JP3526589B2 - Surface coating material with adhesive properties to teeth - Google Patents

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION The present invention, in performing repair and protection of biological hard tissues represented by tooth and bone surface coating material for forming a coating on hard tissue surfaces and it
Concerning product kit including . More specifically, when a hard tissue, particularly a tooth, is bonded to a dental restoration resin such as PMMA-based resin, bonding material, resin cement, composite resin, etc., a film is previously formed on the surface of the hard tissue to provide strong adhesion and sealing property. surface coating material for imparting and it
Related to the product kit .

[0002]

2. Description of the Related Art In dental treatment, it is important to strongly bond a tooth material and a restorative material without a gap. But,
Many of the adhesives that have been proposed so far have insufficient adhesion and sealing properties to the tooth structure, and thus a gap is created between the tooth structure and the adhesive material, resulting in irritation to the pulp, secondary caries and There were problems such as causing coloring and the restoration coming off.

In order to strongly bond the tooth material and the restorative material, it is necessary to ensure that the adhesive material for bonding the both is sufficiently hardened and then hardened. In the restoration of teeth, since the adhesive material itself has low abrasion resistance, it is desirable that the thickness of the adhesive material be as thin as possible, especially in the restoration margin portion.

Many of the adhesives that have been proposed so far do not have sufficient penetrability into the tooth structure, and are unfortunately anaerobic. In the air, the polymerization is suppressed by the influence of oxygen and the curability is lowered. This becomes more remarkable as the thickness of the adhesive material becomes thinner. Further, in the repair using a visible light curable composite resin, which has become popular as a resin for restoration in recent years, if the filled composite resin is cured before the adhesive is cured, the adhesive shrinks due to polymerization shrinkage of the composite resin. It peels off from the surface
There is a problem that the expected adhesive strength and sealing property cannot be obtained.

Etching (Buonocore, MG, J. Dent. Res.,
34, 849-853, 1955) and primer treatment (Munksg
aad, EC, Asmussen, J. Dent. Res., 63, 1087-108
9, 1984, and Japanese Patent Laid-Open No. 63-279851). It is presumed that the etching treatment has an effect of removing a layer of cutting scraps (smear layer) adhered to the surface when removing a beetle by cutting and allowing the adhesive to sufficiently contact and penetrate into the tooth structure. Also,
It is speculated that the primer treatment has an effect of improving the wettability so that the adhesive easily penetrates into the tooth structure.

Although the improvement of the adhesive force is recognized by the etching treatment and the primer treatment on the tooth surface, it has not yet reached the clinically satisfactory performance. Since the etching of dentin facilitates the transmission of external stimuli to the pulp, contacting the etched dentin surface with cold / warm water, a primer, or an adhesive may cause a great pain to the patient. . It is speculated that the cause of this pain is that the dentin covered by the smear layer is exposed by etching, and the myriad dentinal tubules leading to the pulp in the dentin are largely opened at the surface (Takahashi). Kazuto, Yoshiaki Kishi, the Quintessence, 11 (3), 513-520,
1992). Therefore, in the adhesion to dentin, when the etching treatment is performed, the adhesion is improved, but there is a problem that the pulp is easily stimulated during the adhesion operation.
Furthermore, in such a method the bonding operation is etching,
Since the primer and the adhesive are sequentially brought into contact with the tooth structure and the restorative material such as composite resin is applied,
There was a problem that restoration treatment was time-consuming.

As a method for improving the peeling of the adhesive due to polymerization shrinkage of the composite resin, a method of pre-curing the visible light curable adhesive before filling the composite resin has been attempted. However, this method has a problem that the adhesive material must be thick because the polymerization is inhibited by oxygen in the air.

[0008] The Applicant has found that the adhesion to the tooth structure is preferably completed before the filling of the composite resin, for which purpose it is preferable to use a high molecular polymer capable of reacting with the tooth structure component. I found it. That is, there is proposed a surface treatment agent which forms a film of a high-molecular polymer which adheres to the surface of dentin, particularly dentin, without relying on the polymerization of a monomer, before applying the adhesive (Japanese Patent Laid-Open No. 62-62160). -33
No. 109). When the etching treatment or covering is carried out based on the proposal, the above-mentioned polymer film is formed on the surface of the dentin to seal the dentinal tubule, and further the adhesive force with the adhesive resin can be improved. Kinoshita et al. Also investigated and reported the dentin adhesion of such polymers using various dental resins (Dental Materials and Instruments, 8 (6), 913-9).
29, 1989 or 9 (1), 86-101, 1990). According to this report, dentinal tubules can be blocked by reacting with calcium components in the dentin and becoming insoluble in water and deposited on the surface to form a film. Therefore, the irritation generated when the adhesive resin is applied is reduced, and the adhesive force can be improved. However, since the treatment agent is applied to the tooth surface and then rinsed with water, the coating may be insufficiently formed depending on the method of washing and the surface roughness. In the case of covering without water washing, the treatment agent was applied and dried as it was, so the film formation was sufficient, but the high solubility of the film in water reduced the strength and resulted in insufficient adhesion. there were.

