JPH0782115A - Primer composition - Google Patents

Abstract

PURPOSE:To obtain a primer composition showing excellent adhesiveness to both adamantine and dentin by blending a vinyl compound with a water-soluble vinyl compound, water, an aromatic sulfinate and an aromatic secondary and/or tertiary amine in a limited composition ratio. CONSTITUTION:This primer composition comprises (A) 5-30wt.% of an acidic group-containing vinyl compound (e.g. 10-acryloyloxydecyldihydrogenphosphate), (B) 10-50wt.% of a hydroxyl group-containing water-soluble vinyl compound (e.g. 2-hydroxyethyl acrylate), (C) 35-75wt.% of water, (D) 2-15wt.% of an aromatic sulfinate (e.g. benzenesulfinic acid) and (E) 2-15wt.% of an aromatic secondary and/or tertiary amine (e.g. Nmethylaniline). The composition is usable as a one-pack type primer by dissolving the five components collectively. In order to improve storage stability, the components A and D are preferably packed separately not to exist in the same pack.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION The present invention relates to a living body hard tissue which is an adherend for the purpose of strengthening the adhesive force when performing a bonding operation on a living body hard tissue, particularly tooth enamel and dentin with an acrylic adhesive. It relates to a primer composition for applying a pretreatment.

[0002]

2. Description of the Related Art Today, acrylic dental adhesives are often used for dental prostheses to partially repair teeth with a restorative material such as composite resin, dental alloy, or porcelain. Although the adhesiveness of this kind of adhesive to teeth has been dramatically improved by the quality improvement for the past 20 years, it has not yet reached a perfect level. That is, a gap is created at the adhesive interface between the tooth and the restoration, and bacteria invade through the gap to cause secondary caries and pulpitis. If the restoration is dependent on adhesion, the restoration itself falls off. It has been reported that there is a case to do. Efforts have been made to reduce these problems as much as possible, and it has recently been revealed that the application of a certain primer to the tooth surface before the bonding operation enhances the adhesive force between the tooth and the adhesive. .

For example, Journal of Dent
al Research Vol. 63, P1087-
Glutaraldehyde / 2- in 1089 (1984)
It is described that a primer composition composed of hydroxyethyl methacrylate (HEMA) / water exhibits an effect of enhancing adhesion with dentin. However, with this technology, the adhesion enhancing effect does not appear unless the smear layer (cutting dust layer) on the dentin surface is cleaned (decalcified) with an aqueous solution of ethylenediaminetetraacetic acid trisodium salt before applying the primer. There was a weakness. Later, a primer was developed that eliminated this cleaning. For example, in JP-A-62-223289, HEMA solution is added to maleic acid,
It is described that a primer added with an acid such as tribromoacetic acid or hydrochloric acid remarkably improves the adhesion to enamel and dentin without cleaning. Dental Materials and Equipment, Vol. 9, pp. 65-73 (1990), a primer prepared by adding a monomer having an acidic group such as N-methacryloylalanine or N-acryloylalanine to an HEMA aqueous solution is an enamel without cleaning and ivory. It is described that the adhesion to quality is significantly improved. Further, in JP-A-4-8368, (i) water 0.5 to 90% by weight, (ii) hydroxyl group-containing polymerizable compound 5 to 90% by weight, and (iii) acidic group-containing polymerizable compound 0.1. ~ 90
%, And (iv) an amino compound having an acidic group 0.
Primer compositions containing from 01 to 30% by weight are disclosed. The patent claims that the adhesion to dentin is dramatically improved by adding an appropriate amount of an amino compound having an acidic group to a primer obtained by adding a monomer having an acidic group to an HEMA aqueous solution. There is.

