JP2003238325A - Dental adhesive composition and kit - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a dental adhesive composition, demineralizing a part or whole of a smear layer which is a ground scrapes by making a direct contact with tooth material, dispersing a sufficient adhesive component into the substrate of the tooth for exhibiting an adhesion strength and also forming a film having a necessary thickness on the surface of the tooth material. <P>SOLUTION: This dental adhesive composition consists of (A) a radically polymerizable monomer having an acid group in its molecule, (B) a polymerization initiator, (C) a reducing agent and (D) water, and contains 3-80 range pt.wt. component (A), 0.01-30 range pt.wt. component (B), 0.01-20 range pt.wt. component (C) and 10-80 range pt.wt. component (D) based on 100 pts.wt. total of (A)-(D) components. Its cured material has 15-100 range Vickers hardness. <P>COPYRIGHT: (C)2003,JPO

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a dental adhesive composition which is preferably used as a dental adhesive material and a dental coating material, and a kit thereof. More specifically, it is a dental adhesive that has excellent curability even when spread thinly in the temperature range related to the living body, humidity / wet range, and excellent in water resistance, strength, hardness, adhesion performance, color tone and storage stability of the cured product. Sex composition and its kit.
As adherends, dentin hard tissues such as enamel, dentin and cement, dental metals, ceramics such as porcelain, and dental resins such as composite resins, hard resins, denture base resins, and resin cements. The present invention relates to a curable adhesive composition that can be used as a coating material capable of forming a thin and hard coating and / or a bonding material that strongly adheres, and a dental adhesive material or a dental coating material kit.

[0002]

2. Description of the Related Art Dental adhesives, composite resins,
Curable compositions used for hard resins, denture base resins, cements, coating materials, etc. are mainly radically polymerizable monomers such as vinyl monomers typified by styrene derivatives and (meth) acrylic acid derivatives. And a large number of curable compositions comprising a polymerization initiator (sometimes referred to as a catalyst or a curing agent) for polymerizing and curing the same have been proposed.

The properties required of a curable composition for living organisms, especially for dentistry, are that the curing rate can be controlled relatively large in the temperature region and the humidity / humidity region where the living organism can be touched, and the water resistance and strength of the cured product. In addition to high hardness, high adhesion performance, and easy control of color tone, excellent performance (storage stability) in which these performances can be stored while being stably held in the packaging container for a long period of time It is that. In addition, when applied as an adhesive, the adherend may be a variety of materials such as metal, ceramics, resin before hardening or hardening (also called resin), convoygit resin, resin cement, etc. Therefore, it is required to have a performance capable of supporting these adherends. Further, in the coating material, in addition to the above performance, it may be necessary to form a thin film. Forming a thin film, and improving the mechanical strength of the cured product while exhibiting high adhesion performance is very likely to occur in a radically polymerizable composition in which polymerization is apt to be inhibited by oxygen and the polymerization does not proceed sufficiently. It was difficult.

The following proposals have been made in an attempt to achieve the above-mentioned performance improvement by using a curable composition comprising a radically polymerizable monomer and a photopolymerization initiator. Japanese Patent Publication Sho 53
JP-A-33687 and JP-B-54-10986 propose compositions comprising carbonyl compounds such as α-diketones and amines. With this composition, the color tone of the cured product was changed, and the water resistance, strength and adhesive performance were insufficient. Further, JP-A-56-120610 proposes a photocurable composition comprising a vinyl monomer having an acidic group, an α-diketone and an aromatic sulfinate. This composition was excellent in stability of color tone, but had problems in strength and adhesion durability. Japanese Patent Sho 61
JP-A-3684 proposes a composition using a monomer containing a carboxylic acid anhydride, an organic peroxide, an amine and an aromatic sulfinate. This composition did not have sufficient adhesive strength. In addition, JP-A-60-44508
JP-A No. 60-123515 and Japanese Patent Publication No. 7-2613 contain a carboxylic acid-containing monomer and an aromatic sulfinate, and further contain an amine or an α-diketone or a dialdehyde depending on the purpose. Compositions have been proposed for inclusion. Even with these compositions, sufficient adhesive strength has not been obtained. After that, Japanese Patent Fair 6-6268
In JP-A-8, a composition comprising a carboxylic acid-containing monomer, an α-diketone, an amine and an aromatic sulfinic acid (salt) is proposed, and the stability of color tone is remarkably improved, and further the adhesion and durability are improved. It was

The above-mentioned series of proposals all assume that the surface of the tooth structure is previously surface-treated with an etching composition containing an acidic compound. This etching process is a scrape layer (smear layer) that remains on the surface when tooth is ground.
Was removed to improve the adhesive strength. Furthermore, in recent years, a method has been proposed in which the curable composition is applied by surface treatment with a primer composition containing a monomer after the etching treatment or while the smear layer remains.
Such a proposal of improving the adhesive strength by applying a curable composition such as etching or a primer before applying it, on the contrary, makes the practitioner more complicated and the treatment time becomes longer, and the burden on the patient becomes larger. It was

It is generally considered that in order to firmly adhere to the tooth substance for a long period of time, it is necessary to diffuse the adhesive component even to the healthy tooth substance and surely cure the diffused portion. Has become. However, various problems are feared in an adhesive composition in which a curable composition is applied after using an etching material composition or a primer composition that has been conventionally used, or an adhesive material incorporating such a method. . For example, a bonding method consisting of a tooth-etching material and a curable composition is performed by etching for removing a smear layer (cutting scraps) generated when cutting and removing caries.
Even the healthy dentin, which we want to keep, may be invaded, leading to deterioration of the adhesion site.

On the other hand, the adhesive material for the tooth substance strongly adheres the tooth substance and the restorative material without a gap, and since it is an operation in the oral cavity, it can be completed in a simple and short time as much as possible. desirable.

[0008] The following three methods are mainly adopted as the tooth surface treatment method for firmly adhering the resin restoration material to the tooth structure. That is, firstly, an etching method in which a solution having a demineralizing property such as phosphoric acid or citric acid is applied to the surface of enamel and / or dentin, and then washed with water to wash it away, and secondly, an etching method. The etching primer method in which a primer is further applied and dried on the tooth structure after performing the above, and the third is a self-etching primer method in which a primer having a demineralizing function is applied to the tooth structure without etching. These tooth treatment methods are pretreatments when applying a material for supplementing the missing tooth and an adhesive material for adhering the tooth, that is, a bonding material or resin cement, and the pretreatment composition used here. It is not possible to firmly bond the tooth substance and the material that compensates for the defect only with the object.

Japanese Patent Publication No. 63-25562 discloses a dental material comprising a vinyl monomer having an acidic group, α-diketone, aromatic sulfinate or thiourea. Japanese Patent Application Laid-Open No. 10-245525 discloses a composition containing a specific phosphoric acid group-containing polymerizable monomer, a polyvalent carboxylic acid group-containing polymerizable monomer, and a polymerization initiator. Further, JP-A No. 11-240815 proposes a composition in which an organic solvent is used in combination.

[0010]

DISCLOSURE OF THE INVENTION An object of the present invention is to provide a dental adhesive (adhesive composition) having sufficient adhesiveness and durability to teeth and a composition and kit suitable for use as a dental coating material. To provide.

Another object of the present invention is that it is not always necessary to carry out a pretreatment such as an etching treatment or a primer treatment before using the curable composition, especially when it is used for tooth structure, It is intended to provide a composition and a kit which are preferably used as a dental adhesive or a coating material which can be directly applied to

Still another object of the present invention is to provide a sufficient amount of an adhesive component for detoxifying some or all of a smear layer, which is a grinding dust, and exerting an adhesive strength by directly contacting the dentin with a tooth component. It is an object of the present invention to provide a dental adhesive composition (hereinafter sometimes referred to as “self-etching bonding material composition”) that can diffuse into a substrate and form a coating film having a required thickness on the tooth surface.

Still another object of the present invention is to provide a dental adhesive composition in which the bonding operation is greatly simplified and simplified so that the burden on the dentist and the patient can be greatly reduced.

Still another object of the present invention is to be used as a bonding material for adhering a material having no adhesive property to the tooth substance such as a composite resin, and for the purpose of improving the tooth adhesive property of the resin cement. It can be used as a bonding material,
That is, it can be used as a coating material for protecting the surface of tooth substance, metal, ceramics, resin, etc. In particular, it can be applied to the exposed part of dentin that greatly affects the pulp (sometimes called nerve). To provide a dental adhesive composition which, when used as a coating agent, is effective not only for protection against abrasion and mechanical irritation, but also for suppressing hyperesthesia, preventing caries infection, suppressing postoperative pain, etc. It is in.

Still another object of the present invention is that when it is used as a dental coating material, it is very simple and can be operated in a short time, and can form a hard and thin film firmly bonded to the tooth structure. Since it has the advantage that it can be used, it not only functions as an adhesive that bonds other materials such as composite resin and resin cement to the dentine, but the adhesive itself has hard and strong characteristics, and its characteristics are extremely Another object of the present invention is to provide a dental adhesive composition that can exhibit even a thin film.

Still another object of the present invention is that since there are various substances in the adherend, it can be used even if the composition is subjected to etching and / or primer, which are different compositions. An adhesive composition for use is provided.

Still another object of the present invention is to provide a kit capable of stably storing the adhesive composition of the present invention for a long period of time.

Further objects and advantages of the present invention will be apparent from the following description.