[0009]

SUMMARY OF THE INVENTION An object of the present invention is to solve the above problems in the prior art, and to cover the dentin surface and bond the curable composition without opening the dentinal tubule. An object is to provide an effective surface coating material and a method of using simple adhesion.

[0010]

According to the present invention, the above objects and advantages of the present invention are (A) a high molecular polymer having a sulfonic acid group in the molecule, (B) a polymerizable monomer and ( C) A surface coating material (first invention) having adhesiveness to a living hard tissue containing water or a mixed solvent of water and an organic solvent miscible with water (first invention) or (A) containing a sulfonic acid group in the molecule Polymeric polymer, (B) polymerizable monomer (C) water or a mixed solvent of water and an organic solvent that can be mixed with water, and (D) a surface having adhesion to a living hard tissue containing a polymerization initiator This is achieved by the coating material (second invention).

That is, the present invention coats the surface of dentin by forming a coating containing a polymer having a sulfonic acid group in the molecule and a polymerizable monomer on the surface of dentin, particularly dentin. The present invention provides a surface coating material having adhesiveness to a living hard tissue such as dentin, which can adhere an adhesive resin strongly and easily by this coating, and a product kit containing the surface coating material. .

The surface coating material of the present invention is preferably brought into contact with the surface of the tooth as it is, but the tooth surface is previously treated with an etching agent such as an aqueous solution of phosphoric acid, an aqueous solution of citric acid containing a metal salt or an aqueous solution of EDTA. It can also be used afterwards. At that time, an aqueous solution containing ferric chloride and citric acid is preferably used as the etching agent.

In the surface coating material of the present invention, the component (A) is a polymer having a sulfonic acid group in the molecule.
Such high molecular weight polymer is average molecular weight flat is preferably not more than 5,000. The component (A) has a reactivity or a binding property with respect to the tooth surface and has a high molecular weight, so that it plays a role of forming a film on the tooth surface. Therefore,
Examples thereof include natural high molecular weight compounds such as cellulose derivatives and protein derivatives, or synthetic high molecular weight compounds, and further, suspension polymers and emulsion polymers.

When high adhesion to the tooth structure is required for a long period of time, the component (A) simultaneously contains a vinyl monomer unit having a sulfonic acid group and a vinyl monomer unit having no sulfonic acid group. It is preferably a copolymer. Above all, a copolymer of alkyl ether (meth) acrylate and styrene sulfonic acid is particularly preferable.

[0015] As a method for producing a polymer containing a scan sulfonic acid group, for example a sulfonic acid or a pre-co-alone polymerizable monomer having a salt thereof, or other copolymerizable polymerizable monomer It can be isolated after polymerization. Examples of the polymerizable monomer having a sulfonic acid group that can be used here include styrene sulfonic acid and 2-acrylamide 2
-Methyl propane sulfonic acid, allyl sulfonic acid and their metal salts and ammonium salts can be mentioned. As the polymerizable monomer that can be copolymerized with the polymerizable monomer containing a sulfonic acid group, a polymerizable monomer containing a polymerizable group in the molecule is preferable, and further hydroxyl group, carboxylic acid group, phosphoric acid group , Aliphatic and aromatic polymerizable monomers which may contain functional groups such as amino groups and amide groups.

Specific examples of these monomers include aliphatic (meth) acrylates such as methyl (meth) acrylate (MMA), ethyl (meth) acrylate, propyl (meth) acrylate, and butyl (meth) acrylate. ) Acrylic acid esters; styrenes such as styrene and α-methylstyrene; N, N-dimethyl (meth) acrylamide, N, N-
(Meth) acrylamides such as diethyl (meth) acrylamide and N-isopropyl (meth) acrylamide; carboxylic acid group-containing (meth) acrylates such as (meth) acrylic acid and β- (meth) acryloyloxyethyl hydrogen succinate; Examples thereof include 2-hydroxyethyl (meth) acrylate, 2 or 3-hydroxypropyl (meth) acrylate, hydroxyl group-containing (meth) acrylates such as methylol (meth) acrylamide, and (meth) acrylamides. These monomers can be used in combination.

More preferably, as the component (A), the method already reported [Nakabayashi et al., Dental materials and instruments, 6
(6), 873-876, 1987 or Kinoshita et al., Dental Materials and Instruments, 8 (6), 913-921, 1989 and Yamamoto et al., Polymers, 49 (2), 119-12.
3, 1992], and is a sulfonic acid group-containing polymer having an average molecular weight of 5,000 or more, which is a polymer obtained by radically polymerizing the above monomer in advance.

