Further, redox water prepared by electrolysis, for example, strongly acidic water, strongly alkaline water, or the like can be used. The component (E) of the present invention is a water-miscible organic solvent. As such an organic solvent, a solvent that is miscible and / or soluble in water at an arbitrary ratio is preferable. Further, the solvent is a liquid at 25 ° C. and has a boiling point at room temperature of 200 ° C. or lower, preferably 150 ° C. or lower, and most preferably 100 ° C. or lower. Specific examples of the organic solvent usable herein include alcohols such as methanol, ethanol, and propanol; ethers such as tetrahydrofuran (THF); ketones such as acetone and methyl ethyl ketone; N, N-dimethyl sulfoxide ( Sulfoxides such as DMSO);
Amides such as N-dimethylformamide (DMF) can be mentioned. In addition, higher alcohols such as ethylene glycol, propylene glycol, and glycerol can be used. Here, alcohols such as ethanol and propanol, acetone, THF, DMSO and the like are preferable in consideration of safety to living bodies.
Any of the above compounds can be used in combination.

The component (F) of the present invention is a photopolymerization initiator. Such an initiator has a role of being excited by light in the presence of the compound alone or in the presence of another compound to cure the curable composition of the present invention. It is particularly preferable when the composition of the present invention is cured early.
That is, the rate of radical polymerization using the component (C) is generally slow, and it usually takes several minutes or at most about one minute to obtain the hardness of a cured product suitable for the purpose of the present invention. However, the use of the component (F) significantly increases the rate of radical polymerization, and usually has an advantage that 10 to 40 seconds, and if it is fast, several seconds are sufficient. For example, (f1) α-ketocarbonyl compound, (f2) acyl phosphine oxide compound and the like can be mentioned. Specifically, for example, (f1)
Benzyl, 4,4′-dichlorobenzyl,
Benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzophenone, 9,10-anthraquinone, diacetyl,
α-Ketocarbonyl compounds represented by d, l-camphorquinone (CQ) can be mentioned, and they can be used alone or in combination. Further, as the component (f2),
Benzoyldimethoxyphosphine oxide, benzoylethoxyphenylphosphine oxide, benzoyldiphenylphosphine oxide, 2-methylbenzoyldiphenylphosphine oxide, 2,4,6-trimethylbenzoyldiphenylphosphine oxide, and the like can be given. The component (f1) and the component (f2) can be used alone or in combination.

Further, if necessary, (f3) an amine compound can be used. The component (f3) may be any of an aliphatic amine, an alicyclic amine, and an aromatic amine, and may be any of a primary amine, a secondary amine, and a tertiary amine. It is preferably an aromatic amine, and more preferably an aromatic tertiary amine. For example, aliphatic alkylaminoacetylbenzenes and aliphatic alkylaminoacylbenzenes represented by triethylamine, tripropylamine, tribubenzene and the like; N-phenylglycine (NP
G), N-tolylglycine (NTG), N, N- (3-
Methacryloyloxy-2-hydroxypropyl) phenylglycine (NPG-GMA) can be used in combination. These compounds can be used alone or in combination.

In addition to the photopolymerization initiator, if necessary, an organic peroxide, an inorganic peroxide, an organic sulfinic acid or / and a salt thereof, an inorganic sulfur compound, and barbituric acids can be used.