[0019]

According to the present invention, the above objects and advantages of the present invention are as follows: (A) a radical polymerizable monomer having an acidic group in the molecule; and (B) a polymerization. Initiator,
Consisting of (C) reducing agent and (D) water, (A) to (D)
The component (A) is 3 to 80 per 100 parts by weight of the total components.
Parts by weight, component (B) in the range 0.01 to 30 parts by weight, component (C) in the range 0.01 to 20 parts by weight and component (D) in the range 10 to 80 parts by weight, And it is achieved by a dental adhesive composition characterized in that the cured product has a Vickers hardness of 15 to 100. In using this composition, (E) a polyfunctional radically polymerizable monomer having no acidic group may be contained, if necessary. In addition, (A) to (D) or (A) to
The mixture of the component (E) preferably undergoes phase separation at 37 ° C.

Further, (A) to (D) or (A) to
In addition to the component (E), it contains (F) a water-soluble organic solvent having a boiling point of less than 100 ° C., and preferably is in a homogeneous solution state at room temperature.

The component (F) enables the composition of the present invention to form a uniform transparent solution, and the component (F) has a boiling point of 1
By setting the temperature to less than 00 ° C., the composition of the present invention can be taken out at a constant composition ratio when the composition of the present invention is taken out from the packaging container, and when the composition of the present invention is applied, it volatilizes within a relatively short time. It has an advantage that it can be returned to a composition that can be generated and causes phase separation.

The above objects and advantages of the present invention are, secondly, as follows:
(A) Radical polymerizable monomer having an acidic group in the molecule,
Consisting of (B) a polymerization initiator, (C) a reducing agent and (D) water, per 100 parts by weight of the total of components (A) to (D),
The component (A) is in the range of 3 to 80 parts by weight, and the component (B) is 0.
The range of 01 to 30 parts by weight, the component (C) is 0.01 to 20
Parts by weight and component (D) are in the range of 10 to 80 parts by weight and the cured product has a Vickers hardness of 15 to 100.
And a dental adhesive composition kit of the present invention. When the hardness of the coating material is required, the Vickers surface hardness of the cured product is preferably high, and in view of the balance with adhesiveness, it is usually 15 to 100, preferably 20 to 20 for a coating film of 10 microns on dentin. 80 is more preferable, and 25-80 is even more preferable.

The component (A) of the present invention is a radically polymerizable monomer having an acidic group.

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, as the monofunctional polymerizable monomer having a carboxylic acid group or its anhydride group in one molecule, monocarboxylic acid, dicarboxylic acid, tricarboxylic acid, tetracarboxylic acid and polycarboxylic acid or its anhydride can be used. Can be mentioned. Examples of the compound that can be used here include the carboxylic acids and / or their anhydrides described in JP-B-6-62688. In particular, for example, (meth) acrylic acid, β- (meth) acryloxyethyl hydrogen phthalate, 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 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 trimellitate Acid and its anhydride, 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) acryloyloxytyrosine, N- (meth) acryloyloxyphenylalanine, N- (meth) acryloyl p-aminobenzoic acid, N- (meth) acryloyl O-aminobenzoic acid, N-phenylglycine or N-tolyl. An 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, addition product of 2-hydroxyethyl (meth) acrylate and pyromellitic dianhydride (PMDM), 2 mol of 2-hydroxyethyl (meth) acrylate and 1 mol of maleic anhydride or 3,3 '. Addition reaction product obtained by reacting 4,4'-benzophenone tetracarboxylic dianhydride (BTDA) or 3,3 ', 4,4'-biphenyltetracarboxylic dianhydride, 2- (3,4- Dicarboxybenzoyloxy) 1,
Examples thereof include 3-di (meth) acryloyloxypropane. Of these, 11-methacryloyloxy-1,1-undecanedicarboxylic acid (MAC-10)
And 4-methacryloyloxyethyl trimellitic acid (4-MET) or its anhydride (4-META) is preferably used.

Examples of the polymerizable monomer having at least one phosphoric acid 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 oxidedecyl acid phosphate, bis {2- (meth) acryloyloxyethyl} acid phosphate, bis {2 or 3- (meth) acryloyloxypropyl} acid phosphate, 2- (meth) acryloyl Oxyethyl phenyl acid phosphate, 2
Examples thereof include- (meth) acryloyloxyethyl p-methoxyphenyl acid phosphate. The phosphate group in these compounds can be replaced with a thiophosphate group. Examples of the polymerizable monomer having a thiophosphoric acid group include JP-A-54-21438 and JP-A-5-
9-140276 and JP-A-59-14226.
The materials described in Japanese Patent No. 8 can be used. Specific examples include the following compounds,
It may be a tautomer represented by [].

[0027]

[Chemical 1]

Of these, 2- (meth) acryloyloxyethyl phenyl acid phosphate, bis {2- (meth) acryloyloxyethyl} acid phosphate,
10- (meth) acryloyloxydecyl acid phosphate is preferably used. These polymerizable monomers having a phosphoric acid group can be used alone or in combination.
It is a polymerizable monomer having a sulfonic acid group in the molecule. Examples of such a polymerizable monomer include 2-sulfoethyl (meth) acrylate, 2 or 1-sulfo-1 or 2-propyl (meth) acrylate, 1 or 3-sulfo-2-butyl (meth) acrylate, and 3-. Bromo-2
-Sulfo-2-propyl (meth) acrylate, 3-methoxy-1-sulfo-2-propyl (meth) acrylate, 1,1-dimethyl-2-sulfoethyl (meth) acrylamide, 2-methyl-2- (meth) Examples thereof include acrylamide propane sulfonic acid. Of these, 2-methyl-2- (meth) acrylamidopropanesulfonic acid is preferably used.

In the component (A), some or all of the acidic groups are
It can also be used in place of a valent or polyvalent metal salt or ammonium salt. In this case, it is usually preferable that the component (A) acts as an acid when used in combination with another acidic compound.

All the above-mentioned components (A) can be used alone or in combination.

Among the components (A), the solubility in water is 5
A radically polymerizable monomer having a content of less than 10% can be preferably used.

The component (B) of the present invention is a polymerization initiator.
Examples of such a polymerization initiator include a photopolymerization initiator (B1) and / or a peroxide (B2) known as a radical polymerization initiator.

The photopolymerization initiator (B1) has a role of exciting the curable composition of the present invention by being excited by light in the compound alone or in the coexistence with other compounds. For example, (B11) α-ketocarbonyl compound,
(B12) acylphosphine oxide compounds and the like can be mentioned.

Examples of the α-ketocarbonyl compound which is the component (B11) of the present invention include α-diketone and α
Examples thereof include-ketoaldehyde, α-ketocarboxylic acid and α-ketocarboxylic acid ester. More specifically, diacetyl, 2,3-pentadione, 2.3-
Hexadione, benzyl, 4,4'-dimethoxybenzyl, 4,4'-diethoxybenzyl, 4,4'-oxybenzyl, 4,4'-dichlorobenzyl, 4-nitrobenzyl, α-naphthyl, β-naphthyl Α-diketones such as camphorquinone, camphorquinone sulfonic acid, camphorquinone carboxylic acid and 1,2-cyclohexanedione; α-keto aldehydes such as methylglyoxal and phenylglyoxal: pyruvic acid, benzoylformic acid, phenylpyruvic acid, pyruvin Examples thereof include methyl acidate, ethyl benzoylformate, methyl phenylpyruvate and butyl phenylpyruvate. Among these α-ketocarbonyl compounds, α-diketones are preferably used in terms of stability and the like. Among the α-diketones, diacetyl, benzyl and camphorquinone (CQ) are preferable.

Examples of the acylphosphine oxide compound which is the component (B12) of the present invention include, for example, benzoyldimethoxyphosphine oxide, benzoylethoxyphenylphosphine oxide, benzoyldiphenylphosphine oxide, 2-methylbenzoyldiphenylphosphine oxide, 2,4,6-. Examples thereof include trimethylbenzoyldiphenylphosphine oxide.
The components (B11) and (B12) can be used alone or in combination.

Examples of the peroxide (B2) of the present invention include organic peroxides and inorganic peroxides. For example, diacetyl peroxide, dipropyl peroxide, dibutyl peroxide, dicapryl peroxide,
Dilauryl peroxide, benzoyl peroxide (BP
O), p, p'-dichlorobenzoyl peroxide, p,
p'-dimethoxybenzoyl peroxide, p, p'-
Organic peroxides such as dimethyl benzoyl peroxide, p, p'-dinitrodibenzoyl peroxide; inorganic peroxides such as ammonium persulfate, potassium persulfate, potassium chlorate, potassium bromate and potassium perphosphate. it can.

As the radical polymerization initiator, an organic boron compound or a composition containing the organic boron compound may be further mentioned. As the organic boron compound, for example,
Triethylboron, tripropylboron, triisopropylboron, tributylboron, tri-sec-butylboron, triisobutylboron, tripentylboron,
Trialkylborons such as trihexylboron, trioctylboron, tridecylboron, tridodecylboron, tricyclopentylboron, tricyclohexylboron; alkoxyalkylborons such as butoxydibutylboron; butyldicyclohexylborane, diisoamylborane, 9- Examples thereof include dialkylboranes such as borabicyclo [3,3,1] nonane, and some of the above compounds may be partially oxidized. further,
These compounds can be used in combination.
Among these, tributyl boron or partially oxidized tributyl boron is preferably used. As the partially oxidized tributylboron, for example, one obtained by adding 0.3 to 0.9 mol of O ₂ to 1 mol of tributylboron is preferably used.

In addition to the organic boron compound, a composition containing an aprotic solvent and / or a liquid or solid organic oligomer or polymer which is inert to the organic boron compound can be used.