Part of the sulfonic acid group in the component (A) forms a salt with a monovalent cation such as sodium, potassium and ammonium, or a polyvalent cation such as calcium, magnesium, copper, aluminum or iron. You can also

In the surface coating material of the present invention, the component (B) is a polymerizable monomer. The polymerizable group of such a monomer is, for example, (meth) acryloyl group, styryl group, vinyl group,
Examples thereof include radically polymerizable unsaturated groups having an allyl group and the like, and it is sufficient that at least one unsaturated group is contained in one molecule. Monofunctional monomers, difunctional monomers and trifunctional monomers are preferably used as the polymerizable monomers containing one, two and three of the above-mentioned polymerizable groups in one molecule, respectively. Furthermore, these polymerizable monomers can contain functional groups such as a carboxyl group, a phosphoric acid group, a sulfonic acid group, a hydroxyl group, an amino group and a glycidyl group in the molecule.

Examples of the polymerizable monomer that can be used as the component (B) include methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, and neopentyl glycol diester. Aliphatic esters of (meth) acrylic acid such as (meth) acrylate and trimethylolpropane tri (meth) acrylate; 2-hydroxyethyl (meth) acrylate, 2 or 3-propyl (meth) acrylate, glycerol mono (meth) acrylate Acrylate, diethylene glycol mono (meth) acrylate, triethylene glycol mono (meth) acrylate, pentaethylene glycol mono (meth) acrylate, polyethylene glycol mono (meth) acrylate, 2-hydroxy-3-phenoxypropyl (meth) acrylate (Meth) acrylates containing hydroxyl groups such as adducts of lylate, 1 mole of bisphenol A and 2 moles of glycidyl (meth) acrylate; (meth) acrylamides containing hydroxyl groups such as methylol (meth) acrylamide; ethylene glycol di ( Polyethylene such as (meth) acrylate, diethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, pentaethylene glycol di (meth) acrylate, nonaethylene glycol di (meth) acrylate, tetradecaethylene glycol di (meth) acrylate Glycol di (meth) acrylates; propylene glycol di (meth) acrylate, dipropylene glycol di (meth) acrylate,
Polypropylene glycol di (meth) acrylates such as tripropylene glycol di (meth) acrylate and nonapropylene glycol di (meth) acrylate;
Mono (meth) acrylates in which the (meth) acryloyl group of either one of the above polyethylene glycol di (meth) acrylate and polypropylene glycol di (meth) acrylate is substituted with a methyl group, an ethyl group, etc .; 2- (meth ) Acryloyloxyethyl isocyanate or 2,2,4-trimethylhexamethylene diisocyanate or an adduct of 1,3,5-trimethylhexamethylene diisocyanate and 2-hydroxyethyl (meth) acrylate (meth) acrylate having a urethane bond 2,2-bis (4- (meth) acryloyloxypolyethoxyphenyl) propanes obtained by further condensing (meth) acrylic acid to the product obtained by adding oxyethylene to bisphenol A can be exemplified. These polymerizable monomers can be used alone or in combination.

As the polymerizable monomer having at least one carboxyl group in one molecule which can be used as one kind of the component (B), monocarboxylic acid, dicarboxylic acid, tricarboxylic acid and tetracarboxylic acid or derivatives thereof Can be mentioned. For example, (meth) acrylic acid, maleic acid, p-vinylbenzoic acid, 11- (meth) acryloyloxy-1,1-undecanedicarboxylic acid (MA
C-10), 1,4-di (meth) acryloyloxyethylpyromellitic acid, 6- (meth) acryloyloxyethylnaphthalene-1,2,6-tricarboxylic acid, 4-
(Meth) acryloyloxymethyl trimellitic acid and its anhydride, 4- (meth) acryloyloxyethyl trimellitic acid and its anhydride, 4- (meth) acryloyloxybutyl trimellitic acid and its anhydride,
4- [2-hydroxy-3- (meth) acryloyloxy] butyl trimellitic acid and its anhydride, 2,3-
Bis (3,4-dicarboxybenzoyloxy) propyl (meth) acrylate, N, O-di (meth) acryloyloxytyrosine, O- (meth) acryloyloxytyrosine, N- (meth) acryloyloxytyrosine,
N- (meth) acryloyloxyphenylalanine, N
-(Meth) acryloyl p-aminobenzoic acid, N- (meth) acryloyl O-aminobenzoic acid, N- (meth) acryloyl 5-aminosalicylic acid, N- (meth) acryloyl 4-aminosalicylic acid, 2 or 3 or 4 −
(Meth) acryloyloxybenzoic acid, addition product of 2-hydroxyethyl (meth) acrylate and pyromellitic dianhydride (PMDM), 2-hydroxyethyl (meth) acrylate and maleic anhydride or 3,3 ′, 4 ,
4'-benzophenone tetracarboxylic dianhydride (BT
DA) or 3,3 ', 4,4'-biphenyltetracarboxylic dianhydride addition reaction product, 2- (3,4-dicarboxybenzoyloxy) 1,3-di (meth) acryloyloxypropane, N Adduct of phenylglycine or N-tolylglycine with 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 and the like can be mentioned. Of these, 11-methacryloyloxy-1,1-undecanedicarboxylic acid (MAC-1
0), 4-methacryloyloxyethyl trimellitic anhydride (4-META) and N-methacryloyl 5-
Aminosalicylic acid (5-MASA) is preferably used. These polymerizable monomers having a carboxyl group can be used alone or in combination.