The component (G) in the present invention is a filler. Such a filler is at least one filler selected from organic fillers, inorganic fillers, and organic composite fillers. The filler used here is added mainly for the purpose of improving the mechanical strength of the cured product of the curable composition. The organic filler is a powder polymer filler obtained by pulverization or dispersion polymerization of a polymer that does not dissolve in the polymerizable monomer used as the component (B), and conversely, the polymerization used as the component (B) Fillers obtained by polymerizing a polymerizable monomer dissolved in a water-soluble monomer by adding a crosslinking agent thereto and then pulverizing the polymerized monomer. Here, the type of the polymerizable monomer serving as a raw material of the filler that can be used is not particularly limited, but a filler composed of a homopolymer or a copolymer of the polymerizable monomer exemplified as the component (B), or An organic / inorganic filler obtained by blending an inorganic filler with the filler (hereinafter abbreviated as an organic composite filler) can be exemplified. For example, polymethyl methacrylate (PM
MA), polyethyl methacrylate, polypropyl methacrylate, polybutyl methacrylate (PBMA), polyvinyl acetate (PVAc), polyethylene glycol (PE
G), polypropylene glycol (PPG), polyvinyl alcohol (PVA), and the like. These can be insolubilized by a crosslinking agent.

As the inorganic filler, for example, silica,
Silica alumina, alumina, alumina quartz, glass (including barium glass), titania, zirconia (zirconium oxide), calcium carbonate, kaolin, clay, mica, aluminum sulfate, barium sulfate, calcium sulfate, titanium oxide, calcium phosphate, etc. Can be. These inorganic fillers may be previously surface-treated with a silane coupling agent or a titanate coupling agent.

Examples of the organic composite filler include fillers obtained by polymerizing and coating the surface of the above-mentioned inorganic filler with a polymerizable monomer, followed by pulverization.
Specifically, among the inorganic fillers, fine powder silica is converted to trimethylolpropane tri (meth) acrylate (TM).
Filler (TMPT.f) obtained by polymerizing and coating the polymer obtained with a polymerizable monomer containing (PT) as a main component and pulverizing the obtained polymer. Further, a filler obtained by adding and dispersing an inorganic filler such as silica or zirconium oxide to a solution such as acetone in which PMMA is dissolved, evaporating the solvent, drying, and pulverizing the solvent is used.

In the present invention, 100 parts by weight of the composition comprising the components (A) to (D) contains 1 to 5 components (A).
0 parts by weight, preferably 3 to 40 parts by weight, more preferably 5 to 30 parts by weight, and the component (B) is 1 to 60 parts by weight, preferably 5 to 50 parts by weight, more preferably 10 parts by weight.
To 40 parts by weight, and the component (C) is 1 to 60 parts by weight, preferably 5 to 50 parts by weight, more preferably 10 to 40 parts by weight.
And the component (D) is used in an amount of 1 to 70 parts by weight, preferably 3 to 50 parts by weight, more preferably 5 to 30 parts by weight.

In the present invention, the component (E) is added in an amount of 1 to 1 with respect to 100 parts by weight of the composition comprising the components (A) to (D).
00, preferably 5 to 90, more preferably 10 to 80 parts by weight,
The component (F) is further used in an amount of 0.001 to 5 parts by weight, preferably 0.005 to 3 parts by weight, more preferably 0.01 to 2 parts by weight, and the component (G) is used in an amount of 0.1 to 25 parts by weight. , Preferably 1 to 20 parts by weight, most preferably 3 to 15 parts by weight.

The composition of the present invention can contain a surfactant, if necessary. The addition of a surfactant is effective for stably dissolving or dispersing each component in the composition. Such a surfactant includes both an ionic surfactant and a nonionic surfactant, and the critical micelle concentration (cmc) in water at 37 ° C. is usually 0.01 to 1.0.
It is a compound showing a value of% by weight.

When the surfactant is an ionic surfactant, examples of the anionic surfactant include metal salts of aliphatic carboxylic acids such as sodium laurate, sodium stearate and sodium oleate; and sodium dioctyl sulfosuccinate. Metal salts of sulfated aliphatic carboxylic acids; metal salts of higher alcohol sulfates such as sodium dodecyl sulfate, sodium lauryl sulfate, sodium cetyl sulfate, sodium stearyl sulfate, sodium oleyl sulfate; adducts of lauryl alcohol and ethylene oxide Metal salts of higher alkyl ether sulfates, such as sodium lauryl ether sulfate, which is sulfated from
Metal salts of alkylbenzenesulfonic acids such as sodium dodecylbenzenesulfonate; metal salts of α-olefinsulfonic acids synthesized by reacting α-olefin with sulfuric acid; Igepon T obtained by reacting N-methyltaurine with oleic chloride; aerosol Sulfosuccinic acid diesters represented by OT; phosphoric acid ester salts of higher alcohol ethylene oxide adducts; dithiophosphate ester salts and the like.