The component (C) of the present invention is a reducing agent. Examples of the component (C) of the present invention include amine compounds. The component (C) may be any of aliphatic amine, alicyclic amine, and aromatic amine. Further, any of primary amine, secondary amine and tertiary amine may be used. Aromatic amines are preferred, and aromatic tertiary amines are more preferred. Other (C)
Examples of the component include aliphatic alkylaminoacetylbenzene represented by triethylaminoacetylbenzene and aliphatic alkylaminoacylbenzenes;
N-phenylglycine (NPG), N-tolylglycine (NTG), N, N- (3-methacryloyloxy-2
-Hydroxypropyl) phenylglycine (NPG-G
MA) and aromatic substituted glycines such as salts thereof can be used in combination. These compounds can be used alone or in combination.

The component (C) of the present invention is further an organic sulfinic acid and / or a salt thereof, or an aromatic organic acid such as barbituric acid or a derivative thereof or a salt thereof. As the organic sulfinic acid or a salt thereof, sulfinic acid or a usual alkali metal salt of sulfinic acid,
Alkaline earth metal salts, amine salts, ammonium salts are used. It is preferable to use an aromatic sulfinate since the color tone of the cured product is excellent. Examples of the alkali metal salt include lithium salt, sodium salt, potassium salt and the like. Examples of the alkaline earth metal salt include magnesium salt, calcium salt, strontium salt, barium salt and the like. Examples of the amine salt include salts of primary amines such as methylamine, ethylamine, propylamine, butylamine, aniline, toluidine, phenylenediamine, xylylenediamine; dimethylamine, diethylamine, dipropylamine, dibutylamine, piperidine, N-methylaniline. , Secondary amine salts such as N-ethylaniline, diphenylamine and N-methyltoluidine; trimethylamine, triethylamine, pyridine, N, N-dimethylaniline, N, N-di (β-hydroxyethyl) aniline, N, N-diethylamine , N, N
-Dimethyltoluidine, N, N-diethyltoluidine,
Examples thereof include salts of tertiary amines such as N, N- (β-hydroxyethyl) toluidine. Examples of the ammonium compound salt include ammonium salt, tetramethylammonium salt, tetraethylammonium salt, tetrapropylammonium salt, trimethylbenzylammonium salt and the like.

Specific examples of the organic sulfinic acid include:
Alkanesulfinic acids such as ethanesulfinic acid, propanesulfinic acid, hexanesulfinic acid, octansulfinic acid, decanesulfinic acid and dodecanesulfinic acid, cycloaliphatic sulfinic acids such as cyclohexanesulfinic acid and cyclooctanesulfinic acid; benzenesulfinic acid, o Examples thereof include aromatic sulfinic acids such as -toluenesulfinic acid, p-toluenesulfinic acid, ethylbenzenesulfinic acid, decylbenzenesulfinic acid, dodecylbenzenesulfinic acid, chlorobenzenesulfinic acid, and naphthalenesulfinic acid.

Specific examples of the organic sulfinate include lithium benzenesulfinate, sodium benzenesulfinate, potassium benzenesulfinate, magnesium benzenesulfinate, calcium benzenesulfinate, strontium benzenesulfinate, barium benzenesulfinate, and benzene. Sulfinic acid butylamine salt, benzenesulfinic acid aniline salt, benzenesulfinic acid toluidine salt, benzenesulfinic acid phenylenediamine salt, benzenesulfinic acid diethylamine salt, benzenesulfinic acid diphenylamine salt, benzenesulfinic acid triethylamine salt, benzenesulfinic acid ammonium salt, benzenesulfinic acid salt Acid tetramethylammonium, benzenesulfinate trimethylbenzylammonium It can be mentioned. Furthermore, o
-Lithium toluenesulfinate, sodium o-toluenesulfinate, potassium o-toluenesulfinate, calcium o-toluenesulfinate, o-toluenesulfinic acid cyclohexylamine salt, o-toluenesulfinic acid aniline salt, o-toluenesulfinic acid Ammonium salt, tetraethylammonium o-toluenesulfinate, lithium p-toluenesulfinate, p-
Sodium toluenesulfinate, potassium p-toluenesulfinate, p-toluenesulfinic acid, barium p-toluenesulfinate, p-toluenesulfinic acid ethylamine salt, p-toluenesulfinic acid toluidine salt, p-toluenesulfinic acid N-methylaniline salt,
p-toluenesulfinic acid pyridine salt, p-toluenesulfinic acid ammonium salt, p-toluenesulfinic acid tetramethylammonium, β-naphthalenesulfinic acid sodium salt, β-naphthalenesulfinic acid strontium, β-naphthalenesulfinic acid triethylamine,
β-naphthalene sulfinic acid N-methyltoluidine, β
Examples thereof include ammonium naphthalene sulfinate and trimethylbenzyl ammonium β-naphthalene sulfinate.

The barbituric acid derivative as the component (C) is
1,3,5-Trimethylbarbituric acid, 1,3,5-Triethylbarbituric acid, 1,3-Dimethyl-5-ethylbarbituric acid, 1,5-Dimethylbarbituric acid, 1-
Methyl-5-ethyl barbituric acid, 1-methyl-5-
Propyl barbituric acid, 5-ethyl barbituric acid,
5-propyl barbituric acid, 5-butyl barbituric acid, 5-methyl-1-butyl barbituric acid, 1-benzyl-5-phenyl barbituric acid, 1-cyclohexyl-5-ethyl barbituric acid or alkalis thereof It is preferably a metal salt or the like, and its concentration is preferably 0.1 to 10% with respect to the entire dental adhesive.

The component (C) is preferably dissolved or dispersed alone or under conditions exhibiting neutrality to alkalinity in order to stably store the composition of the present invention for a long period of time. The component (C) is a sponge ball, a sponge such as a sponge piece, a cotton ball, a brush, a brush, a danish dish, a kneading paper, and a sponge ball which are brought into contact when the composition of the present invention is used in order to simplify the operation during use. It may be pre-loaded or adsorbed on or adsorbed onto an applicator such as a spatula, and necessarily ready for mixing with the composition. Further, since such an applicator can be used as a disposable, it is effective as a countermeasure against infection in dental treatment.

Of these, N-phenylglycine (N
PG) and salts thereof (alkali metal salts, alkaline earth metal salts) are preferred.

When two or more reducing agents are used in combination, they are usually used in the same amount, but their compounding ratio may be changed if necessary. For example, when two kinds of reducing agents are used, the amount of one reducing agent can be changed to about 1/10 to 10 times.

The component (D) of the present invention is water. The component (D) has a role of lowering the pH of the composition of the present invention. Due to this effect, when it is applied to ground dentin, it dissolves the hydroxyapatite in the smear layer in a relatively short time. The component may diffuse into the dentin. As another effect, there is an advantage that the component (D) is promptly dissolved in the composition. Examples of water that can be used here include distilled water,
Examples include ion-exchanged water, purified water and physiological saline. In particular, distilled water, purified water and ion exchange water are preferably used. Also, redox water prepared by electrolysis, such as strongly acidic water or strong alkaline water, can be used.

The component (E) of the present invention is a polyfunctional radically polymerizable monomer having no acidic group. The component (E) mainly has a role of increasing the surface hardness when the composition of the present invention is cured. The component (E) is a radical-polymerizable monomer having no acidic group other than the component (A). As such a polymerizable monomer, one in which 5% by weight is added to distilled water, and phase separation is observed (not dissolved) when visually observed by shaking at 37 ° C. for 10 minutes Is preferred. That is, generally, the solubility at 37 ° C. is 5% by weight or less. Specifically, for example, aromatic vinyl compounds such as divinylbenzene, aliphatic esters of (meth) acrylic acid such as neopentyl glycol di (meth) acrylate, trimethylolpropane tri (meth) acrylate; 1 mol of bisphenol An adduct of A and 2 moles of glycidyl methacrylate (Bis-GMA),
Addition polymer of 1 mol of bisphenol A glycidyl ether and condensate of 2 mol of (meth) acrylic acid (VR9
0) Condensation product of 1 mole of ethylene oxide adduct of bisphenol A and 2 moles of (meth) acrylic acid (number of addition chains of ethylene oxide m + n ≧ 2; m + n = 2.6 is 2.6E).
Abbreviated) and the like aromatic (meth) acrylates; 1 mol of 2,2,4- (or 2,4,4-) trimethyl-1,
Addition product of 6-hexamethylene diisocyanate and 2 mol of 2-hydroxyethyl (meth) acrylate (UDM
Urethane bond-containing (meth) acrylate represented by A); 1,6-hexamethylene dimethacrylate (1,6-
HX), neopentyl glycol di (meth) acrylate, trimethylolpropane tri (meth) acrylate and other aliphatic esters of (meth) acrylic acid; ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, triethylene Polyethylene glycol di (meth) acrylates such as glycol di (meth) acrylate (chain number n = less than 6); propylene glycol di (meth) acrylate, dipropylene glycol di (meth) acrylate, tripropylene glycol di (meth) acrylate , Polypropylene glycol di (meth) acrylates such as nonapropylene glycol di (meth) acrylate (chain number n = 12
The following); 1,3-butanediol (meth) acrylate, 1,4-butanediol di (meth) acrylate,
Pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, tricyclodecane di (meth) acrylate, glycerol di (meth) acrylate, glycerol acrylate / methacrylate, tris ((meth) acryloxyethyl)
Isocyanate, di (meth) acrylated isocyanate, caprolactone-modified dipentaerythritol hexaacrylate and ditrimethylolpropane tetra (meth) acrylate,

[0049]

[Chemical 2] (Hydroxyethyl acrylate ester of tris (2-carboxyethyl) isocyanurate)

[0050]

[Chemical 3] (Addition product of hydroxyethyl methacrylate and diarylidene pentaerythritol)

[0051]

[Chemical 4] (Addition product of trimethylolpropane dimethacrylate and diarylidene pentaerythritol)

[0052]

[Chemical 5] (Acrylate ester of tris (2-hydroxyethyl) isocyanurate, NK ester A-9300,
CAS No. 40220-08-4), polyester (meth) acrylate, polyester polyurethane (meth) acrylate, and other polymerizable monomers.