Examples of the polymerizable monomer having at least one phosphoric acid group in one molecule used as one type of component (C) 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 Alternatively, 3- (meth) acryloyloxypropyl} acid phosphate, 2- (meth) acryloyloxyethylphenyl acid phosphate, 2- (meth) acryloyloxyethyl p-methoxyphenyl acid phosphate and the like can be mentioned. The phosphate group in these compounds can be replaced with a thiophosphate group.
Among these, 2- (meth) acryloyloxyethyl phenyl acid phosphate and 10- (meth) acryloyloxydecyl acid phosphate are preferably used. These polymerizable monomers having a phosphoric acid group can be used alone or in combination.

As the polymerizable monomer having at least one sulfonic acid group in one molecule used as one type of the component (B), 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-
Examples thereof include propyl (meth) acrylate, 3-methoxy-1-sulfo-2-propyl (meth) acrylate, and 1,1-dimethyl-2-sulfoethyl (meth) acrylamide. Of these, 2-methyl-2-
(Meth) acrylamide propane sulfonic acid is preferably used. These polymerizable monomers having a sulfonic acid group can be used alone or in combination.

As the component (B), the above polymerizable monomers can be used alone, but can also be used in combination.

In the surface coating material of the present invention, the component (C) is water or an aqueous solvent. As the component (C),
It is a solvent in which water is used alone or mixed with an organic solvent that can be mixed with water. Examples of water that can be used here include distilled water, ion-exchanged water and physiological saline, and distilled water and ion-exchanged water are preferably used here. Further, as the above-mentioned organic solvent that can be mixed with water, those that uniformly dissolve or disperse the components (A) and (B) are particularly preferably used. For example, alcohols such as methanol, ethanol and propanol;
Examples thereof include ketones such as acetone and methyl ethyl ketone; ethers such as tetrahydrofuran (THF); amides such as N, N-dimethylformamide. Of these, ethanol and acetone are preferably used. Of these water-based solvents, it is particularly preferable to use water alone or a mixed solution of water and ethanol or acetone in consideration of toxicity and irritation to a living body when used for teeth.

The surface coating material according to the first aspect of the present invention is based on the total weight of the components (A), (B) and (C) for each of the components (A), (B) and (C). Then, the component (A) is 0.1 to 70 parts by weight, and the component (B) is 1
To 95 parts by weight and (C) component in the range of 1 to 95 parts by weight. More preferably (A)
The components are used in the range of 1 to 30 parts by weight, the component (B) in the range of 3 to 80 parts by weight, and the component (C) in the range of 1 to 50 parts by weight.

In the second invention of the present invention, the above (A),
In addition to the components (B) and (C), a polymerization initiator (D)
Used as an ingredient. Examples of such a polymerization initiator include diacetyl peroxide, dipropyl peroxide, dibutyl peroxide, dicapryl peroxide,
Dilauryl peroxide, dilauryl peroxide, benzoyl peroxide (BPO), p, p'-dichlorobenzoyl peroxide, p, p'-dimethoxybenzoyl peroxide, p, p'-dimethylbenzoyl peroxide,
Examples thereof include organic peroxides such as p, p'-dinitrodibenzoyl peroxide. Of these,
BPO is preferred. Further, there may be mentioned inorganic peroxides such as ammonium persulfate, potassium persulfate, potassium chlorate, potassium bromate and potassium perphosphate.

The polymerization can also be carried out by irradiating with ultraviolet rays or visible rays. There are no particular restrictions on the polymerization initiator that can be used in such photopolymerization, but for example, benzyl, 4,4′-dichlorobenzyl, benzoin, benzoin methyl ether, benzoin ethyl ether,
Benzoin isopropyl ether, benzophenone,
Examples thereof include ultraviolet or visible light sensitizers such as 9,10-anthraquinone, diacetyl and camphorquinone (CQ).

