JPH03247679A - Adhesive composition - Google Patents

Abstract

PURPOSE:To obtain an adhesive composition, composed of a specific 4- vinylbenzoic acid, specified alpha-amino acid or a derivative thereof, etc., and capable of saving labor and preventing tooth surfaces from their being lost by dissolution with an acid in dental treatment and having excellent adhesion. CONSTITUTION:The objective composition composed of (A) 0.1-10wt.% compound expressed by formula I [R1 is H or methyl; R2 is H, (halogen-substituted) 1-5C alkylene oxide, a group expressed by formula II (n is 1-4) which may be substituted with halogen or methyl group], (B) 0.1-10wt.% alpha-amino acid or a compound of the alpha-amino acid derivative having an aliphatic or aromatic nucleus expressed by formula III (R1 is H, methyl, etc.; R2 is H, phenyl, etc.; R3 is H or methacryloxy), (C) 70-99wt.% compound selected from acrylic compounds, styrene and divinylbenzene, (D) 70-99wt.% free radical former and/or photosensitizer capable of absorbing visible light or ultraviolet light, etc., and forming free radicals and (E) 0.1-5wt.% free radical formation accelerator.

Description

DETAILED DESCRIPTION OF THE INVENTION [Field of Industrial Application] The present invention relates to a new adhesive composition, particularly an adhesive composition suitable for dental materials.

[Conventional technology]

Conventionally, as adhesives, (1) 2-cyanoacrylic acid ester adhesives or epoxy adhesives are known.
(2) Copolymers of vinyl compounds such as methyl methacrylate polymer and 2,2-bis[4-(2-hydroxy-3-methacryloxypropoxy)phenyl]propane and triethylene glycol dimethacrylate as tooth adhesives. Consolidation has been used, (3) and also recently 4
- Adhesive compositions containing methacryloxyethyl trimellitic anhydride, which exhibit adhesive properties while polymerizing themselves, have been proposed.

[Problem to be solved by the invention]

However, conventional adhesives, for example, 2-
Cyanoacrylic acid ester-based adhesives and epoxy-based adhesives have the disadvantage of poor water resistance and durability, and are particularly unsuitable as adhesives for teeth due to the harsh conditions of the oral cavity. Adhesives have insufficient adhesion to teeth, so it is necessary to treat the teeth with strong acid in advance, which has disadvantages such as excessive dissolution loss of the tooth surface and complicated dental treatment.

In addition, the conventional products described in (3) above, which exhibit adhesive properties while polymerizing themselves, have excellent water resistance and durability and can withstand use in the oral cavity. When a polymerization catalyst is used, the aromatic tertiary amine, which should originally act as an accelerator in this catalyst system, and the anhydride group of 4-methacryloxyethyltrimellitic anhydride form a charge transfer complex, and the original polymerization catalyst Therefore, the room-temperature polymerization catalyst used in this adhesive system has generally been limited to tri-n-butylborane oxide. Although this material has the advantage of providing strong adhesion to tooth dentin, the polymerization reaction is slow and it may take several minutes for final hardening in some cases, and it is extremely unstable in air. There were many problems from a dental clinical standpoint, such as the difficulty in handling it.

[Means to solve the problem]

The present inventors have conducted extensive research to solve the above-mentioned problems with conventional adhesives, and first found that (A) general formula (I), [wherein R1 is hydrogen or a methyl group, R2 is hydrogen, An alkyl group having 1 to 5 carbon atoms which may be substituted with a halogen, an alkylene oxide group having 2 to 4 carbon atoms which may be substituted with a halogen, or - which may be substituted with 10 or a methyl group. (CH,CH20) -n
H group (representing an integer of 1 to 4)], (B) a vinyl compound, and optionally (C) a free radical generator and/or a photosensitizer by using as an adhesive component, Instead of tri-n-butylborane oxide, which has a slow polymerization reaction and is conventionally used as a room-temperature polymerization reaction catalyst for use in the oral cavity, a so-called ordinary free radical generator can be used as a catalyst, and moreover, it has an excellent adhesive effect. Proposed adhesive (Special Publication No. 63-4479)
No. 2).

Furthermore, as a result of further research, the present inventors have found that by adding a new α-amino acid or α-amino acid derivative compound having an aliphatic or aromatic nucleus to the adhesive component previously proposed, adhesive properties can be improved. We have discovered that the effect can be further improved, and have arrived at the present invention.