Although these primers have an adhesive effect in the usages claimed by the respective patents, it must be said that they are still incomplete in practical use. For example, the primer of JP-A-62-223289 shows a remarkable adhesion enhancing effect when used in combination with a photopolymerization type dental adhesive, but the effect is slight when combined with a chemical polymerization type adhesive. . In addition,
It has been pointed out that the non-polymerizable acid component contained in the primer is eluted and has harmful effects on the dental pulp. The primer described in Dental Materials and Instruments, Volume 9, pages 65-73 (1990), in combination with a chemical polymerization type adhesive,
It shows an adhesion enhancing effect, but its degree is 103 kg / cm ² for bovine enamel and 80 kg / cm ² for bovine dentin.
Therefore, it is still insufficient to completely solve the problems caused by insufficient adhesion such as secondary caries, loss of restorations, and pulpitis. The primer composition disclosed in JP-A-4-8368 shows an excellent adhesion enhancing effect in combination with a photopolymerization type adhesive, but its effect is low in combination with a chemical polymerization type adhesive.

[0005]

In view of the above situation, the present invention can remarkably improve the adhesiveness to both enamel and dentin regardless of the polymerization method of the acrylic dental adhesive. It is intended to provide a primer for living hard tissue.

[0006]

Means for Solving the Problems The inventors of the present invention have made extensive studies in order to achieve the above object, and as a result, achieved the object in a primer composition prepared by mixing specific components in a limited composition ratio as described below. The inventors have found what is possible and have reached the present invention. That is, the present invention includes (a) a vinyl compound having an acidic group of 5 to 30% by weight, and (b) a water-soluble vinyl compound having a hydroxyl group of 10 to 50.
% By weight (c) water 35-75% by weight (d) aromatic sulfinate 2-15% by weight and (e) aromatic secondary or / and tertiary amine 2-1
It relates to a primer composition containing 5% by weight. The composition can be used as a one-pack type primer in which the above-mentioned five components (a) to (e) are collectively dissolved. However, in order to improve storage stability, the composition is not packaged in the same package (a) and (d). It is desirable to package them separately so that they are not needed.

The present invention will be described in more detail below.
The acidic group of the vinyl compound having an acidic group used in the present invention means a phosphoric acid derivative such as a phosphoric acid monoester group, a phosphoric acid diester group, a phosphonic acid group, a phosphonic acid monoester group, a phosphinic acid group, a carboxyl group, and a sulfone. It is an acid group. Examples of the vinyl compound having such an acidic group include 2- (meth) acryloyloxyethyl dihydrodiene phosphate, 6- (meth) acryloyloxyhexyl dihydrodiene phosphate, 10- (meth) acryloyloxydecyl dihydrodiene phosphate, 2- (Meth) acryloyloxyethylphenylhydrogenene phosphate, bis (2- (meth) acryloyloxyethyl) hydrogen phosphate, 2- (meth) acryloyloxyethyl hydrogendienephenylphosphonate, 6- (meth) acryloyloxyhexylphosphinate, Phosphoric acid derivatives such as N- (10-phosphonodecyl) (meth) acrylamide, 4-vinylbenzenephosphonic acid, 4-vinylbenzyl phononic acid, (meth) acrylic acid, co- Click acid mono (2
(Meth) acryloyloxyethyl), isophthalic acid (2- (meth) acryloyloxyethyl), 4- (meth) acryloyloxyethyl trimellitic acid, 11,
11-dicarboxyundecyl (meth) acrylate,
Carboxylic acid compounds such as N- (meth) acryloylalanine, N- (meth) acryloyl-5-aminosalicylic acid, 4-vinylbenzoic acid, 2- (meth) acrylamido-2-methylpropanesulfonic acid, styrenesulfonic acid, etc. Mention may be made of sulfonic acid compounds.

Among these compounds, a compound group having a particularly large adhesion-enhancing effect is a phosphoric acid derivative, and 10-
Typical examples are (meth) acryloyloxydecyldihydrodiene phosphate, 2- (meth) acryloyloxyethylphenylhydrogenphosphate and 2- (meth) acryloyloxyethylhydrogenphenylphosphonate. 1 vinyl compound having an acidic group
Not only the types but also a plurality of types may be used in combination. The preferred concentration thereof is 5 to 30% by weight, and if it deviates from this range, the adhesion enhancing effect is significantly reduced.