Examples of the cationic surfactant include, for example, an adduct of a higher alkylamine such as stearylamine and ethylene oxide; an amine formed from a lower amine represented by solomin A, sapamin A, arcove A or arcove G, onixan HSB, etc. Alkyltrimethylammonium salts such as lauryltrimethylammonium chloride; quaternary ammonium salts formed from higher alkylamines represented by alkyldimethylbenzylammonium salts such as lauryldimethylbenzylammonium chloride; sapamin such as sapamin MS and sapamin BCH -Type quaternary ammonium salts and catanac SN; lower amines represented by pyridinium salts such as gellan AP and belan PF, meta having radical polymerizability It can be mentioned quaternary ammonium salt type cationic surfactant made from Leroy oxyethyl tri ammonium chloride (MAC).

Examples of the amphoteric surfactant include metal salts of higher alkylaminopropionic acids such as sodium laurylaminopropionate and sodium stearylaminopropionate; betaines such as lauryldimethylbetaine, stearyldimethylbetaine and lauryldihydroxyethylbetaine; Can be mentioned.

Examples of the nonionic surfactant include higher alcohols such as lauryl alcohol represented by polyethylene glycol mono-p-isooctylphenyl ether and polyethylene sorbitan monolaurate, alkylphenols such as nonylphenol, and oleic acid. Glycol-type or polypropylene glycol-type nonionic surfactants obtained by adding ethylene oxide or propylene oxide to fatty acids or higher aliphatic amines such as stearylamine or aliphatic amides such as oleamide; glycerin, pentaerythritol Polyhydric alcohols such as sorbit, sorbitan, sorbitan, sorbitan trioleate, and monoethanolamine and diethanolamine And the like diethanolamines or polyhydric alcohol type nonionic surfactant represented by sugars and sugar such.

As the surfactant, in addition to the compounds mentioned above, for example, compounds described in "Introduction to New Surfactants" (Takehiko Fujimoto, published by Sanyo Kasei) can be mentioned. The surfactant is incorporated into the composition of the present invention preferably at 0.01 to 5% by weight, more preferably 0.02 to 3% by weight, and most preferably 0.03 to 1% by weight.

When a tooth surface is coated with the composition of the present invention, it can be usually applied to the tooth surface at a thickness of 1 to 500 μm. The thickness of the film can be selected according to the purpose of use and application, and by adjusting the viscosity of the composition by changing the ratio of the components in the composition, or by the amount of application to the tooth surface or the method of blowing off by air blow etc. Can also be prepared. In the present invention, a curable composition having a Brinell hardness of preferably 7 or more, more preferably 8 or more, and still more preferably 9 or more as measured by the method described in the Examples can be suitably used. .

The curable composition of the present invention has not only the hardness required for protecting the dentin of the cured product, but also the wettability and the reactivity of the dentin with respect to the tooth surface where a large amount of water is present. And at the same time have necessary conditions for adhesion such as tooth diffusibility and dentin permeability, and can firmly adhere to hard tissue of a living body, especially tooth, without any gap. When the curable composition of the present invention is applied to the dentin, it is preferable that the curable composition is brought into contact with a wet state or after being lightly dried by air blow in consideration of safety. However, in order to maintain cleaning and hygiene of the tooth surface, an etching material such as a solution or gel containing phosphoric acid, nitric acid, hydrochloric acid, sulfuric acid, citric acid, maleic acid, ethylenediaminetetraacetic acid, etc. which may contain a metal salt. Alternatively, a pretreatment such as coating with a conditioner and washing with water can be performed. In addition, hypochlorite or /
And compositions containing it. The tooth material washed with water by applying the pretreatment material can be wet and / or dried, and the dental adhesive composition of the present invention can be applied.