That is, the present invention provides (1) (A) general formula (1), [wherein R
1 is hydrogen or a methyl group, R2 is hydrogen, an alkyl group having 1 to 5 carbon atoms that may be substituted with a halogen, an alkylene oxide group having 2 to 4 carbon atoms that may be substituted with a halogen, or a halogen or methyl -(CH, CH20) -n H group (n=1
(B) a compound of the general formula (II) [wherein R□ is hydrogen, a methyl group, or an isopropyl group.

isobutyl group, 5ec-butyl group, benzyl group or p-hydroxybenzyl group, R2 is hydrogen, phenyl group or tolyl group, R3 is hydrogen, methacryloxy group, methacryloxyethyl group or 2-hydroxy-3-methacryloxypropyl group an α-amino acid or an α-amino acid derivative compound having an aliphatic or aromatic nucleus, (C) a compound selected from acrylic compounds, styrene, and divinylbenzene, and (D) a free radical generating (E) containing a radical generator and/or a photosensitizer that generates free radicals by absorbing visible light, ultraviolet rays, etc., or (E) the free radicals shown in (D) above; It consists of a generator and/or a photosensitizer to which a free radical generation promoter is added, and the composition ratio of (A), (B), (C), (D), and (E) is (A) 0. 1 to 10% by weight, (B) 0.1 to 10% by weight
, (C) 70 to 99% by weight, (D) 0.1 to 5% by weight,
(E) an adhesive composition that is 0.1 to 5% by weight, (2) (
A) General formula (1), [wherein R1 is hydrogen or a methyl group, R2 is hydrogen, an alkyl group having 1 to 5 carbon atoms that may be substituted with a halogen, or a carbon number that may be substituted with a halogen. -(CH,C
H20) -n represents an H group (n = an integer of 1 to 4)]
and (B) general formula (II) [wherein R1 is hydrogen, methyl group, isopropyl group].

Isobutyl group, 5ee-butyl group, benzyl group or p-hydroxybenzyl group, R2 is hydrogen, phenyl group or tolyl group, R□ is hydrogen, methacryloxy group, methacryloxyethyl group or 2-hydroxy-3-methacryloxypropyl group (C) an acrylic compound, styrene,
2 mixed with a compound selected from divinylbenzene.
A mixture component in which (D) a free radical generator and/or a photosensitizer is mixed into one side of the mixture of seeds, and (E) a free radical generation promoter and/or photosensitizer in the other side. (1) consisting of a two-component system including a mixture component of
The present invention relates to an adhesive composition.

The α-amino acid or α-amino acid derivative compound having an aliphatic or aromatic nucleus used in the present invention has been taken up as a substance in a series of dental adhesive research in the past, and has been used as a dental adhesive. As a practical example, a material in which N-phenylglycine, N-phenylglycine-glycidyl methacrylate, or N-tolylglycine-glycidyl methacrylate is dissolved in an acetone solvent is known. However, in these studies, these α-amino acids or α-amino acid derivative compounds were used alone and dissolved in a diluent;
This material was expected to form a chelate bond between the α-amino acid derivative compound and the dentin calcium component, but since the solvent was highly volatile acetone, it did not adhere to the dentin surface. There are many problems such as it is difficult to apply uniformly, and the acetone evaporates before it fully penetrates into the tooth structure, causing crystals of α-amino acid or its derivatives to precipitate on the tooth surface. Furthermore, since the solvent does not have a reactive group, it was not possible to obtain sufficient adhesion for practical use.

In the present invention, in order to make it possible to uniformly apply the α-amino acid or α-amino acid derivative compound represented by the general formula (II) to the dentin-attached surface and to sufficiently penetrate the dentin, the general formula α-amino acid or α-
An adhesive composition containing an amino acid derivative compound, a compound represented by general formula (I), an acrylic compound, styrene, or divinylbenzene, and further using a free radical generator, such as a redox polymerization solvent or a photosensitizer. With this, we have obtained an adhesive with high practicality as an adhesive, especially a dental adhesive, and have put a composition containing α-amino acids or α-amino acid derivatives into practical use as adhesives. This was accomplished for the first time in the present invention.