Among these polyfunctional radically polymerizable monomers, a compound containing a triazine ring, a compound having a urethane bond, or a compound having an aromatic ring is preferably used.

Among the components (E), the solubility in water is 5
A radically polymerizable monomer having a content of less than 10% can be preferably used.

The component (F) of the present invention is an organic solvent,
As mentioned above, each component is uniformly dissolved or dispersed to improve the handling of the composition of the present invention. (F)
It is preferable that the components are usually limited to an amount necessary to dissolve or disperse so that the components volatilized in a short time when applied to an adherend such as tooth substance and the remaining components cause phase separation.
The solvent used here is capable of dissolving the components (A) and / or (B), and is water of the component (D) and (A) and / or
Alternatively, it is preferable that the component (B) has a property capable of being uniformly or stably dispersed or dissolved for a certain period. The organic solvent that can be used here is preferably an organic solvent capable of dissolving 30% by weight or more of water at 37 ° C., more preferably 50% by weight or more, and particularly preferably miscible and / or soluble with water in an arbitrary ratio. It is a solvent. Specifically, alcohols such as methanol, ethanol and propanol; ethers such as dimethoxyethane, 1,2-dimethoxyethane, tetrahydrofuran (THF) and dioxane; ketones such as acetone and methyl ethyl ketone;
Sulfoxides such as N, N-dimethyl sulfoxide (DMSO); N, N-dimethylformamide (DMF)
Examples thereof include amides. In addition, higher alcohols such as ethylene glycol, propylene glycol and glycerol can also be used. Here, alcohol, acetone, TH
F and DMSO are especially preferred.

In the composition of the present invention, when the total amount of the components (A) to (D) is 100 parts by weight, the content of the component (A) is usually 3 to.
80 parts by weight, preferably 5 to 70 parts by weight,
More preferably, it is in the range of 10 to 65 parts by weight,
The component (B) is in the range of 0.01 to 30 parts by weight, preferably 0.05 to 20 parts by weight, more preferably 0.1 to 20 parts by weight.
It is in the range of 10 parts by weight, and the component (C) is 0.01 to 20.
Parts by weight, preferably 0.05 to 15 parts by weight, more preferably 0.1 to 10 parts by weight, and the component (D) is 10 to 80 parts by weight, preferably 15 to 70 parts by weight. Range of parts by weight, more preferably 20-60
It can be used in the range of parts by weight.

When the total amount of the components (A) to (D) is 100 parts by weight, the component (E) is 10 as an additional component.
To 200 parts by weight, preferably 20 to 150
It can be used in the range of parts by weight, more preferably 30 to 100 parts by weight. When the component (E) having a solubility in water of 5% or more is used, when the total amount of the components (A) to (D) is 100 parts by weight, it is usually 0.1 to 10 as a component to be further added. Range of parts by weight, preferably 0.1-5
It can be used in the range of parts by weight, more preferably in the range of 0.1 to 3 parts by weight.

When the total amount of the components (A) to (D) is 100 parts by weight, the amount of the component (F) is 50 as an additional component.
To 300 parts by weight, preferably 70 to 250
It can be used in the range of parts by weight, more preferably 80 to 200 parts by weight.

In the present invention, a monofunctional radically polymerizable monomer can be used in addition to the above components (A) to (F). Specifically, styrene, vinyl acetate, methyl (meth) acrylate, ethyl (meth) acrylate,
Aliphatic alkyl esters of (meth) acrylic acid such as propyl (meth) acrylate, butyl (meth) acrylate, pentyl (meth) acrylate, and hexyl (meth) acrylate; (meth) acrylic acid 2-hydroxy- Examples thereof include aromatic esters of (meth) acrylic acid such as 3-phenoxypropyl and 2-hydroxy-3- (β-naphthoxy) propyl (meth) acrylic acid.

Further, a silane coupling agent and a sulfur compound suitable for application to the surface of a noble metal can be contained.

As the silane coupling agent usable in the present invention, a polymerizable monomer having an alkoxysilyl group in the molecule can be mentioned as a preferable example. Examples of the polymerizable monomer having an alkoxysilyl group include vinyltriethoxysilane and vinyl-tris (2-
(Methoxyethoxy) silane, allyltriethoxysilane, γ- (meth) acryloyloxypropyltrimethoxysilane, 2-styrylethyltrimethoxysilane,
(Meth) acryloyloxyethyldimethyl (3-trimethoxysilylpropyl) ammonium chloride, 3
Examples thereof include-(N-styrylmethyl-2-aminoethylamino) propyltrimethoxysilane hydrochloride and trimethoxysilylpropylallylamine. Of these, γ- (meth) acryloyloxypropyltrimethoxysilane and 2-styrylethyltrimethoxysilane are preferably used.

The above-mentioned polymerizable monomers can be used alone or in combination.

Further, as long as the effects of the present invention are not impaired, fluorine-containing compounds such as sodium fluoride, fluorine-releasing fillers, polymerization inhibitors, pigments, dyes, polymers,
A filler, an antifungal agent, an antibacterial agent, a surfactant and the like may be contained, and these are usually the composition 100 of the present invention.
0.01 to 10 parts by weight, preferably 0.1 part by weight.
It is used in the range of 1 to 5 parts by weight.

It is predicted that the adhesive composition of the present invention is effective for dentinal tissues which are said to be difficult to adhere because it has the following adhesion mechanism. That is, a large amount of water is present in dentin tissue, especially dentin. It is said that in order to apply an adhesive to this tissue and bring out sufficient adhesive performance, it is necessary that the adhesive component sufficiently penetrates into the tissue and hardens, and an adhesive having good adhesive performance was used. In some cases, it has been clarified that a resin-impregnated layer in which the tooth structure and the adhesive component are mixed is formed near the bonding interface with the tooth structure. Generally, it is said that it is preferable to use a polymerizable monomer or a polymerization initiator that is easily mixed with water in the tooth structure in order to diffuse the adhesive component into the tooth structure. This method provides good adhesive strength in the short term, but has poor long-term adhesive durability. The cause is presumed to be a decrease in water resistance due to the use of a component that is easily dissolved in water. On the other hand, although there is a composition using a water-soluble volatile organic solvent such as ethanol as proposed in Japanese Patent Publication No. 6-62688, the adhesive performance is not sufficient. It is considered that this is because the water in the dentinous tissue could not be successfully replaced by the proposed composition. In addition, JP-A-11-24
A composition that uses an organic solvent in combination, as in JP-A-08815,
For example, when it is applied to dentine dentin having living pulp, transient pain may be felt. Further, when applied to a hardened resin such as a denture or a denture base, cracks may be generated in the resin depending on the type of the organic solvent selected, and thus the intended use may be limited.

The present inventor has conducted a study for the purpose of the above improvement and is easily incorporated into the tooth substance together with the polymerizable monomer (A) having an acidic group, the polymerization initiator (B) and the reducing agent (C). A method of temporarily emulsifying water (D) and bringing it into contact with the tooth surface in a state where water and oil are emulsified was found.

When the components of the present invention and their compositions are applied to the dentin, the following adhesion mechanism is inferred. That is,
Usually, the composition of the present invention which has been phase-separated at room temperature is shaken well to be emulsified before application. The degree of emulsification depends on the properties of the adherend, but it is usually preferable to carry out until it becomes uniform. When the emulsion is brought into contact with the dentin surface, first, while the composition of the present invention having a low pH dissolves the hydroxyapatite on the dentin surface, the components of the composition diffuse into the healthy dentin and form dentin tissue. Adsorb. Generally, a polymerizable monomer having a hydrophilic group and a hydrophobic group in a molecule in a well-balanced manner is said to be easily diffused in the tooth tissue, and therefore, an acidic group and / or a carboxylic acid anhydride is included in the molecule. It is presumed that the radical-polymerizable monomer having is diffused and adsorbed preferentially. Moisture present inside the dentinous tissue and the composition of the present invention are rapidly mixed in the vicinity of the adhesive interface, and in the process in which the composition of the present invention diffuses into the dentin and is adsorbed to the dentinous tissue, at the same time, it becomes The undissolved components are gradually separated from the water. When the dentinous tissue and the polymerizable monomer are adsorbed, water is gradually driven to the surface and becomes a water droplet state on the oil film which is the polymerizable monomer. At this time, by applying compressed air or warm air to the application site, it is possible to exclude water and residue of dissolution of dentin components unnecessary for adhesion from the adhesive surface. After that, radical polymerization is caused to proceed by irradiation of visible light or hot air as much as necessary for adhesion. When used as a coating material, the removal of a small amount of unpolymerized polymerizable monomer remaining on the surface layer with a cotton ball containing ethanol ends, but if necessary, apply a restoration product such as a composite resin. Treatment can be terminated. As described above, moisture in the vicinity of the adhesive interface is gradually removed to the outside of the tissue by the composition of the present invention containing an organic solvent, and the curable composition is deeply penetrated into the dentinous tissue, and an effective film exposure is obtained. It is considered that by ensuring the strength, a strong adhesive strength can be obtained even in a wet condition and a cured product which is insoluble or hardly water-soluble can be formed, and thus excellent water resistance can be obtained.