The dental adhesive composition of the present invention is preferably divided and stored in a container containing the component (C) and a container containing the other components, and it is preferable to mix them immediately before use. As a more preferred dividing method, the container (C) / (A) +
(B) + (D) container, (C) container / (A) + (B)
+ (D) + (E) container, (C) container / (A) +
(B) + (D) + (E) + (F) container, (C) container / (A) + (B) + (D) + (F) container, (C) container / (A) ) + (B) + (D) container / (G) container,
(C) container / (A) + (B) + (D) + (G) container, (C) container / (A) + (B) + (D) + (E) container / (G) ) Container, (C) container / (A) + (B) +
(D) + (F) container / (G) container, (C) container /
(A) + (B) + (D) container / (G) + (E) container, (C) container / (A) + (B) + (D) container /
(G) + (F) containers and the like can be mentioned, and it is preferable to mix and use the components stored separately just before use.

The dental adhesive composition of the present invention may contain a coloring agent such as a dye or a pigment for coloring a cured product. It is preferable to color the cured product, particularly when used as a coating material applied directly to the tooth surface. That is, after the cavity formed for removing the worm teeth is coated with the curable composition of the present invention on the surface of the dentin to form a cured film, and then temporarily filled into the cavity. Apply sealing material. At a later date, when the temporary sealing material is removed, the temporary sealing material and foreign matter may remain, and if the coating film is colored, there is an advantage that the coating film can be visually confirmed easily.

Hereinafter, the dental adhesive coating material of the present invention will be described in detail with reference to examples, but the present invention is not limited to the examples.

(Measurement of Brinell Hardness) In the present invention,
Brinell hardness is measured using a micro-Brinell hardness tester according to JIS-
It measured according to Z-2243. However, the sample used was produced by the following procedure. That is, the component (D) among the components constituting the curable composition is used in a state where it is substantially evaporated and removed by air blow. However, in order to carry out the Brinell hardness test, the thickness of the sample is extremely large as compared with the state actually used, so that it is extremely difficult to remove the component (D). In this test, a curable composition containing no aqueous solvent as the component (D) was prepared in advance to prepare a cured product sample, which was then used in the test.

(Adhesion operation to tooth substance 1) A fresh bovine mandibular front tooth was extracted, frozen in water and stored, and used as a tooth substance sample. Rotary grinder ECOMET so that the thawed bovine teeth can be exposed with fresh enamel or dentin
-III (manufactured by BUEHLER) was injected with water and polished to a water-resistant emery paper # 80 under acupressure to obtain a smooth surface. The ground beef was once removed with a pneumatic gun to remove moisture, and immediately a cellophane tape having a circular hole with a diameter of 4.8 mm was stuck thereon to define an adhesion area.

As the composition of the present invention, immediately before use, a component comprising a container containing a mixture of components other than the component (C) and a catalyst (Super Bond C & B Catalyst, Sun Medical) container as the component (C). Were mixed at the weight ratios shown in the table of Examples. 3 ~ by one sponge
Stir quickly for 5 seconds. Using the used sponge, a large amount was applied to the dentin whose area was defined, and the mixture was allowed to stand for 30 seconds. Excess liquid was blown off while gently blowing air. When light irradiation was not performed, the curable composition of the present invention was cured by being left standing for 3 minutes. At this time, the coating thickness of the cured product was about 30 μm. In the case of performing light irradiation, an excess liquid is blown off, and then a visible light irradiator (Tra
(nslux CL, Kulzer) for 20 seconds to cure the curable composition. A piece of cardboard having an inner diameter of 5.1 mm and a thickness of 1 mm with an adhesive material on one side was fixed and fixed. The hole was filled with a composite resin (Epic-TMPT, Sun Medical) and covered with a polyester film having a thickness of 50 μm. From above the film, use a visible light irradiator (Translux CL, Kulzer) for 40 minutes.
After the composite resin was cured by irradiating with light for 2 seconds, the film was peeled off, and an acrylic rod was planted with Metafast (Sun Medical) and allowed to stand for 15 minutes.