When an organic peroxide or a photopolymerization initiator is used, for example, N, N-dimethylaniline, N, N-dimethyl p-toluidine (DMPT), N, N-diethyl p-toluidine, N, N- Diethanol p-toluidine, N, N-dimethyl p-tert-butylaniline,
N, N-dimethylanisidine, N, N-dimethyl p-chloroaniline, N, N-dimethylaminoethyl (meth) acrylate, N, N-diethylaminoethyl (meth) acrylate, N, N-dimethylaminobenzoic acid and The alkyl ester thereof, N, N-diethylaminobenzoic acid and the alkyl ester thereof, and aromatic amines such as N, N-dimethylaminobenzaldehyde can be used in combination. In addition, aromatic sulfinic acid or salts thereof such as benzenesulfinic acid, o-toluenesulfinic acid, p-toluenesulfinic acid, ethylbenzenesulfinic acid, decylbenzenesulfinic acid, dodecylbenzenesulfinic acid, chlorobenzenesulfinic acid, and naphthalenesulfinic acid are used. It can also be used together.

In addition, trialkylboron or its partial oxide can be used. Specifically, trialkyl boron, tripropyl boron, triisopropyl boron, tri-n-butyl boron, tri-n-amyl boron, triamyl boron, triisoamyl boron, tri-sec-amyl boron or a part thereof. It is possible to use a trialkylboron oxide which is oxidized. Among these, tri-n-butylboron or its partial oxide is preferably used.

The surface coating material according to the second aspect of the present invention is the same as the above components (A), (B), (C) and (D), but these components (A), (B), (C) and ( Of the total weight of 100 parts by weight of component (D), component (A) is 0.1 to 7
It is preferable to contain 0 parts by weight, 1 to 95 parts by weight of the component (B), 1 to 95 parts by weight of the component (C), and 0.01 to 20 parts by weight of the component (D). More preferably, the component (A) is 1 to 30 parts by weight and the component (B) is 3 to 8 parts.
0 parts by weight, 1 to 50 parts by weight of the component (C), and (D)
The components are used in the range of 0.1 to 10 parts by weight.

The surface coating material of the present invention comprises the above (A),
In addition to the components (B), (C), and optionally (D), as a film-forming accelerator, beryllium, magnesium, calcium, alkaline earth metals such as strontium and barium, and II.
A group I metal, a group IV metal such as germanium, tin or lead, and a hydroxide, halide or oxide of a polyvalent metal such as a transition metal such as iron, copper, cobalt or nickel may be contained. .

The surface coating material of the present invention comprises the above (A),
The components (B), (C) and, optionally, the component (D) can be premixed and applied to the tooth substance. When the mixture of these 3 to 4 components changes over a long period of time and may impair the effects of the present invention, the mixture can be divided and stored. As a storage method, in the case of the surface coating material of the first invention, for example, A
/ C mixture and B divided into two, A / C mixture and B / C mixture divided or A / B / C
And a mixture of B / C and the like.
In the case of the surface coating material of the second invention, for example, A / C /
When dividing into a mixture of D and B, when dividing into a mixture of A / C / D and B / C or A / B /
Examples thereof include a mixture of C / D and a mixture of B / C. This combination is not limited to those described above.

[0034]

EXAMPLES The present invention will be described below with reference to examples, but the present invention is not limited to these examples.

[0035] Example 1 polymer having a sulfonic acid group in the molecule (A) of 33g Synthesis 2l flask p- styrene sodium sulfonate (p-SSA, Wako Pure Chemical), 144 g of methyl methacrylate (MMA , Wako Junyaku) and 2.26 g of 2,
2'-azobisisobutyronitrile under nitrogen atmosphere 1.
6 l of water / ethanol (EtOH) mixed solvent (water / E
(tOH = 1 / 0.6 volume ratio), followed by 7
The mixture was placed in a 5 ° C. oil bath and stirred for 11 hours. The solution was returned to room temperature and the EtOH content was distilled off under reduced pressure. The remaining solution was packed in a dialysis tube (Union Carbide, Sanko Junyaku) and dialyzed in ion-exchanged water for 3 days. Collect the solution in the tube and collect 1.5 Kg of ion exchange resin (Amberlite I
It was desalted by passing through a column packed with R-118, organo).
Water was distilled off to obtain the desired polymer. The obtained polymer is
1H-NMR, elemental analysis and GPC analysis were performed, and a methyl methacrylate-p-styrene sulfonic acid copolymer having a number average molecular weight of 100,000 or more (MMA content of about 90 mol%, hereinafter abbreviated as copolymer A) ) Was confirmed.

In the examples, the adhesive strength and the closed state of the dentinal tubules were evaluated as follows.