Thus, in the present invention, represented by general formula (II),
The α-amino acid or α-amino acid derivative compound is blended with a compound represented by general formula (I) that has a high affinity for tooth structure, and an acrylic compound with a high boiling point and a reactive group, styrene or divinylbenzene is added. By using this product, it is possible to apply it uniformly to the dentin-attached surface, and it is also possible to sufficiently penetrate the dentin, and a uniform and strong polymerization (adhesion) reaction occurs at the bonding interface, resulting in good adhesive properties. This is what was created.

In the present invention, (A) the compound of general formula (1) is R1=
In the case of H, specific examples include 4-vinylbenzoic acid, methyl 4-vinylbenzoate, chloromethyl 4-vinylbenzoate, bromomethyl 4-vinylbenzoate, ethyl 4-vinylbenzoate, and 4-vinylbenzoic acid. 2-chloroethyl, 4-
2-Bromoethyl vinylbenzoate, n-propyl 4-vinylbenzoate, 3-chloropropyl 4-vinylbenzoate, 3-bromopropyl 4-vinylbenzoate, isopropyl 4-vinylbenzoate, 1-vinylbenzoate 4- (Chloromethyl 1)ethyl, 1-(bromomethyl)ethyl 4-vinylbenzoate, n-butyl 4-vinylbenzoate, 4-
4-chlorobutyl vinylbenzoate, 4-bromobutyl 4-vinylbenzoate, isobutyl 4-vinylbenzoate, 4
-3-chloro-1-methylpropyl vinylbenzoate, 4
-3-bromo-1-methylpropyl vinylbenzoate, 4
-n-pentyl vinylbenzoate, 4-vinylbenzoic acid 5
-chloropentyl, 5-bromopentyl 4-vinylbenzoate, isopentyl 4-vinylbenzoate, 4-chloro-1-methylbutyl 4-vinylbenzoate, 4-bromo-1-methylbutyl 4-vinylbenzoate, 4-vinyl Epoxyethyl benzoate, 2,3-epoxypropyl 4-vinylbenzoate, 2,3-epoxybutyl 4-vinylbenzoate, 2,3-epoxy-4-chlorobutyl 4-vinylbenzoate, 2-vinylbenzoate , 3-epoxy-4-bromobutyl, 2-hydroxyethyl 4-vinylbenzoate, 2-hydroxy-2-methylethyl 4-vinylbenzoate, 2-(2-hydroxyethoxy)ethyl 4-vinylbenzoate, 4- 2-(2-hydroxypropoxy)ethyl vinylbenzoate, 2-chloro-2-4-vinylbenzoate
-(2-hydroxyethoxy)ethyl, 2-bromo-2-(2-hydroxyethoxy)ethyl 4-vinylbenzoate, 3,6-thioxer-8-hydroxyoctyl 4-vinylbenzoate, 3° 4-vinylbenzoate 6-Shioxer 8-hydroxynonyl, 5-chloro3,6-thioxer 8-hydroxyoctyl 4-vinylbenzoate, 5-bromo 3,6-thioxer 8-hydroxyoctyl 4-vinylbenzoate, 4-vinylbenzoate 3 , 6.9-trioxa-11-hydroxyundecyl, 3.6.9-trioxa-11-hydroxydodecyl 4-vinylbenzoate,
4-vinylbenzoic acid 8-chloro-11-hydroxy-3
, 6,9-trioxaundecyl, 8-bromo-11-hydroxy-3,6,9-trioxaundecyl 4-vinylbenzoate, and the like. Also, in the case of R□=CH,
Specific examples include benzoic acids in which the 4-vinyl group of the above-mentioned 4-vinylbenzoic acids is changed to a 4-allyl group.

These can be used alone or as a mixture; for example, a mixture of 4-vinylbenzoic acid or 4-allylbenzoic acid and other compounds of general formula (1) can be used.