(Operation 2 for Adhering to Teeth) A fresh bovine mandibular front tooth was extracted, frozen in water and stored, and used as a tooth sample. Rotary grinder ECOMET so that the thawed bovine teeth can be exposed with fresh enamel or dentin
-III (manufactured by BUEHLER) was injected with water and polished to a water-resistant emery paper # 80 under acupressure to obtain a smooth surface. EDTA3-2 (Dental Materials and Instruments, Vol. 6, No. 1,
23-36, 1987) was applied in a sufficient amount with a sponge S, washed with water after 10 seconds for both enamel and dentin, and dried by air blowing. A cellophane tape having a circular hole of 4.8 mm in diameter for defining an adhesion area was attached to the surface to which the etching material was applied.

As the composition of the present invention, immediately before use, a component comprising a container containing a mixture of components other than the component (C) and a catalyst (Super Bond C & B Catalyst, manufactured by Sun Medical) container as the component (C). Were mixed at the weight ratios shown in the table of Examples. 3 ~ by one sponge
Stir quickly for 5 seconds. Using the sponge used, a large amount was applied to the dentin whose area was regulated, and allowed to stand for 30 seconds. Thereafter, excess liquid was blown off while lightly blowing air. When light irradiation was not performed, the curable composition of the present invention was cured by being left standing for 3 minutes. At this time, the coating thickness of the cured product was about 30 μm. In the case of performing light irradiation, an excess liquid is blown off, and then a visible light irradiator (Tra
(nslux CL, Kulzer) for 20 seconds to cure the curable composition. A piece of cardboard having an inner diameter of 5.1 mm and a thickness of 1 mm with an adhesive material on one side was fixed and fixed. The hole was filled with a composite resin (Epic-TMPT, Sun Medical) and covered with a polyester film having a thickness of 50 μm. From above the film, use a visible light irradiator (Translux CL, Kulzer) for 40 minutes.
After the composite resin was cured by irradiating with light for 2 seconds, the film was peeled off, and an acrylic rod was planted with Metafast (Sun Medical) and allowed to stand for 15 minutes.

After performing the above two bonding operations, 37
The sample was immersed in water at 24 ° C. for 24 hours, taken out, and subjected to a tensile test at room temperature within 30 minutes using a Shimadzu Autograph at a crosshead speed of 2 mm / min.

[0050]

EXAMPLES Examples are shown in Tables 1, 2 and 3. The mixtures of the components (A) and (B) described in Examples 1 to 20 all had a solubility in water of less than 5% by weight.
In Examples 1 to 10 and 14 to 19, as a method of storing by dividing, the container of (C) / a container containing a mixture of components other than (C) is divided into two parts. (C) container / (A) + (B) + (D) + (E)
+ The container of (F) / the container containing the other and / or the component of (G) was divided into three parts.

In Examples 1 to 2 and 7 and 8, the adhesive composition of the present invention was allowed to stand for 3 minutes without irradiation with light, and then filled with a composite resin and cured as described above. In Examples 3 to 6, the adhesive composition of the present invention was irradiated with light, and the composite resin was immediately cured as described above. () Shows parts by weight of each component contained in the composition of the present invention.