Another feature of the present invention is that the surface hardness is high even when cured in a thin coating film state. The dental adhesive composition of the present invention is generally 1 to 30 microns, preferably 1 to 30 microns.
Used with a cured film thickness of 10 microns. Generally, a radically polymerizable composition is susceptible to polymerization inhibition by oxygen at the time of curing, and therefore, when cured in a thin film state, the polymerization becomes insufficient and the surface hardness becomes low. Further, in the case of an adhesive composition containing a polymerizable monomer having an acidic group and water, the polymerizability is often lowered and the surface hardness of the cured product is often lowered. However, in the adhesive composition of the present invention, an unexpected new property of having both adhesive performance and surface hardness was found. In particular, this property is likely to be exhibited by using a water-soluble compound such as a sulfinate or an N-aromatic group-substituted glycine salt as the reducing agent (C). It was found to be noticeable when the glycine salt was used simultaneously.

Furthermore, the transient pain which may occur when applied to dentin dentin having living pulp is remarkably reduced by applying the composition of the present invention which does not use an organic solvent. An unexpected effect was observed.
From this effect, when predicting the cause of transient pain that occurred when an adhesive containing an organic solvent was applied to myelinated dentin, it could be predicted that it was due to a local temperature decrease due to volatilization of the organic solvent. Therefore, it is presumed that the composition of the present invention containing no organic solvent did not contain a volatile organic solvent, so that local temperature decrease did not occur, and as a result, pain was suppressed. Further, it can be applied not only to the dentin but also to hardened resins such as dentures and denture bases as adherends, and suppresses the rapid cracking of the resin that has occurred when an adhesive containing an organic solvent was applied so far. effective.

Among the adhesive compositions of the present invention, the solvent (F)
The components and a mixture obtained by removing all or part of the polymerization initiator (B) are strongly stirred for 24 hours in a constant temperature water tank at 30 to 40 ° C in the same sealed packaging container to sufficiently mix the components. . After that, when the composition is once brought to room temperature (23 ° C.) and then vigorously shaken for about 15 seconds, it is usually not completely dissolved and dispersed as an emulsion, or phase separation occurs within 5 minutes. It has the characteristic of causing When the residual composition obtained by evaporating the component (F) around room temperature is vigorously shaken for about 15 seconds, is it not usually completely dissolved but dispersed as an emulsion? Alternatively, it has a characteristic of causing phase separation within 5 minutes.

[0070]

EXAMPLES In order to further enhance the effect of the present invention, when the composition of the present invention is applied to tooth structure, it is allowed to stand for 5 seconds or more, preferably 10 seconds or more, more preferably 30 seconds or more after application. To do. It is presumed that this is the time required for the composition of the present invention to dissolve and diffuse some or all of the smear layer on the dentin surface and / or the tooth matrix. However, the longer the standing time is, the more the effect of the present invention is enhanced. However, in consideration of use in the oral cavity, it is preferable that the time is at most about 1 minute. Further, it can also be applied to tooth material which has been surface-treated in advance with an inorganic acid such as phosphoric acid or citric acid which may contain a metal compound, and an organic acid. Hereinafter, the present invention will be described with reference to examples, but the present invention is not limited to these examples.

(Phase Separation Test) 30 to 4 in the same packaging container in which the composition comprising the components (A) to (D) of the present invention is sealed.
Stir vigorously for 24 hours in a constant temperature water bath at 0 ° C. to thoroughly mix the components. Then, after the composition was brought to room temperature (23 ° C.), it was vigorously shaken again for about 15 seconds, and when it was not a transparent homogeneous solution, that is, when it was not completely dissolved and was emulsified and dispersed, or 5 minutes. If some of them are oil droplets or solids, they are defined as "phase separation". In addition, the same test can be performed for the composition which is cured within the main test time depending on the type of the polymerization initiator (B) except the component (B).

When the component (F) is included, (F)
When the residual composition obtained by evaporating the components near room temperature is vigorously shaken for about 15 seconds, and the composition is not a clear homogeneous solution, that is,
It was defined as "phase separation" when it did not completely dissolve and was emulsified and dispersed, or when there were some oil droplets or solid particles within 5 minutes.

(Solubility Test of Polymerizable Monomer in Water) A radical polymerizable monomer corresponding to the component (A) or (E) of the present invention was added to distilled water so as to be 5%. After shaking for 10 minutes at a temperature of ° C, the mixture was allowed to stand for 4 hours, and the presence or absence of phase separation was visually observed. Solubility was less than 5% for those with phase separation, and solubility was 5% or more for those that were dissolved, including the case of uniform emulsification. In this way
The solubility of component (A) or (E) at 37 ° C is 5
It was judged whether or not the radical polymerizable monomer was less than%.

Example 1 of Method for Producing Sponge Containing Components (B) and / or (C): For example, a sponge containing sodium p-toluenesulfinate (p-TSNa: first grade deer, Kanto Kagaku) is prepared. If you do: p-TSNa
Grind 0.05g in a mortar for 10 minutes to make powder, put in a 20cc glass bottle, and then add Super Bond C
Sponge S (& polyurethane foam size ¢ 3x
3 mm: Weight of one piece (8.3 mg) is added to 0.05 to 0.1 g. Shake the bottle vigorously for 3 minutes to sponge and p-TSNa.
To make uniform contact. Separate the powder and sponge,
The sponge was called as a cat sponge and used as it was. P-TSNa contained per sponge is
The average was 0.4 mg.

Benzoyl peroxide (BPO), sodium benzenesulfinate (BSNa), lithium p-toluenesulfinate (p-TSLi), N-phenylglycine (NPG), sodium N-phenylglycine (NPG.Na). A cata sponge containing parbituric acid and sodium barbital and a cata sponge containing a mixture thereof were prepared in the same manner.

Example 2 of preparation method of sponge containing component (B) or / and (C): For example, p-TSNa and N
When preparing a sponge containing PG / Na: 0.0
0.2 g of p-TSNa and 0.02 g of NPG.Na.
An aqueous solution is prepared by adding 96 g of ion-exchanged water. 0.11 g (13 pieces) of sponge S attached to Super Bond C & B was added to this aqueous solution, and the bottle was shaken vigorously for 3 minutes to contain the solution in the sponge. The sponge containing the aqueous solution is transferred onto a stainless steel mesh and spread, and dried while moving the mesh under an atmosphere of 55 ° C. The sponge after drying was referred to as "cata sponge" and used as it was. P-TSNa and NPG contained in one sponge
The Na content was 0.1 mg on average, and the total amount was 0.2 mg.

Benzoyl peroxide (BPO), sodium benzenesulfinate (BSNa), lithium p-toluenesulfinate (p-TSLi), N-phenylglycine (NPG), sodium N-phenylglycine (N
Cata sponges containing PG.Na), barbituric acid and sodium barbital and mixtures thereof were prepared in the same manner. In addition, ethanol or acetone was used about the compound which does not dissolve in water.

Example 3 of a method for producing a sponge containing the components (B) and / or (C): 0.4 g of sodium p-toluenesulfinate tetrahydrate (Wako Pure Chemical Industries, Ltd.) and 16 g of distilled water were dissolved. Then, put 3g of it into a 10cc glass bottle, and sponge S (urethane foam size: 3x3mm; seat weight: 8.3) attached to Super Pond C & B.
0.05 to 0.1 g of (mg) is added and the solution is sufficiently impregnated. This was referred to as a cata sponge, and the composition of the present invention was prepared as one sponge impregnated with the liquid when used as it was. About 1 liquid is contained per sponge
It was 6 mg.

(Surface Treatment of Tooth: None) Fresh bovine lower anterior teeth were removed, frozen and stored in water, and used as a tooth sample. Rotate grinding machine ECOMET-II so that the enamel and dentin are exposed to the thawed bovine tooth.
I (manufactured by BUEHLER) was used for water injection and water-resistant emery paper # 180 was used for polishing under finger pressure to obtain a smooth surface. The ground bovine tooth was once removed of water with an air gun, and immediately a cellophane tape with a circular hole having a diameter of 4.8 mm was pasted for defining an adhesion area.

(Surface Treatment of Tooth: Etching Treatment) Fresh bovine lower anterior teeth were removed, frozen and stored in water, and used as a tooth sample. Rotate grinding machine ECO so that enamel and dentin are exposed to the thawed bovine tooth.
Water was poured with MET-III (manufactured by BUEHLER), and water-resistant emery paper # 180 was ground under finger pressure to obtain a smooth surface. Immediately after removing water from the ground bovine teeth with a pig iron, the surface treatment material red (65% phosphoric acid solution; made by Sun Medical) or the surface treatment material green (10%) is used as an etching material.
A sufficient amount of a mixed aqueous solution of citric acid and 3% ferric chloride (manufactured by Sun Medical Co., Ltd.) was applied with Sponge S (not Catass bondage), washed for 5 seconds with water, and dried by air blow. A cellophane tape having a circular hole with a diameter of 4.8 mm was attached to the surface to which the etching material was applied in order to define the adhesion area.

(Surface Treatment of Tooth: Treatment with Sodium Hypochlorite) Fresh bovine lower anterior teeth were extracted, frozen and stored in water, and used as a tooth sample. Water the thawed bovine teeth with a rotary polishing machine ECOMET-III (made by BUEHLER) so that the enamel and dentin are exposed,
Water-resistant emery paper # 180 was ground under finger pressure to obtain a smooth surface. The ground bovine tooth was once attached with a cellophane tape with a circular hole having a diameter of 4.8 mm for removing water with a pig iron and defining an adhesion area. 10 in the area specified area
% Aqueous solution of sodium hypochlorite was applied, allowed to stand for 30 seconds, and thoroughly washed with water. Excess water on the dentin surface was wiped gently with absorbent cotton to keep the surface dry.