(B)-As the compound of formula (Il), an aliphatic α-
As amino acids, glycine, alanine, valine, leucine, and isoleucine; as α-amino acids with an aromatic nucleus, phenylalanine and tyrosine; and as derivative compounds with an α-amino acid skeleton, when R2 = hydrogen,
Specifically, N-methacryloxyglycine, N-methacryloxyalanine, N-methacryloxyphenylalanine, N-methacryloxytyrosine, N-methacryloxyvaline, N-methacryloxyleucine, N-methacryloxyisoleucine, N-methacryloxyleucine, Loxyethylglycine, N-methacryloxyethylalanine, N-methacryloxyethylphenylalanine, N-methacryloxyethyltyrosine, N-methacryloxyethylvaline, N-methacryloxyethylleucine, N-methacryloxyethylisoleucine, N-(2 -hydroxy-3-methacryloxypropyl)glycine, N-(2-hydroxy-3
-methacryloxypropyl)alanine, N-(2-hydroxy-3-methacryloxypropyl)phenylalanine, N-(2-hydroxy-3-methacryloxypropyl)tyrosine, N-(2-hydroxy-3-methacryloxypropyl) Valine, N-(2-hydroxy-3-methacryloxypropyl)leucine, N-(2-hydroxy-3-methacryloxypropyl)isoleucine, etc., R
When 2=phenyl group, specifically, N-phenylglycine, N-phenylalanine, N-phenylvaline, N
- Phenylleucine, N-methacryloxy-N-phenylglycine, N-methacryloxy-N-phenylalanine, N-methacryloxy-N-phenylvaline, N-methacryloxy-N-phenylleucine, N-methacryloxyethyl-N-phenylglycine, N-methacryloxyethyl-N-phenylalanine, N-(2-hydroxy-3-methacryloxypropyl)-N-phenylglycine, N-(2-hydroxy-3-methacryloxypropyl)-N-phenylalanine, etc., R2= When it is a tolyl group, specifically, N-tolylglycine, N-tolylalanine, N-tolylvaline, N-tolylleucine, N-methacryloxy-N-)-lylglycine, N-methacryloxy-N-tolylalanine, N- Methacryloxyethyl-N-tolylglycine, N-methacryloxyethyl-N-tolylalanine, N-(2-hydroxy-3-methacryloxypropyl)-N-)-lylglycine, N-(2-hydroxy-3-methacrylglycine) (roxypropyl)-N-)-lylalanine and the like.

(C) Acrylic compounds, styrene, and divinylbenzenes used in combination with the compounds represented by (A) general formula (I) and (B) general formula (II).

Methyl methacrylate, ethyl methacrylate, butyl methacrylate, polyethylene glycol dimethacrylates, 2-hydroxyethyl methacrylate, tetrahydrofurfuryl methacrylate, 2,2-bis(4-
(2-methacryloxyethoxy)phenyl]propane,
Examples include acrylonitrile, vinyl acetate, 2-cyanoacrylate, styrene, divinylbenzene, polymethyl methacrylate, polyethyl methacrylate, and the like, which may be used alone or in combination.

Among them, triethylene glycol dimethacrylate and 2-
Hydroxyethyl methacrylate, 2,2-bis[4-
(2-Methacryloxyethoxy)phenyl]propane is preferably used.

In the present invention, (A) a compound represented by general formula (1), and (B) an α-amino acid or α-amino acid derivative compound represented by general formula (II), and (C) various acrylic compounds, styrene, The usage ratio with divinylbenzene can be changed depending on the purpose of use of the adhesive or dental adhesive, but generally (A) general formula (■), and (B)
It is preferable that the compound represented by the general formula (II) accounts for 0.1 to 10% by weight based on the total amount of (C) various acrylic compounds, styrene, and divinylbenzene.

Free radical generators (D) used include various peroxides such as benzoyl peroxide and dicumyl peroxide, azobisisobutylnitrile, etc., and photosensitizers (D) include polymerized adhesives under ultraviolet irradiation. Examples of benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, etc.
In the case of visible light irradiation, examples include camphorquinone. As the free radical generation promoter (E) used in combination, N
, N-dimethyl-P-toluidine, N,N-jetanol-P-toluidine, and N,N-dimethylaminoethyl methacrylate.

In the case of polymerization adhesion at room temperature, various free radical generators, for example, various peroxides such as benzoyl peroxide, and free radical generation promoters, for example, aromatic compounds such as N,N-dimethyl-p-toluidine, etc. Examples include redox polymerization catalysts in combination with tertiary amines, and benzoyl peroxide-N,N-jetanol-p-toluidine is particularly preferably used. In addition, as photosensitization accelerators, triethanolamine, n-butylamine, Michler's ketone, 4,4'-diethylaminophenone, 4-
Ethyl dimethylaminobenzoate, N.