Next, the water-soluble vinyl compound having a hydroxyl group used in the present invention will be described. The hydroxyl group means an alcoholic hydroxyl group and does not include carboxylic acid and phenols. Water-soluble means a solubility of 10% by weight or more at room temperature. Specific examples include 2-hydroxyethyl (meth) acrylate, propylene glycol mono (meth) acrylate, glycerin mono (meth) acrylate, erythritol mono (meth) acrylate, pentaerythritol di (meth) acrylate, N-methylol (meth) acrylamide. , N-hydroxyethyl (meth) acrylamide and N, N-di (hydroxyethyl) (meth) acrylamide.

Among these compounds, particularly preferred from the viewpoint of the effect of enhancing adhesion are polyol mono (meth) acrylate represented by 2-hydroxyethyl (meth) acrylate, glycerin mono (meth) acrylate and erythritol mono (meth) acrylate. Is. These are 1
Not only the species but also a plurality of species may be used in combination, and the preferable concentration is 10 to 50% by weight. If it deviates from this range, the adhesion-enhancing effect remarkably decreases, which is not preferable.

Next, the water used in the present invention does not contain microorganisms and harmful components for its purpose, and water purified by distillation and / or membrane filtration is preferably used. The content of water is 35 to 75% by weight, more preferably 50 to 65% by weight. If it deviates from this range, the adhesion enhancing effect will be adversely affected.

In the present invention, the above-mentioned three main components, namely (a)
In addition to the vinyl compound having an acidic group, the water-soluble vinyl compound having a hydroxyl group (b), and (c) water, (d) an aromatic sulfinate and (e) an aromatic secondary amine or / and a tertiary An amine is added as a polymerization initiator or accelerator. When the aromatic sulfinic acid salt comes into contact with the vinyl compound having an acidic group, aromatic sulfinic acid is produced, and when the aromatic acid sulfinic acid / aromatic secondary or tertiary amine combination is obtained, room temperature polymerization is started. Further, when the primer composition is brought into contact with a room temperature curing type dental acrylic adhesive, the organic peroxide usually blended in the adhesive migrates to the primer side, and the sulfinic acid / amine / organic peroxide A system is formed and the polymerization reaction will proceed more rapidly.

The aromatic sulfinic acid salt used in the present invention includes benzenesulfinic acid, p-toluenesulfinic acid, o-trienesulfinic acid, ethylbenzenesulfinic acid, decylbenzenesulfinic acid, dodecylbenzenesulfinic acid, 2,4,4. Lithium salts such as 6-trimethylbenzenesulfinic acid, 2,4,6-triisopropylbenzenesulfinic acid, chlorobenzenesulfinic acid and naphthalenesulfinic acid, sodium salts, potassium salts, rubidium salts, cesium salts, magnesium salts, calcium salts, Strontium salt, iron salt, copper salt, zinc salt,
Examples thereof include ammonium salt, tetramethylammonium salt, and tetraethylammonium salt. These may be used in combination of not only one type but also a plurality of types. The preferred concentration is 2 to 15% by weight, and if it deviates from this range, the adhesion enhancing effect is significantly reduced.

Next, as aromatic secondary and tertiary amines used in the present invention, N-methylaniline, N-methyl-p-toluidine, N-methyl-m-toluidine,
N-methyl-o-toluidine, N-ethanol-p-toluidine, N-ethanol-m-toluidine, N-ethanol-o-toluidine, ethyl p-methylaminobenzoate, ethyl m-methylaminobenzoate, o- Ethyl methylaminobenzoate, p-methylaminoanisole, m
-Methylaminoanisole, o-methylaminoanisole, 1-methylaminonaphthalene, 2-methylaminonaphthalene, N, N-dimethylaniline, N, N-dimethyl-p-toluidine, N, N-dimethyl-m-toluidine, N, N-dimethyl-o-toluidine, N, N-diethanol-p-toluidine, N, N-diethanol-m
-Toluidine, N, N-diethanol-o-toluidine, ethyl p-dimethylaminobenzoate, ethyl m-dimethylaminobenzoate, ethyl o-dimethylaminobenzoate, p-dimethylaminoanisole, m-dimethylaminoanisole, o -Dimethylaminoanisole, 1-
Examples thereof include dimethylaminonaphthalene and 2-dimethylaminonaphthalene. These may be used in combination of not only one type but also a plurality of types. The preferred concentration is 2-1
It is within the range of 5% by weight, and if it deviates from this range, the effect of enhancing adhesion will be significantly reduced.