[0052]

[Table 1]

[0053]

[Table 2]

[0054]

[Table 3]

E: enamel D: dentin 4-META: 4-methacryloxyethyl trimellitic anhydride 4-MET: 4-methacryloxyethyl trimellitic acid PSMR-M: 2-methacryloxyethyl acid diphosphate MMA: methacryl Methyl acrylate 2.6E: Condensation product of 1 mol of ethylene oxyto adduct of bisphenol A and 2 mol of methacrylic acid (the number of addition chains of ethylene oxytom: m + n = 2.6) UDMA: 1 mol of 2,2,4- (or 2, Adduct of 4,4-) trimethyl-1,6-hexamethylene diisocyanate and 2 mol of 2-human peroxyethyl (meth) acrylate HPPM: 2-human peroxy-3-phenoxypropyl methacrylate 3G: triethylene glycol methacrylate TBB: tributyl Partial oxide of borane (Super Copper C & B, catalyst) CQ: d, l-camphaquinone TMDPO: 2,4,6-trimethylbenzene Distearate phenylphosphine oxy preparative Bu DMABA-BE: N, N- di-methylamino benzoic acid n- Bed Tokishiechiru dsNA: Dode sill sodium sulfate R812: silica, SiO ₂ content of 99.8%, average particle size 7 ×
10 ^-3 μm

 ──────────────────────────────────────────────────続 き Continuing on the front page (72) Inventor Tetsuya Toida 571-2 Furutakacho, Moriyama City, Shiga Prefecture Inside (72) Inventor Shozo Arata 571-2 Furutakacho, Moriyama City, Shiga Prefecture Sun Medical Corporation (72) Inventor Hideyuki Ueki 571-2 Furutakacho, Moriyama City, Shiga Prefecture Inside Sun Medical Co., Ltd.

Claims (12)

[Claims] (1) 1 to 50 parts by weight of a radical polymerizable monomer having an acidic group or a salt thereof in a molecule, (B) 1 to 70 parts by weight of a radical polymerizable monomer, and (C) a boron-containing monomer. A dental adhesive composition comprising 1 to 60 parts by weight of a polymerization initiator and 1 to 70 parts by weight of (D) water, and wherein the total of the components (A) to (D) is 100 parts by weight. 2. 0.001 parts by weight of (E) a water-miscible organic solvent and / or (F) a photopolymerization initiator, based on 100 parts by weight of the total of components (A) to (D). ~
The dental adhesive composition according to claim 1, which is contained in an amount of 5 parts by weight. 3. The dental adhesive composition according to claim 1, further comprising (G) 0.1 to 25 parts by weight of a filler based on 100 parts by weight of the total of components (A) to (D). . 4. The solubility of water in a mixture comprising components (A) and (B) in water is less than 5% by weight.
A dental adhesive composition according to item 1. 5. The component (A) is a polymerizable monomer containing at least one acid group or acid anhydride selected from a carboxylic acid and / or an anhydride thereof, a phosphoric acid group and a sulfonic acid group. Item 5. The dental adhesive composition according to any one of Items 1 to 4. 6. The dental adhesive composition according to claim 1, wherein the component (B) has a solubility in water of less than 5% by weight. 7. The component (B) is represented by the following formula (1): 7. The dental adhesive composition according to claim 1, wherein R ¹ is H or CH ₃ and R ² is a phenyl group or a naphthyl group. 8. The dental adhesive composition according to claim 1, wherein the component (C) is a di- or tri-alkylborane and / or a partial oxide thereof. 9. The method according to claim 2, wherein the component (E) is at least one water-miscible organic solvent selected from ethanol, propanol, acetone, methyl ethyl ketone, tetrahydrofuran, and dimethyl sulfoxide. Dental adhesive composition. 10. The dental according to claim 2, wherein the component (F) is at least one photosensitizer selected from (f1) an α-ketocarbonyl compound and (f2) an acylphosphine oxide compound. Adhesive composition. 11. The dental adhesive composition according to claim 10, wherein the component (F) further contains (f3) an amine compound. 12. The dental adhesive composition according to claim 1, wherein the cured product has a Brinell hardness of 7 or more.