Examples include N-dimethylaminoethyl methacrylate, and in the case of visible light, a combination of a photosensitizer, such as camphorquinone, and a photosensitization accelerator, N,N-dimethylaminoethyl methacrylate, is preferably used.

The usage amounts of these (D) and (E) are (A) general formula (1)
and (B) a compound represented by general formula (I[) and (C)
0.0% for the total amount of various acrylic compounds, styrene, and divinylbenzene. 1 to 5 weight degrees.

(A) and (B) in the adhesive composition of the present invention.

To summarize the blending ranges of (C), (D), and (E), generally (A) 0.1 to 10% by weight, (B) 0.1
~10% by weight, (C) 70-99% by weight, (D) 0.1
-5% by weight, (E) 0.1-5% by weight, and preferred ranges are (A) 1-5% by weight, (B) 1-5% by weight, and (C) 87-97% by weight. , (D) 1 to 3% by weight,
(E) 1 to 3% by weight.

In the present invention, an adhesive composition that does not contain the free radical generator and/or photosensitizer (D) and the promoter (E) includes the free radical generator and/or photosensitizer (D) , (E
) can be used in combination with other adhesive compositions containing promoters.

The adhesive composition of the present invention further includes other additives, such as inorganic powder fillers such as kaolin, talc, clay, silica, alumina, and glass, other tackifiers, polymerization accelerators, polymerization regulators, A polymerization inhibitor and the like can also be added. Tackifiers include wax, ethylene-vinyl acetate copolymer, polymethyl methacrylate,
Polyethyl methacrylate and the like also fall under this category, and polymethyl methacrylate and polyethyl methacrylate are also used as aggregates in the same way as inorganic powder fillers. Examples of polymerization accelerators include so-called free radical generators, and examples of polymerization regulators include nitro compounds such as nitrobenzene. Examples of the polymerization inhibitor include hydroquinone, hydroquinone monomethyl ether, butyrateidohydroxytoluene, and 2-hydroxy-3-methoxybenzophenone.

In a preferred embodiment of the adhesive according to the present invention, for example, a compound represented by (A) general formula (1) and (B) general formula (II) is combined with (D) benzoyl peroxide,
(E) A method of forming an adhesive layer by mixing with (C) methyl methacrylate and polymethyl methacrylate at room temperature in the presence of N,N-jetanol-p-toluidine, similarly (A) general formula (1) and (B) a compound represented by general formula (II), (D) benzoyl peroxide,
(E) N,N-jetanol-p-toluidine in the presence of (C) 2,2-bisC4-<2-methacryloxyethoxy)phenyl]propane, triethylene glycol dimethacrylate and silica mixed at room temperature. Method of producing an adhesive layer, further comprising (A) general formulas (I) and (B)
The compound represented by the general formula (II), (C)2.2-
Bis[4-(2-methacryloxyethoxy)phenyl]
This method involves mixing propane, triethylene glycol dimethacrylate, and alcohol at room temperature, evaporating the alcohol, and then building up a dental material such as a so-called composite resin to bond by copolymerization.

[Effect]

The present inventors previously proposed a compound selected from (A) a compound of general formula (I), 4-vinylbenzoic acid, (C) an acrylic compound, styrene, divinylbenzene, and (D ) By adding and blending (B) α-amino acid or α-amino acid derivative in addition to a free radical generator or photosensitizer, it can be used as an adhesive with not only water resistance and durability but also excellent adhesive strength. It can be used as a variety of adhesives, especially as a dental adhesive.

〔Example〕

The present invention will be explained below with reference to Examples, but the present invention is not limited thereto.

Example 1 A composition consisting of two types of liquid compositions was prepared as an adhesive and used as a part A.

Part A: 1 part by weight methyl methacrylate 97.04-vinylbenzoic acid
1.5 benzoyl peroxide
1.52 Liquid Methyl Methacrylate 97.5N-Phenylglycine 1.5 After polishing the anterior labial dentin of a cow with No. 800 emery paper to make it smooth, shape it into a cylinder with a diameter of 4 mm and a height of 2 mm. A Teflon split mold with holes was placed on it and fixed. A mixture of equal amounts of Parts 1 and 2 of Agent A is applied to the surface of the natural tooth dentin in this circular hole, and after removing the excess with dry air, a composite resin/clear film for filling and restoration is applied. F3 (manufactured by Kuraray Co., Ltd.) was charged and cured.