(Application of the composition of the present invention to the dentin 1) The curable composition of the present invention was shaken well immediately before use to give an emulsion, and immediately 2 drops (0.1 g) were taken in a danish dish. Within 30 seconds, the sponge S attached to Super Bond C & B was used to sprinkle a large amount (about 0.0
15 g) was applied and allowed to stand for 20 seconds, and then excess liquid was blown off while lightly blowing air. After sufficiently stirring the liquid remaining in the dabbing dish with the same sponge and applying it several times repeatedly, and after confirming the formation of a film on the surface with the naked eye,
Visible light irradiator (TransluxCL, Kulzer
(Manufactured) for 10 seconds to cure the curable composition of the present invention.

(Application of the composition of the present invention to tooth structure 2) 2 drops (0.1 g) of an emulsion excluding the component (C) of the curable composition of the present invention was taken in a tapped dish, and the Catass bondage ( One prepared by any of the above methods) was stirred for 3-5 seconds to mix and emulsify all ingredients in a dapu dish. A large amount of the cata sponge was applied to the dentin of which the area was defined, left standing for 20 seconds, and then the excess liquid was blown off while lightly blowing air.
After the liquid remaining in the dabbing dish was thoroughly stirred with the same sponge and repeatedly applied several times to confirm the formation of a film on the surface with the naked eye, a visible light irradiator (TransluxC
L, manufactured by Kulzer) for 10 seconds to cure the curable composition of the present invention.

(Adhesion Test Method) The composition of the present invention was applied to the dentin by the above method (application 1 or application 2), and immediately after that, a thickness having an inner diameter of 5.1 mm circular hole with an adhesive on one side Fix 1mm base paper so that the specified surface can be seen,
This hole was filled with a convoygit resin (Metafil C, manufactured by Sun Medical Co., Ltd.) and covered with a polyester film having a thickness of 50 mm. This film is irradiated with visible light for 20 seconds with a visible light irradiator (Translux CL, manufactured by Kulzer) to cure the convolgit resin, and then the film is peeled off, and an acrylic stick is planted with Meta First (manufactured by Sun Medical). And left for 15 minutes. After soaking in 37 ° C water for one day, a tensile test was performed with a crosshead speed of 2 m.
It was performed at m / min.

(Vickers hardness test method) JIS Z-
According to 2251, the composition of the present invention is applied to bovine dentin without surface treatment by the above method, and immediately thereafter, the unpolymerized portion of the outermost layer is removed by a cotton ball containing ethanol. The film thickness at this time is about 10 μm. The hardness of this surface is measured with a Vickers hardness meter (Shimadzu HMV-2000) at a load of 50 g for about 12 seconds to measure the Vickers hardness (H
V) was calculated.

(Film Thickness Test) Fresh bovine lower anterior teeth were extracted, frozen and stored in water, and used as a dentin sample. The thawed bovine tooth is rotated by a polishing machine ECOMET-III (BU to expose enamel and dentin.
Water made by EHLER), water resistant emery paper # 18 under shiatsu pressure
Polishing with 0 gave a smooth surface. Moisture was removed from the ground bovine teeth with an air gun. Cellophane tape was attached to one half of the ground surface, the adhesive composition of the present invention was applied to the other half of the dentin surface for 20 seconds, and thinned and uniformed by air blow. Light was irradiated for 10 seconds with a visible light irradiator (Translux CL, manufactured by Kulzer), and the uncured composition on the surface was wiped off with a cotton ball containing ethanol. Remove the cellophane tape, fix the bovine teeth horizontally with the acrylic plate and the viscosity as the grinding surface upwards, and measure the film measuring device DIGIMATIC INDI.
The film thickness was calculated by measuring the difference between the surface (ground surface) covered with cellophane tape and the surface to which the composition of the present invention was applied, after being set in CATOR (manufactured by MITUTOYO).

(Adhesion test to porcelain) One side of dental porcelain (Super Boselen AAA, E3 (manufactured by Noritake); 15 × 15 × 10) is a rotary polishing machine ECO.
Water was poured with MET-III (manufactured by BUEHLER), and water-resistant emery paper # 2000 was polished under finger pressure to obtain a flat surface.
Polished surface with phosphoric acid solution (high viscosity red (Sun Medical))
After applying 0.3 g, the mixture was allowed to stand for 30 seconds, thoroughly washed with water, and dried by air blow. A cellophane tape with a circular hole having a diameter of 4.8 mm was pasted on the surface to which the phosphoric acid solution was applied to define the adhesion area.

From 4-MET (2.5 parts by weight), γ-methacryloyloxypropyltrimethoxysilane (γ-METS; 2.5 parts by weight) as a silane coupling agent, and 95 parts by weight of methyl methacrylate (MMA). The resulting solution was prepared immediately before use, taken out with a 0.015 g dropper, applied onto a surface-defined surface, and after 10 seconds, air blown to dry. The composition of the present invention was applied to this surface, and the adhesive strength was calculated according to the above-mentioned adhesion test method.

(Adhesion Test to Dental Precious Metal (Gold / Silver Paranium)) The surface of the precious metal for dentistry (gold / silver palladium alloy: prime cast (manufactured by Ishifuku Metal Co., Ltd.) 10 × 10 × 3 mm) is a rotary polishing machine ECOMET-III (BUEHLER). Manufactured) and water-resistant emery paper # 600 was polished under finger pressure to obtain a flat surface. Polished surface with alumina sand plast (Sa
Hara (JELENKO); 50 μm aluminum oxide) was treated at 5 kg / cm 2 for about 10 seconds, ultrasonically washed in water, and dried by air blow. A cellophane tape with a circular hole having a diameter of 4.8 mm was attached to the treated surface to define the adhesion area.

6- (4-Pinylpentyrrheno-propyl) amino-1,3.5-triazine-2,4-dithione (VTD.0.5 parts by weight) and acetone (99.5 parts by weight)
About 0.015 g of a solution containing the above was taken out with a dropper and applied on the surface having a defined area, and after 10 seconds, it was blown with air and dried. The composition of the present invention was applied to this surface, and the adhesive strength was calculated according to the above-mentioned adhesion test method.

Example 1 20 parts by weight of 4-META, 0.5 parts by weight of camphorquinone, 0.5 parts by weight of NPG.Na, and 17 parts by weight of distilled water were put in a glass bottle and mixed, while shielding from light. Shake vigorously at 25 ° C for 15 minutes to form a uniform emulsion. When the emulsion was allowed to stand at room temperature for about 10 minutes while blocking visible light, phase separation could be clearly confirmed with the naked eye. Further, the viscosity may increase after about 1 hour or more. Therefore,
Immediately after preparation and immediately before use, it was shaken vigorously for about 15 seconds and subjected to the test as an emulsion.

An adherence test was carried out by applying bovine dentin as an adherend, without surface treatment of dentin, and applying 1 to dentin, and an adhesion test was conducted. The adhesive strength was 6 MPa and the fracture state was that of dentin. Interfacial peeling was included in part, and it was cohesive failure of the cured product of the composition of the present invention and the composite resin. The surface hardness was 15 HV.

Example 2 20 parts by weight of 4-META, 0.5 parts by weight of 2,4,6-
Trimethylbenzoyldiphenylphosphine oxide (DTMPO), 0.5 parts by weight of p-TSNa, and 17 parts by weight of distilled water were put in a glass bottle and mixed, and shaken vigorously at 25 ° C for 15 minutes while shaking to obtain a uniform emulsion. Made into liquid. When this emulsion was allowed to stand at room temperature for about 10 minutes, phase separation could be clearly confirmed with the naked eye. Immediately before use, it was shaken vigorously for about 15 seconds and subjected to the test as an emulsion. The viscosity of this solution sometimes increased in a few days.

An adherence test was carried out by applying bovine dentin as the adherend, without surface treatment of the dentin, and application 1 to the dentin, and an adhesion test showed that the adhesive strength was 5 MPa and the fracture state was the composition of the present invention. It was interfacial peeling that partially included cohesive failure of the cured product and the composite resin. The surface hardness was 15 HV.

Example 3 20 parts by weight of bis (2-methacryloyloxyethyl)
Acid phosphate, 5 parts by weight of 2-methacryloyloxyethyl acid phosphate, 0.5 part by weight of camphorquinone, 0.5 part by weight of 2,4,6-trimethylbenzoyldiphenylphosphine oxide (DTMPO),
0.5 parts by weight of p-TSNa, 0.5 parts by weight of NPG · N
a, 10 parts by weight of ion-exchanged water was put in a glass bottle and mixed, and shaken vigorously at 25 ° C. for 15 minutes while shielding from light to obtain a uniform emulsion. When this emulsion was allowed to stand at room temperature for about 10 minutes, phase separation could be clearly confirmed with the naked eye. Also, about 1
The viscosity may increase after a lapse of time. Therefore, immediately after preparation and immediately before use, it was shaken vigorously for about 15 seconds and subjected to the test as an emulsion.

An adherence test was carried out by applying bovine enamel as an adherend, without surface treatment of the tooth substance, and applying 1 to the tooth substance, and an adhesion test was conducted. The adhesive strength was 5 MPa and the fracture state was the composition of the present invention. It was interfacial peeling that partially included cohesive failure of the cured product and the composite resin. Surface hardness is 15H
It was V.

Example 4 20 parts by weight of 4-META, 0.5 parts by weight of camphorquinone, 0.5 parts by weight of NPG.Na, 17 parts by weight of distilled water and 40 parts by weight of acetone were put in a glass bottle and mixed. Then, it was shaken vigorously at 25 ° C. for 15 minutes while being shielded from light to form a uniform transparent solution. No phase separation could be confirmed even when the solution was kept closed at room temperature for several months. The viscosity of this solution sometimes increased in a few days.