Example 2 Evaluation of Adhesion Strength Fresh bovine lower anterior teeth were extracted, frozen and stored in water, and used as a dentin sample. The thawed bovine tooth enamel and dentin were removed using the rotary polishing machine ECOMET-III (BUE
HLER) was used for water injection and water-resistant emery paper No. 600 was ground under finger pressure to obtain a smooth surface. The ground bovine tooth was immersed in 37 ° C. water for 15 minutes. The bovine tooth was removed from the water and the water was removed with an air gun. The surface coating material of the present invention was applied to the ground surface with a sponge, allowed to stand for 15 seconds, and dried by blowing air with an air gun for about 20 seconds. The surface coated with the surface coating material was observed with an optical microscope, and it was confirmed that the surface treatment material completely covered the tooth surface. A double-sided pressure-sensitive adhesive tape having a circular hole with a diameter of 5.1 mm was fixed on this to define the adhesion area. In Examples 4 to 9, Superbond D liner (Sun Medical), which is a dental adhesive, was applied, and the excess adhesive was removed with an air gun. In addition, place a 1 mm thick cardboard with a 5.1 mm diameter circular hole and fix it, and put the composite resin (Silux Pl
us, 3M). Visible light irradiator (Translux CL, Kul
zer) to irradiate light for 60 seconds to cure the composite resin, and then an acrylic rod was adhered with Metafast (Sun Medical) and left standing for 15 minutes. After being immersed in 37 ° C. water for 24 hours, a tensile adhesion test (crosshead speed 2 mm / min) was performed. Examples 10-12
Then, instead of using the Superbond D liner and the composite resin among the above methods, the prototype visible light-curable resin cement is a powder agent and a liquid agent used in Chemieace (Sun Medical) of the dental composite resin cement. As 65 parts by weight of HEMA, 35 parts by weight of 2,2,4-trimethylhexamethylenediamine dimethacrylate (UDMA), 0.5 parts by weight of d, -camphaquinone (CQ) and 0.5 parts by weight of N, A solution consisting of N-diethylaminobenzoic acid (DEABA) was kneaded at a weight ratio of 1: 1 and filled with the mixture within 2 minutes to a thickness of 50 μm.
m polyester film. Then, light irradiation was performed for 60 seconds from above. Regarding Example 13, except that the composite resin (Silux Plus, Universal) was directly filled instead of the visible light curable resin cement,
The adhesive strength was evaluated in the same procedure as in Examples 10-12.

Example 3 Evaluation of closed state of dentinal tubules In order to investigate the state of film formation on the dentin surface of the surface coating material of the present invention, the closed state of dentinal tubules on the dentin surface after the coating material treatment. Was observed with an optical microscope.

Example 4 10 parts by weight of the copolymer A of Example 1 as a surface coating material
And a solution consisting of 50 parts by weight of water and 10 parts by weight of 2-hydroxyethyl methacrylate (HEMA) was used. It can be visually confirmed that the film is well formed, and it has tackiness (stickiness). Observation with an optical microscope revealed that the dentinal tubule had no opening and was in a good closed state.
As a result of the adhesion test, the adhesion strength to dentin is 99 ± 17.
It was kgf / cm ² , and it was cohesive failure of the surface coating material.

Example 5 10 parts by weight of the copolymer A of Example 1 as a surface coating material
And a solution of 40 parts by weight of water, 50 parts by weight of EtOH, 10 parts by weight of triethylene glycol dimethacrylate (3G) and 3 parts by weight of 4-MATA was used.
The formation of the film was good by visual observation, and good blockage of the dentinal tubule was confirmed by an optical microscope. As a result of the adhesion test, the adhesion strength to dentin was 49 ± 10 kgf / cm ² , which was cohesive failure of the surface coating material.

Example 6 10 parts by weight of the copolymer A of Example 1 as a surface coating material
And a solution consisting of 40 parts by weight of water, 50 parts by weight of EtOH and 3 parts by weight of 4-MATA was used. The formation of the film was good by visual observation, and good blockage of the dentinal tubule was confirmed by an optical microscope. As a result of the adhesion test, the adhesion strength to dentin was 46 ± 6 kgf / cm ² , which was cohesive failure of the surface coating material.

Example 7 10 parts by weight of the copolymer A of Example 1 as a surface coating material
And a solution consisting of 40 parts by weight of water, 50 parts by weight of HEMA, 10 parts by weight of 3G and 3 parts by weight of 4-MATA were used. The formation of the film was good by visual observation, and good blockage of the dentinal tubule was confirmed by an optical microscope. As a result of the adhesion test, the adhesion strength to dentin is 68 ± 16 kgf / cm
² , which was cohesive failure of the surface coating material.

Example 8 10 parts by weight of the copolymer A of Example 1 as a surface coating material
And a solution consisting of 40 parts by weight of water, 50 parts by weight of HEMA and 3 parts by weight of 4-MATA was used. The formation of the film was good by visual observation, and good blockage of the dentinal tubule was confirmed by an optical microscope. As a result of the adhesion test, the adhesion strength to dentin was 66 ± 16 kgf / cm ² , which was cohesive failure of the surface coating material.