In addition to the above-mentioned essential components, a volatile water-soluble organic solvent may be added to the primer composition of the present invention, if necessary. Specific examples include ethyl alcohol, propyl alcohol, isopropyl alcohol, acetone and the like. These are used by adding at a ratio of 0 to 500 parts by weight to 100 parts by weight of the primer composition [(a) + (b) + (c) + (d) + (e)]. Addition of more than 500 parts by weight weakens the adhesion enhancing effect.

In addition to the above components, the primer composition of the present invention may optionally contain a photopolymerization initiator, a polymerization inhibitor, a pigment,
Additives such as fragrances and fillers can be added if desired. As the photopolymerization initiator, those having an effective wavelength of ultraviolet light and / or visible light are preferable, for example, camphorquinone / 4-dimethylaminobenzoic acid ester type, camphorquinone / 4-dimethylaminobenzophenone type, caferquinone / aromatic sulfinic acid salt. System, caferquinone / 2-mercaptobenzoxazole system, caferquinone / 5-alkyl barbituric acid system, benzoin alkyl ether, benzyl dialkyl ketal, chlorothioxanthone, 2,4,6-trimethylbenzoyldiphenylphosphine oxide, etc. are preferably used. .

Mixing (a) a vinyl compound having an acidic group and (d) an aromatic sulfinic acid salt, which compose the primer composition of the present invention, in the same solution markedly lowers the storage stability. If the product is to be used for a long period of time, both components must be stored in separate containers in a two-part packaging form. The component (a) can coexist with all components other than the component (d), and the component (d) can coexist with all components other than the component (a). There are many, but a typical example is [(a) + (b)] / [(c) + (d) +
(E)], [(a) + (b) + (c)] / [(c) +
(D) + (e)], [(a) + (b) + (c) +
(E)] / [(c) + (d) + (e)], [(a) +
(C) + (e)] / [(b) + (d) + (e)] and the like.

The primer composition of the present invention is used for adhering a living hard tissue according to the following procedure. (1) The primer composition is applied to an adherend, that is, tooth enamel, tooth dentin,
Or it is applied to the surface of bone (2) It is left for 10 seconds to 10 minutes to allow the primer composition to penetrate into the adherend (3) Excessive primer is removed by air blow (4) Acrylic dental or orthopedic A surgical adhesive is applied on the surface to which the primer has been applied, and is adhered to the other adherend (dental coposit resin, metal, ceramics, resin, living hard tissue).

The acrylic adhesive used in combination with the primer composition of the present invention includes (i) an acrylic monomer having an acidic group, (ii) an acrylic monomer having no acidic group, and (iii) initiation of polymerization. The agent is preferably used, which further comprises (iv) a filler if necessary.

As the acrylic monomer having an acidic group, 10- (meth) acryloyloxydecyldihydrodiene phosphate, 2- (meth) acryloyloxyethylphenylhydrogen phosphate, bis [2- (meth) acryloyloxyethyl] Examples thereof include hydrogen phosphate, 4- (meth) acryloyloxyethyl trimellitic acid, and 11,11-carboxyundecyl (meth) acrylate.

Examples of acrylic monomers having no acidic group are methyl (meth) acrylate, butyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2- (dimethylamino) ethyl (meth) acrylate, and γ-methacryloyloxy. In addition to mono (meth) acrylates such as propyltrimethoxysilane, triethylene glycol di (meth) acrylate, neopentyl glycol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, 1,10-decanediol Di (meth) acrylate, 2,2'-bis [((meth) acryloyloxypolyethoxy) phenyl] propane, 2,2'-bis [4- (3- (meth) acryloyloxy-2-hydroxypropoxy) phenyl ] Propane (Bis-GMA Referred), trimethylolethane tri (meth) acrylate, di-2- (meth) acryloyloxyethyl, such as 2,2,4-trimethyl hexamethylene carbamate and the like.