After one hour had passed, the Teflon split mold was removed, and the natural tooth with the clear film F3 adhered thereto was immersed in water at 37°C. After 24 hours had passed, the raw tooth bonded sample was taken out from the water and the bond strength was measured using an autograph.

Similar tests were conducted on 5 samples, and the average value was 47.8 kgf/J.

As a comparative example, among the two-liquid composition of agent A of Example 1, N-
A solution containing 1.5 parts by weight of phenylglycine and 1.0 parts by weight of N,N-jetanol-P-toluidine dissolved in 99.0 parts by weight of methyl methacrylate was prepared and used together with 1 part of agent A. The same operation as in Example 1 was performed. The adhesive strength at that time was 30.9 kgf/d.

In addition, as a comparative example, in the one-liquid composition of Part A of Example 1, 1.5 parts by weight of 4-vinylbenzoic acid was not included, 98.5 parts by weight of methyl methacrylate, and 1.5 parts by weight of benzoyl peroxide. A partially dissolved solution was prepared, and the same operation as in Example 1 was performed using it together with the two liquids of agent A. The adhesive strength at that time was 22.1 kgf/a#.

Furthermore, in the two-part composition of Agent A of Example 1, 1.5 parts by weight of N-phenylglycine was not included, 99.0 parts by weight of methyl methacrylate, and N,N-jetanol-P-
Prepare a solution containing 1.0 parts by weight of toluidine and use it together with the above-mentioned 1 solution not containing 4-vinylbenzoic acid,
When the same operation as in Example 1 was carried out and the adhesive strength was measured, it was found to be 3.3 kgf/1ffl.

Example 2 As an adhesive, a composition consisting of two types of liquid compositions containing a photosensitizer component was prepared and used as a B agent.

Part B: 1 part by weight triethylene glycol dimethacrylate
51.02-Hydroxyethyl methacrylate
46.54-vinylbenzoic acid
1.5 Camphorquinone
1.02 liquid triethylene glycol dimethacrylate 42
．． 0 ethanol
55. ON-phenylglycine
2. ON, N-dimethylaminoethyl methacrylate 1.0 In the same manner as in Example 1, after fixing a Teflon split mold to the labial dentin part of a natural tooth, B After applying a mixture of equal amounts of 1 and 2 parts of the agent and removing the excess with dry air, irradiate it with visible light for 30 seconds using a visible light irradiator and Visor Light (manufactured by Nihon Higiri). went.

Thereafter, visible light polymerizable composite resin Panagraph LCR (manufactured by Nippon Kakiri Co., Ltd.) for filling and repair was inserted and cured by irradiating visible light for 40 seconds.

After 1 hour, remove the Teflon split mold and use Banagraph L.
The natural teeth with CR adhered to them were immersed in water at 37°C. After 24 hours had passed, the raw tooth bonded sample was taken out of the water and the bond strength was measured using an autograph.

Similar tests were conducted on five samples, and the average value was 65.9 kgf/ait.

As a comparative example, N-
Example 2 Using a liquid composition that did not contain 2.0 parts by weight of phenylglycine and instead contained 44.0 parts by weight of triethrene gelicoldimethacrylate and 1 solution of B.
The same operation was performed. The adhesive strength at that time was 44.1
kgf/ffl. Also, as a comparative example, in the one-liquid composition of Agent B of Example 2, 1.5 parts by weight of 4-vinylbenzoic acid 9 was not contained, and instead 48 parts by weight of 2-hydroxyethyl methacrylate was used. The same operation as in Example 2 was carried out using the two liquids, the liquid composition and B agent, each having a concentration of .0 parts by weight. The adhesive strength at that time was 39
．． It was 7 kgf/d.

Furthermore, as a comparative example, among the one-liquid compositions of agent B of Example 2,
N-phenylglycine 2 is the liquid composition containing 48.0 parts by weight of 2- and droxyethyl methacrylate instead of 1.5 parts by weight of 4-vinylbenzoic acid, and the B agent. The same operation as in Example 2 was carried out using a liquid composition containing 57.0 parts by weight of ethanol instead of 57.0 parts by weight. The adhesive strength at that time was 7.8 kgf/cxl.