Example 9 10 parts by weight of the copolymer A of Example 1 as a surface coating material
And a solution consisting of 40 parts by weight of water and 10 parts by weight of methoxynonaethylene glycol monomethacrylate (M90G). The formation of the film was good by visual observation, and good blockage of the dentinal tubule was confirmed by an optical microscope. As a result of the adhesion test, the adhesion strength to dentin is 49 ± 8 kg.
The f / cm ² was cohesive failure of the surface coating material.

Comparative Example 1 Bonding without using a surface coating material in Example 4 revealed that the bond strength to dentin was 18 ± 14 kgf / cm.
^{Was 2} .

Comparative Example 2 In Example 4, a solution comprising 65 parts by weight of water and 35 parts by weight of HEMA was used without using the copolymer A as the surface coating material. No film was confirmed by visual observation or observation with an optical microscope, and no difference from the untreated surface was observed. Adhesive strength to dentin is 36 ± 20
It was kgf / cm ² .

Comparative Example 3 In Example 4, 10 parts by weight of the copolymer A of Example 1, 40 parts by weight of water and 50 parts by weight of EtOH were used without using a polymerizable monomer as the surface coating material. The solution was used. Although the formation of the film was visually confirmed, it was not tacky. Adhesion strength to dentin is 17 ± 4k
It was gf / cm ² .

Comparative Example 4 As an example of the prior art, a commercially available photo bond (Kuraray Co., Ltd.) was used, and according to the manufacturer's instructions, a photo bond as an adhesive was applied after etching, and a composite resin was applied to the dentin surface of the bovine tooth. Glued. The dentinal tubules were large open on the surface of the etched dentin in the scanning electron microscope. The adhesive strength was 44 ± 18 kgf / cm ² .

Comparative Example 5 As an example of the prior art, a commercially available Scotchbond II (3M
The composite resin was adhered to the dentin surface of bovine teeth by applying Scotch prep as a primer and Scotch bond 2 as an adhesive according to the manufacturer's instructions. The adhesive strength was 22 ± 5 kgf / cm ² .

The results of Examples 4 to 9 and Comparative Examples 1 to 5 are summarized in Table 1.

[0051]

[Table 1]

COPOLY-A: Polymer (A) having a sulfonic acid group in the molecule, HEMA: 2-hydroxyethyl methacrylate, EtOH: ethanol, 3G: triethylene glycol dimethacrylate, 4-META: 4-methacryloyloxyethyl Trimellitic anhydride, M90G: methoxynonaethylene glycol methacrylate

Example 10 As a surface coating material, 10 parts by weight of the copolymer A of Example 1 was used.
And 40 parts by weight of water, 10 parts by weight of triethylene glycol dimethacrylate (3G), 50 parts by weight of 2-hydroxyethyl methacrylate (HEMA) and 0.1 parts by weight of d, l- which is a visible light polymerization initiator. A solution consisting of camphorquinone was used. It can be visually confirmed that the film is well formed, and it has tackiness (stickiness). Observation with an optical microscope revealed that the dentinal tubule had no opening and was in a good closed state. As a result of the adhesion test using resin cement, the adhesion strength to dentin is 165 ± 13k.
It was gf / cm ² , and all were cohesive failure of the resin cement.

Example 11 10 parts by weight of the copolymer A of Example 1 as a surface coating material
And 40 parts by weight of water, 10 parts by weight of 3G, 50 parts by weight of H
A solution consisting of EMA, 3 parts by weight of 4-methacryloyloxyethyl trimellitic anhydride (4-MATA) and 0.5 parts by weight of CQ was used. The formation of the film was good by visual observation, and good blockage of the dentinal tubule was confirmed by an optical microscope. As a result of the adhesion test using resin cement, the adhesion strength to dentin is 75 ± 54 kgf.
/ Cm ² , which was cohesive failure of 1 part resin cement and cohesive failure of the surface coating material.

Example 12 10 parts by weight of the copolymer A of Example 1 as a surface coating material
And 40 parts by weight water, 50 parts by weight EtOH, and 10
Parts by weight of nonaethylene glycol dimethacrylate (9
A solution consisting of G) was used. The formation of the film was good by visual observation, and good blockage of the dentinal tubule was confirmed by an optical microscope. As a result of the adhesion test, the adhesion strength to dentin is 9
It was 4 ± 29 kgf / cm ² , which was cohesive failure of the surface coating material.