Adhesion test was carried out by applying bovine dentin as an adherend, without surface treatment of tooth structure, and application to tooth structure 1 (no shaking required immediately before use), and adhesion strength was 6M.
It was Pa, and the state of fracture was cohesive failure of the cured product of the composition of the present invention and the composite resin, including a part of interfacial peeling from the tooth structure. The surface hardness was 15 HV.

Example 5 In Example 4, after the composition of the present invention was collected in a dappen dish, air blowing (about 30 seconds) was performed until the amount of the collected liquid was reduced to about half, and acetone in the composition was volatilized. Immediately before use, the same procedure as in Example 4 was performed, except that the liquid was thoroughly stirred with a sponge to emulsify the liquid that had been phase-separated. The adhesion test shows that the bond strength is 6M.
It was Pa, and the state of fracture was cohesive failure of the cured product of the composition of the present invention and the composite resin, including a part of interfacial peeling from the tooth structure. The surface hardness was 15 HV.

Example 6 NPG.Na and p-TSNa which are components (C) in advance.
A cata sponge containing 0.4 part by weight of each of the above was produced according to Example 1 of the sponge producing method. Also, 3 parts by weight of 2-methyl-2-acrylamidosulfonic acid (TBA
S), 0.1 part by weight camphorquinone, 0.1 part by weight DTMPO, 17 parts by weight distilled water, 15 parts by weight ethoxylated isocyanuric acid triacrylate (A-9300).
And 12 parts by weight of MMA in a glass bottle and mixed,
The mixture was vigorously shaken for 30 minutes at 25 ° C. while protected from light to give a uniform emulsion. With this solution, phase separation could be visually confirmed in about 30 minutes at room temperature in a sealed state.

A cata sponge prepared in advance and 2 drops (about 0.1 g) of the liquid which was shaken well just before use and emulsified were applied to give bovine enamel, no surface treatment of tooth substance, and When the adhesion test is conducted according to application 2, the adhesion strength is 5
It was MPa, and the fractured state was cohesive failure of the cured product of the composition of the present invention and the composite resin, including a part of interfacial peeling from the tooth structure. The surface hardness was 20 HV.

Example 7 A cata sponge containing 0.8 parts by weight of NPG.Na as the component (C) was prepared in advance according to Example 1 of the sponge preparation method. Also, 13 parts by weight of 4-META, 0.2 parts by weight of camphorquinone, 20 parts by weight of distilled water, and 15 parts by weight of A-9300 were put in a glass bottle and mixed, and vigorously kept at 25 ° C for 30 minutes while shielding from light. Shake to make a uniform emulsion. With this solution, phase separation could be visually confirmed in about 30 minutes at room temperature in a sealed state.

A cata sponge prepared in advance and 2 drops (about 0.1 g) of the liquid which was shaken well just before use and emulsified were applied to apply bovine dentin, no surface treatment of tooth substance, and When the adhesion test is conducted according to application 2, the adhesion strength is 6MP.
a, and the state of destruction includes interfacial delamination with the tooth structure,
This was cohesive failure of the cured product of the composition of the present invention and the composite resin. The surface hardness was 30 HV.

Example 8 NPG.Na and p-TSNa which are components (C) in advance.
A cata sponge containing 0.7 part by weight of each of the above was prepared according to Example 1 of the sponge preparation method. Also, 13 parts by weight of 4-META, 0.3 parts by weight of camphorquinone, and 0.3 parts by weight.
3 parts by weight of DTMPO, 13 parts by weight of distilled water, 15 parts by weight of A-9300 and 12 parts by weight of MMA were put in a glass bottle and mixed, and shaken vigorously for 30 minutes at 25 ° C while shielding from light to obtain a uniform emulsion. Made into liquid. With this solution, phase separation could be visually confirmed in about 30 minutes at room temperature in a sealed state.

A cata sponge prepared in advance and 2 drops (about 0.1 g) of the liquid which was shaken well just before use and emulsified were applied to apply bovine dentin, no surface treatment of tooth substance, and When the adhesion test is conducted according to application 2, the adhesion strength is 7MP
a, and the state of destruction includes interfacial delamination with the tooth structure,
This was cohesive failure of the cured product of the composition of the present invention and the composite resin. The surface hardness was 40 HV.

Example 9 NPG.Na and p-TSNa which are components (C) in advance.
A cata sponge containing 0.3 part by weight of each of the above was prepared according to Example 2 of the sponge preparation method. Also, 22 parts by weight of 4-MET, 0.2 parts by weight of camphorquinone, 0.2
Parts by weight of DTMPO, 15 parts by weight of distilled water, 15 parts by weight of A-9300 and 12 parts by weight of MMA are mixed in a glass bottle and shaken vigorously at 25 ° C. for 30 minutes while shielding from light to obtain a uniform emulsion. I chose With this solution, phase separation could be visually confirmed in about 30 minutes at room temperature in a sealed state.

A cata sponge prepared in advance and 2 drops (about 0.1 g) of a liquid which was shaken well just before use and emulsified were applied to apply bovine dentin, no surface treatment of dentin, and dentin When the adhesion test is conducted according to application 2, the adhesion strength is 7MP
a, and the state of destruction includes interfacial delamination with the tooth structure,
This was cohesive failure of the cured product of the composition of the present invention and the composite resin. The surface hardness was 40 HV.

Example 10 NPG.Na and p-TSNa which are components (C) in advance.
A cata sponge containing 0.4 parts by weight of each of the above was prepared according to Example 2 of the sponge manufacturing method. Also, 10 parts by weight of 4-META, 3 parts by weight of bis (2-methacryloyloxyethyl) acid phosphate, 0.1 part by weight of camphorquinone, 0.1 part by weight of DTMPO, 15 parts by weight of distilled water, 12 parts by weight. Parts by weight MMA and 15 parts by weight U
Put the DMA in a glass bottle and mix, and keep it at 25 ℃
Shake vigorously for 30 minutes to form a uniform emulsion. With this solution, phase separation could be visually confirmed in about 30 minutes at room temperature in a sealed state.

A cata sponge prepared in advance and 2 drops (about 0.1 g) of the liquid which was shaken well and emulsified immediately before use (approx. 0.1 g) were applied to the bovine dentin, without the surface treatment of the dentin, to the dentin. When the adhesion test was conducted according to application 2, the adhesion strength was 8MP.
a, and the state of destruction includes interfacial delamination with the tooth structure,
This was cohesive failure of the cured product of the composition of the present invention and the composite resin. The surface hardness was 35 HV.

Example 11 NPG.Na and p-TSNa which are components (C) in advance
A cata sponge containing 0.4 parts by weight of each of the above was prepared according to Example 2 of the sponge manufacturing method. Also, 10 parts by weight of 4-META, 3 parts by weight of bis (2-methacryloyloxyethyl) acid phosphate, 0.1 part by weight of camphorquinone, 0.1 part by weight of DTMPO, 1 part by weight of benzoyl peroxide ( BPO), 15 parts by weight of distilled water,
12 parts by weight of MMA and 15 parts by weight of UDMA were put in a glass bottle and mixed, and vigorously shaken at 25 ° C. for 30 minutes while shielding from light to form a uniform emulsion. With this solution, phase separation could be visually confirmed in about 30 minutes at room temperature in a sealed state.

A cata sponge prepared in advance and 2 drops (about 0.1 g) of a liquid which was shaken well just before use and emulsified were applied, and the surface of bovine dentin and dentin was not treated, and After applying the composition to the dentin surface, filling the composite resin directly without irradiating light, and irradiating the composite resin with light after about 3 minutes, an adhesion test was conducted according to application 2 to the dentin. The adhesive strength was 6 MPa, and the state of failure was cohesive failure of the cured product of the composition of the present invention and the composite resin in part, but it was interfacial peeling from the tooth structure. The surface hardness (with light irradiation) was 35 HV.

Example 12 Preliminarily (C) component NPG, NPG · Na and p-
Cata sponges containing 0.5, 0.4, and 0.4 parts by weight of TSNa, respectively, were prepared according to Example 1 of the sponge preparation method. Also, 10 parts by weight of 4-META, 0.1 parts by weight of camphorquinone, 0.1 parts by weight of DTMPO, 15 parts by weight.
Parts by weight ion-exchanged water, 10 parts by weight MMA, 5 parts by weight resorcin dimethacrylate (RDMA), 10 parts by weight TEGDMA, 2 parts by weight NK ester (U-4H
(A: Shin-Nakamura Kagaku) was placed in a glass bottle and mixed, and the mixture was vigorously shaken at 25 ° C. for 30 minutes while being protected from light to form a uniform emulsion. With this solution, phase separation could be visually confirmed in about 30 minutes at room temperature in a sealed state.

A cata sponge prepared in advance and 2 drops (about 0.1 g) of the liquid which was shaken well just before use and emulsified were applied to apply bovine dentin, no surface treatment of tooth substance, and When the adhesion test is conducted according to application 2, the adhesion strength is 6MP.
a, and the state of destruction includes interfacial delamination with the tooth structure,
This was cohesive failure of the cured product of the composition of the present invention and the composite resin. The surface hardness was 25 HV.

Example 13 NPG.Na and p-TSNa which are components (C) in advance.
A cata sponge containing 0.7 part by weight of each of the above was prepared according to Example 1 of the sponge preparation method. Also, 22 parts by weight of 4-META, 0.3 parts by weight of camphorquinone, and 0.3 parts by weight.
3 parts by weight of DTMPO, 13 parts by weight of distilled water, 15 parts by weight of A-9300, 12 parts by weight of MMA and 36 parts by weight of acetone were mixed in a glass bottle and shaken vigorously at 25 ° C. for 30 minutes while shading. A uniform solution was obtained. No phase separation or viscosity increase could be confirmed even when the solution was left in a sealed state at room temperature for several months.