As the polymerization initiator, a benzoyl peroxide / aromatic sulfinate / aromatic secondary or / and tertiary amine type, partially oxidized tributylborane, barbituric acid / copper salt type or the like is used. In addition, camphorquinone / 4-dimethylaminobenzoate ethyl type, camphorquinone / 4-dimethylaminobenzophenone type, camphorquinone / aromatic sulfinate type, camphorquinone / 2-mercaptobenzoxazole type,
A photopolymerization type initiator such as 2,4,6-trimethylbenzoyldiphenylphosphine oxide is preferably used.

As the filler, polymethylmethacrylate, polyethylmethacrylate, organic-inorganic composite filler, silica, alumina, barium glass, lanthanum glass, zirconia glass, etc. are preferably used.

[0024]

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

Examples 1 to 7 6-methacryloyloxyhexyl dihydrodiene phosphate as a vinyl compound having an acidic group, 2-hydroxyethyl methacrylate as a water-soluble vinyl compound having a hydroxyl group, distilled water, and benzenesulfinate as an aromatic sulfinate. Sodium acid, N, N-diethanol-p-toluidine were used as the aromatic tertiary amine, and their composition ratios were changed within the scope of the present invention 7.
Different types of primers (compositions listed in Table 1) were prepared.

[0026]

[Table 1]

On the other hand, a human front tooth was resin-embedded in a 20 mmφ × 15 mm metal ring and polished in a direction parallel to the tooth axis to obtain a flat enamel sample. Similarly, embedding a person's molars,
A flat dentin sample was obtained by polishing in the direction parallel to the tooth axis. Each sample was stored in water until just before use.

Immediately before use, the enamel plane and the dentin plane were wet-polished with No. 1000 silicon carbide abrasive paper, washed with water, and the surface water was blown off gently with a dental air syringe. A primer (one of Examples 1 to 7) immediately after preparation was applied to these surfaces with a brush, left alone for 60 seconds, and then lightly dried with an air syringe. Next, a commercially available dental adhesive "Panavia EX"
4 mm using (manufactured by Kuraray Co., Ltd., an acrylic monomer having an acidic group, an acrylic monomer having no acidic group, a polymerization initiator and a filler as constituent components)
A φ × 4 mm cylindrical stainless steel tip was adhered to the enamel and dentin planes. The adhesive sample was immersed in 37 ° C. water 15 minutes after the adhesion, and the shear adhesive strength was measured after 24 hours (cross head speed = 0.5 mm).
/ Min). Seven samples under one condition were measured, and their average values are shown in the lower part of Table 1. In all Examples 1-7, enamel bond strength is at 201kg / cm ² or more, dentin bond strength was 130 kg / cm ² or more. The sum of both was 359 kg / cm ² or more.

By the way, the adhesive strength of the enamel when gluing with Panavia EX only without using a primer is 137.
kg / cm ^2, dentin bond strength was 81 kg / cm ^2. The sum of both was 218 kg / cm ² .

Comparative Examples 1 to 11 Examples using 11 kinds of primers (Comparative Examples 1 to 11) prepared by using the same components as those in Examples 1 to 7 but having a composition ratio outside the scope of the present invention Adhesion experiments similar to 1 to 7 were performed. The results are shown in the lower part of Table 2. In all of Comparative Examples 1 to 11, the enamel bond strength was 192
kg / cm ² or less, dentin adhesive strength is 113 kg
/ Cm ² or less. The sum of both is 299 kg / c
It was less than m ² .