Example 13 10 parts by weight of the copolymer A of Example 1 as a surface coating material
And a solution consisting of 40 parts by weight of water, 50 parts by weight of HEMA, 10 parts by weight of 3G, 3 parts by weight of 4-MATA, and 0.5 parts by weight of CQ. The formation of the film was good by visual observation, and good blockage of the dentinal tubule was confirmed by an optical microscope. As a result of the adhesion test using the composite resin, the adhesion strength to dentin is 64 ± 6 kgf / c.
It was m ² , which was a cohesive failure of the surface coating material.

Comparative Example 6 In Example 10, resin cement or composite resin was adhered without using the surface coating material, but the adhesive strength to dentin was 0.

Comparative Example 7 In Example 13, 40 parts by weight of water and 50 parts by weight of H were used without using the copolymer A of Example 1 as the surface coating material.
EMA, 10 parts by weight of 3G, 3 parts by weight of 4-MATA,
And Example 7 except that a solution consisting of 0.5 parts by weight of CQ was used. The film was not confirmed by visual observation or observation with an optical microscope, and no clear difference from the untreated surface was observed. The adhesive strength to dentin was 0.

As described above, Examples 10 to 13 and Comparative Examples 6 to 7
The results are shown in Table 2 together.

[0060]

[Table 2]

COPOLY-A: Polymer (A) having a sulfonic acid group in the molecule, HEMA: 2-hydroxyethyl methacrylate, EtOH: ethanol, 3G: triethylene glycol dimethacrylate, 4-META: 4-methacryloyloxyethyl Trimellitic anhydride, 9G: nonaethylene glycol dimethacrylate, CQ: d, l-camphaquinone

[0062]

EFFECT OF THE INVENTION The surface coating material having adhesiveness to the tooth structure of the present invention can be applied to the surface of the tooth structure to form a film to protect the surface of the tooth structure. Further, this coating can strongly and easily adhere the adhesive resin to the teeth, especially dentin. Although the cause of the effect of the present invention has not been sufficiently clarified, when the surface coating material of the present invention is applied to the tooth surface, first, the high molecular polymer having a sulfonic acid group reacts and becomes insoluble on the tooth surface. Since a film containing a polymerizable monomer is deposited to form a film, the polymerizable monomer contained in the film can always be present on the surface in a certain ratio even if air is blown and dried. . If an adhesive resin is used after forming this film, the polymerizable monomer in the film is polymerized and hardened together with the adhesive resin, so it is presumed that the adhesive force between the tooth substance and the adhesive resin is improved.

─────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor Akifumi Kasagi 6-1-2 Waki, Waki-cho, Kuga-gun, Yamaguchi Prefecture Mitsui Petrochemical Industry Co., Ltd. (72) Shozo Arata Waki, Waki-cho, Kuga-gun, Yamaguchi Prefecture 6-1-2, Mitsui Petrochemical Co., Ltd. (72) Inventor Nobuo Nakabayashi 5-6-20 Koganehara, Matsudo City, Chiba (56) Reference JP-A-3-255109 (JP, A) JP Flat 3-74310 (JP, A) (58) Fields investigated (Int.Cl. ⁷ , DB name) A61K 6/083 A61K 6/00

Claims (9)

(57) [Claims] 1. (A) a polymer having a sulfonic acid group in the molecule, (B) a polymerizable monomer and (C) water or a mixed solvent of water and an organic solvent miscible with water, A surface coating material having adhesiveness to a hard tissue of a living body, which comprises: 2. When the total amount of the components (A), (B) and (C) is 100 parts by weight, the amount of the component (A) is 0.1 to 70.
The surface coating material according to claim 1, wherein the content of the component (B) is 1 to 95 parts by weight, and the content of the component (C) is 1 to 95 parts by weight. 3. The surface coating material according to claim 1, further comprising (D) a polymerization initiator. 4. When the total amount of the components (A), (B), (C) and (D) is 100 parts by weight, the amount of the component (A) is 0.1.
1 to 70 parts by weight, component (B) is 1 to 95 parts by weight, (C)
1-95 parts by weight of component, and 0.01-part of component (D)
The surface coating material according to claim 3, which is contained in a range of 20 parts by weight. 5. The surface coating material according to claim 1, wherein the component (A) has an average molecular weight of 5,000 or more. 6. The surface coating material according to claim 1, wherein the component (A) is a copolymer containing a vinyl monomer unit having a sulfonic acid group and a vinyl monomer unit having no sulfonic acid group at the same time. 7. The surface coating material according to claim 1, wherein the component (A) is a copolymer of alkyl (meth) acrylate and styrenesulfonic acid. 8. The hard tissue according to claim 1, which is divided into two or more and stored in any combination of (A), (B) and (C), and has an adhesive property. Surface coating product kit. 9. The living body hard tissue according to claim 3, wherein (A), (B), (C) and (D) are divided into two or more and stored in any combination. Adhesive surface coating product kit.