A cata sponge prepared in advance and 2 drops (about 0.1 g) of the solution were applied, and an adhesion test was conducted by application 2 to the dentin without surface treatment of bovine dentin and dentin. The breaking state was cohesive failure of the cured product of the composition of the present invention and the composite resin, including a part of interfacial peeling from the tooth structure. Surface hardness is 40H
It was V.

Example 14 NPG.Na and p-TSNa which are components (C) in advance.
A cata sponge containing 0.7 part by weight of each of the above was prepared according to Example 1 of the sponge preparation method. Also, 22 parts by weight of 4-META, 0.3 parts by weight of camphorquinone, and 0.3 parts by weight.
3 parts by weight DTMPO, 13 parts by weight distilled water, 15 parts by weight A-9300, 12 parts by weight MMA, 1 part by weight H
EMA and 35 parts by weight of acetone were put in a glass bottle and mixed, and vigorously shaken at 25 ° C. for 30 minutes while shielding from light to obtain a uniform solution. No phase separation or viscosity increase could be confirmed even when the solution was left in a sealed state at room temperature for several months.

A cata sponge prepared in advance and 2 drops (about 0.1 g) of the solution were applied, and an adhesion test was carried out by application 2 to the dentin without bovine enamel and no tooth surface treatment. The breaking state was cohesive failure of the cured product of the composition of the present invention and the composite resin, including a part of interfacial peeling from the tooth structure. Surface hardness is 4
It was 0 HV.

Example 15 NPG.Na and p-TSNa which are components (C) in advance.
A cata sponge containing 0.7 part by weight of each of the above was prepared according to Example 1 of the sponge preparation method. Also, 22 parts by weight of 4-META, 0.3 parts by weight of camphorquinone, and 0.3 parts by weight.
3 parts by weight DTMPO, 10 parts by weight distilled water, 15 parts by weight A-9300, 10 parts by weight MMA, 1 part by weight H
EMA and 40 parts by weight of ethanol were put in a glass bottle and mixed, and vigorously shaken at 25 ° C. for 30 minutes while shielding from light to obtain a uniform solution. No phase separation or viscosity increase could be confirmed even when the solution was left in a sealed state at room temperature for several months.

A cata sponge prepared in advance and 2 drops (about 0.1 g) of the solution were applied, and an adhesion test was conducted by applying 2 to the dentin without surface treatment of bovine dentin and dentin. The breaking state was cohesive failure of the cured product of the composition of the present invention and the composite resin, including a part of interfacial peeling from the tooth structure. Surface hardness is 35H
It was V.

Example 16 NPG.Na and p-TSNa which are components (C) in advance.
A cata sponge containing 0.4 part by weight of each of the above was produced according to Example 1 of the sponge producing method. Also, 13 parts by weight of 4-META, 0.3 parts by weight of camphorquinone, and 0.3 parts by weight.
3 parts by weight of DTMPO, 17 parts by weight of distilled water, 15 parts by weight of A-9300, 12 parts by weight of MMA, 2.5 parts by weight of HEMA and 40 parts by weight of acetone were mixed in a glass bottle and shielded from light. While vigorously shaking at 25 ° C for 30 minutes, a uniform solution was obtained. No phase separation or viscosity increase could be confirmed even when the solution was left in a sealed state at room temperature for several months.

A cata sponge prepared in advance and 2 drops of the solution (about 0.1 g) were applied, and an adhesion test was carried out by application 2 to the dentin without surface treatment of bovine dentin and dentin. The breaking state was cohesive failure of the cured product of the composition of the present invention and the composite resin, including a part of interfacial peeling from the tooth structure. Surface hardness is 40H
It was V.

Example 17 Bovine dentin and dentin were surface-treated with the surface treatment material Red (65
%), An adhesion test was performed in the same manner as in Example 16 except that etching was performed using phosphoric acid), and the adhesive strength was 10 MPa, and the fracture state partially included interfacial delamination with the tooth structure. It was cohesive failure of the cured product of the composition of the present invention and the composite resin.

Example 18 An adhesive test was conducted in the same manner as in Example 16 except that the surface treatment of the tooth structure was performed with the surface-treating material green, and the adhesive strength was 10 MPa and the state of fracture was found. Was the cohesive failure of the cured product of the composition of the present invention and the composite resin.

Example 19 An adhesion test was conducted in the same manner as in Example 16 except that sodium hypochlorite was used as the surface treatment of the dentin, and the dentin was kept wet. However, the adhesive strength was 7 MPa, and the fractured state was interfacial peeling with the tooth substance which partially contained cohesive failure of the cured product of the composition of the present invention and the composite resin.

Example 20 An adhesion test was carried out using porcelain as the adherend and the same composition as in Example 13 in accordance with the method of the adhesion test to porcelain. The adhesion strength was 11 MPa.
The state of destruction was cohesive failure of porcelain.

Example 21 An adhesive test was carried out using a dental precious metal as an adherend and the same composition as in Example 13 according to the method of adhesion test to a dental precious metal. It was 10 MPa, and the fracture state was cohesive failure of the cured product of the composition and the composite resin.

Example 22 A dental floor resin (Metafast: manufactured by Sun Medical) was used as an adherend to prepare a 10 × 10 × 3 mm cured product. When the adhesion test was performed using the same composition as in Example 13 according to the method of the adhesion test, the adhesion strength was 10
It was MPa, and the failure state was cohesive failure of the cured product of the composition of the present invention and the composite resin.

Example 23 A composite resin (Metafil C: manufactured by Sun Medical) was used as an adherend to prepare a 10 × 103 mm cured product. An adhesion test was conducted using the same composition as in Example 13 according to the method of adhesion test to porcelain.
The adhesive strength was 12 MPa, and the failure state was cohesive failure of the pre-cured composite resin.

[0129]

Industrial Applicability The dental adhesive composition of the present invention serves as a bonding material for adhering a non-adhesive material to a tooth substance such as a composite resin, and also improves the tooth substance adhesive performance of resin cement. It can be used as a bonding material to be used for the purpose, and can also be used as a coating material for protecting the surface of various adherends, that is, tooth substance, metal, ceramics, resin, etc. When used as a coating agent on exposed dentin, which has a large effect on nerves (sometimes called nerves), it not only protects against abrasion and mechanical irritation, but also suppresses hyperesthesia, prevents caries infection, It is effective for suppressing postoperative pain. The dental coating material of the present invention is very simple and can be operated in a short time, and since it has the advantage of being able to form a hard and thin film firmly bonded to the tooth substance, it is simply a composite resin or resin cement. In addition to the function as an adhesive for adhering the tooth substance to other materials such as, the adhesive itself has a hard and strong property, and the property can be exhibited even in a very thin film.

Continued front page    (72) Inventor Haruka Otsuki             572-1 Furutakacho, Moriyama City, Shiga Prefecture             Ikaru Co., Ltd. F-term (reference) 4C089 AA01 AA10 BC02 BC07 BC09                       BC11 BC12 BD01 CA02 CA07

Claims (11)

[Claims] 1. A component comprising (A) a radically polymerizable monomer having an acidic group in the molecule, (B) a polymerization initiator, (C) a reducing agent and (D) water, and components (A) to (D). In the range of 3 to 80 parts by weight per 100 parts by weight of the component (A),
The component (B) is in the range of 0.01 to 30 parts by weight, the component (C) is in the range of 0.01 to 20 parts by weight and the component (D) is 10 parts by weight.
A dental adhesive composition, characterized in that it is in the range of -80 parts by weight and the cured product has a Vickers hardness of 15-100. 2. A polyfunctional radically polymerizable monomer having no acidic group (E) is further contained in an amount of 10 to 200 parts by weight per 100 parts by weight of the components (A) to (D), and The dental adhesive composition according to claim 1, wherein the component (E) is at least one selected from a compound containing a triazine ring, a compound having a urethane bond, and a compound having an aromatic ring. 3. (F) a water-soluble organic solvent having a boiling point of less than 100 ° C. per 100 parts by weight of the total of components (A) to (D),
The dental adhesive composition according to claim 1 or 2, further comprising 50 to 300 parts by weight. 4. Dental adhesive composition according to claim 1 or 2, wherein the mixture of constituents undergoes phase separation at 37 ° C. 5. The dental adhesive composition according to claim 1, wherein the cured product has a Vickers hardness of 20 to 80. 6. The polymerization initiator (B) is (B1) a photopolymerization initiator and / or (B2) a peroxide, and the photopolymerization initiator (B1) is a (B11) α-ketocarbonyl compound. And / or (B12) an acylphosphine oxide compound, The dental adhesive composition according to any one of claims 1 to 3. 7. The reducing agent (C) is (C1) sulfinate, (C2) N-aromatic group-substituted glycine or a salt thereof,
The dental adhesive composition according to any one of claims 1 to 3, which is at least one selected from the group consisting of and (C3) barbituric acid or a salt thereof. 8. The dental adhesive composition according to claim 7, wherein the reducing agent (C) comprises at least one reducing agent (C1) and at least one reducing agent (C2). 9. A combination of an applicator containing at least one reducing agent (C1) and at least one reducing agent (C2), and one or more containers containing the remaining ingredients. A kit of the dental adhesive composition according to any one of claims 1 to 3. 10. The kit according to claim 9, wherein the dental adhesive composition is a dental adhesive. 11. The kit according to claim 9, wherein the dental adhesive composition is a dental coating material.