[0031]

[Table 2]

Examples 8 to 14 M shown in Table 3 as the vinyl compound (a) having an acidic group.
Dp, phenyl-p, 4-MET, 4-AET, 11-
5 types of DCUM, 2 types of HEMA and EM as water-soluble vinyl compounds having a hydroxyl group (b), 2 types of distilled water (c) aromatic sulfinates (d) of BSS and PTSK
DE as a seed, aromatic secondary or tertiary amine (e)
Components (a), (b), using two types of PT and EPT,
The composition ratio of (c), (d) and (e) is 10:30:50:
Fixing at 5: 5, seven kinds of primers of Examples 8 to 14 shown in Table 3 were prepared.

Using these primers, Examples 1 to 1
The enamel and dentin bond strengths were determined according to the methods up to 7, and the results are shown in the lower row of Table 3. Enamel bond strength is 228 kg / cm ² or more, dentin bond strength is 1
31 kg / cm ² or more, and the sum of both is 361 k
It was g / cm ² or more. When the vinyl compound (a) having an acidic group is a phosphoric acid derivative, that is, MDP and phenyl-P, a vinyl compound having another acidic group, that is, 4-M
It is clear from Table 3 that significantly superior bond strengths are obtained over ET, 4-AET, and 11-DCU.

[0034]

[Table 3]

Example 15 A two-component type primer composition "Primer (I)" consisting of the following solutions A and B was prepared. On the other hand, a two-paste (chemical polymerization type) acrylic adhesive "Adhesive DP" consisting of the following A paste and B paste
Was prepared. A paste: MDP 5 wt% Bis-GMA 15 1,6-hexanediol dimethacrylate 4.5 Silane-treated silica powder 75 Benzoyl peroxide 0.5 B paste: Bis-GMA 15 wt% 1,6-hexanediol di Methacrylate 9.4 Silane-treated silica powder 75 DEPT 0.3 2,4,6-Triisopropylbenzenesul 0.3 Sodium Phinate However, Bis-GMA is 2,2'-bis [4- (3-
Methacryloyloxy-2-hydroxypropoxy) phenyl] propane.

The following experiment was conducted in order to evaluate the adhesive force to the teeth of the adhesive set consisting of the primer (I) and the adhesive DP. First, a solution prepared by mixing 0.1 g of each of the solutions A and B of the primer (I) was applied to the human enamel flat surface samples prepared in Examples 1 to 7, and left alone for 60 seconds, and then the dental rare Lightly dried with a syringe. Next, knead 0.2 g each of A paste and B paste of the adhesive DP, and then mix this with 4 mmφ × 4 mm
It was applied to the cylindrical stainless steel tip of and was pressed against the flat surface of the enamel. Similarly, a stainless chip was adhered to a human dentin plane using the primer (I) and the adhesive DP. The adhesive sample was immersed in 37 ° C. water after 15 minutes from the adhesion, and the shear adhesive strength was measured after 24 hours (cross head speed = 0.5 mm / min).

The average of the measured values of seven samples under one condition was enamel adhesive strength = 295 kg / cm ² , and dentin adhesive strength = 216 kg / cm ² . The sum of both is 511kg
/ Cm ² . By the way, the enamel bond strength and the dentin bond strength are 145 kg / cm ² and 92 kg / c, respectively, when the adhesive DP alone is used without using the primer (I).
It was m ² .

Example 16 A photopolymerization type acrylic adhesive "adhesive MP" consisting of the following 1 paste was prepared. Adhesive MP: MDP 2.5 parts by weight Bis-GMA 15 1,6-hexanediol dimethacrylate 6.9 Silane-treated silica powder 75 Camphorquinone 0.3 4-Dimethylaminoethyl benzoate 0.3

The primer (I) of Example 15 was applied to an adherend (human enamel plane, dentine plane), and then a 4 mmφ × 4 mm cylindrical dental composite resin “Clearfill” was applied using an adhesive MP. A cured product of "Photocore" (manufactured by Kuraray) was pressed onto it. Next to the lick of the cured body,
A dental light irradiator "Litel-II" (manufactured by Gunma Ushio Denki Co., Ltd.) was used to irradiate the light 4 times from each of 4 directions for 20 seconds. 15 from adhesion
Immerse the adhesive sample in water at 37 ° C for 24 minutes,
The shear bond strength was measured after a period of time.

Enamel bond strength is 273 kg / cm ²
(Η = 7), and the dentin adhesive strength was 231 kg / cm ² . The sum of both is 504 kg / cm ² . By the way, the enamel adhesive strength and the dentin adhesive strength were 132 kg / cm ² and 101 kg / cm ^{2 when} they were adhered only by the adhesive MP without using the primer (I).

From Examples 15 and 16, the primer of the present invention was used regardless of the polymerization method of the acrylic adhesive to be combined.
It is clear that it has the effect of significantly enhancing the adhesion to both enamel and dentin.

Comparative Examples 12 and 13 The following one-pack type primer composition "primer (II)" containing camphorquinone / 4-dimethylaminobenzoate ethyl system as a photopolymerization initiator was prepared. Primer (II): MDP 15% by weight HEMA 25 water 59 camphorquinone 0.5 ethyl 4-dimethylaminobenzoate 0.5

An adhesion test was conducted according to Example 15 using a combination of the primer (II) and the adhesive DP (Comparative Example 12). As a result, the enamel adhesive strength was 165 kg / cm ² , and the dentin adhesive strength was 83 kg / cm. ^{Was 2} . The sum of both is 248 kg / cm ² .

On the other hand, when an adhesion test was conducted according to Example 16 using the combination of the primer (II) and the adhesive MP (Comparative Example 13), the enamel adhesive strength was 240 kg / c.
m ² , and the dentin adhesive strength was 156 kg / cm ² . The sum of both is 396 kg / cm ² .

It is clear from Comparative Examples 12 and 13 that the primer (II) has a large difference in the adhesion enhancing effect due to the difference in the polymerization method of the combined adhesive.

Example 17 A one-pack type photopolymerizable acrylic adhesive "Adhesive ML" shown below was prepared. Adhesive ML: MDP 15 HEMA 30 Bis-GMA 51 Camphorquinone 2 4-Dimethylaminoethyl benzoate 2

The primer (I) of Example 15 was applied to an adherend (human enamel plane, dentin plane), left for 60 seconds, and then gently blown with a dental air syringe to blow off excess primer. did. Adhesive ML is applied on top of this, and a hole of 4 mmφ is drilled on top of it to a thickness of 2 mm.
The split mold made of Teflon was placed and irradiated with a dental light irradiator toward the adhesive ML inside the hole for 20 seconds. Next, the dental composite resin "Photo Clear Fill A" (made by Kuraray) was filled into the inside of this hole, and light irradiation was repeated from above 4 times.
It went for 0 seconds. The adhesive sample was immersed in 37 ° C. water 15 minutes after the last light irradiation, and the shear adhesive strength was measured after 24 hours.

Enamel bond strength is 312 kg / c
m ² , and the dentin adhesive strength was 226 kg / cm ² . The sum of both is 538 kg / cm ² .

[0049]

EFFECTS OF THE INVENTION The primer composition of the present invention is applied to living hard tissues, particularly tooth enamel and dentin in advance, and then bonded with an acrylic adhesive for living hard tissues to bond the adhesives. The power is significantly increased.

Claims (3)

[Claims] 1. A vinyl compound having an acidic group (a) 5:
30% by weight, (b) 10 to 50% by weight of a water-soluble vinyl compound having a hydroxyl group, (c) 35 to 75% by weight of water, (d)
A primer composition comprising 2 to 15% by weight of an aromatic sulfinate and (e) 2 to 15% by weight of an aromatic secondary or / and tertiary amine. 2. The (a) vinyl compound having an acidic group and the (d) aromatic sulfinate are separately packaged so as not to enter the same solution.
The described primer composition. 3. An acrylic adhesive comprising the primer composition according to claim 1, (i) an acrylic monomer having an acidic group, (ii) an acrylic monomer having no acidic group, and (iii) a polymerization initiator. An adhesive set characterized by being composed of.