Example 3 A composition consisting of two liquid compositions similar to the B agent of Example 2 was prepared as an adhesive. However, 4-vinylbenzoic acid in the 1-liquid component of Agent B has the general formula (A) in the present invention (
Among the compounds represented by I), six typical compounds shown in A to F below are substituted, and N-phenylglycine in the two-liquid component of Agent B is replaced with (B) in the present invention. ) Among the compounds represented by the general formula (II), six representative compounds shown below as a = f are substituted.

Thirty-six types of adhesive compositions are prepared by considering all combinations of these six types of compounds A to F and six types of compounds a to f. The parts by weight of the six types of compounds A to F in the adhesive composition were the same as the parts by weight of 4-vinylbenzoic acid in the 1-liquid component of Agent B in Example 2, and
The parts by weight of the six types of compounds f in the adhesive composition are the same as the parts by weight of N-phenylglycine in the two-part component of Agent B in Example 2.

The 36 types of adhesive compositions prepared in this manner are collectively referred to as Agent C.

Agent C: 1 liquid (6 types)
Part by weight Triethylene glycol dimethacrylate
51.02-Hydroxyethyl methacrylate
6 types of compounds of 46゜5A-F
1.5 Camphorquinone
1.02 liquid (6 types) Triethylene glycol dimethacrylate 42
．． 0 ethanol
6 types of compounds with 55.0a = f
2. ON, N-dimethylaminoethyl methacrylate 1.0 (A) Six types of compounds A-F represented by general formula (I) A: Methyl 4-vinylbenzoate B: 2-chloroethyl 4-vinylbenzoate C : 2-Hydroxyethyl 4-vinylbenzoate D = Epoxyethyl 4-vinylbenzoate E: 4-allylbenzoic acid F: Ethyl 4-allylbenzoate (B) represented by the general formula (II), of a '' f Six types of compounds a nigericin b: tyrosine c: N-methacryloxyethyltyrosine d: N-(2-
Hydroxy-3-methacryloxypropyl)alanine e: N-(2-hydroxy-3-methacryloxypropyl)-N-phenylglycine f: N-methacryloxy-N-tolylglycine 36 types prepared with the above compounds Using an adhesive, apply a mixture of equal amounts of C agent 1 and 2 to the labial dentin attachment surface of a natural tooth, and perform visible light polymerization for filling restoration. Mold composite resin Panagraph LCR
(manufactured by Ryosho, Japan) was cured and adhered, and the adhesive strength was measured. The measurement results are listed in [Table 1].

[Table 1] Adhesive strength of adhesive/C agent (unit: kgf/J) Looking at the results of the adhesive strength of the above adhesive/C agent, compounds represented by general formula (I) and general formula Although the adhesive strength differs slightly depending on the combination of the compounds represented by (II), the compounds represented by the general formula (I) and the general formula (II), which were carried out as a comparative example in Example 2, A much higher adhesive strength is obtained than the adhesive strength of 7.8 kgf/a1 measured using an adhesive composition containing no compound.

Example 4 A composition consisting of two types of liquid compositions was prepared as an adhesive and used as Agent D.

Agent D: 1 part by weight triethylene glycol dimethacrylate
36.02-Hydroxyethyl methacrylate
46.04-vinylbenzoic acid
1.5 benzoyl peroxide
1.52 liquid triethylene glycol dimethacrylate 42
．． 0 ethanol
45. ON-phenylglycine
2. ON, N-getanol-P-toluidine 1.0 A metal piece with a flat surface of approximately 1010 mm x 10 is polished with No. 800 emery paper to make a smooth surface, and a vinyl patch with a circular hole of 6 mrn in diameter is pasted there. . A mixture of equal amounts of Parts 1 and 2 of D-type was applied to the metal surface inside the circular hole, and after removing the excess, a stainless steel rod with a diameter of 6 mm was attached with adhesive. After 1 hour, remove the metal piece with the stainless steel rod attached to 37
immersed in water at ℃. After 24 hours, the metal piece was removed from the water and the adhesive strength was measured. The results are shown in Table 2.

As a comparative example, among the two-part composition of Agent D of Example 4, a liquid composition that did not contain N-phenylglycine and contained 44.0 parts by weight of triethylene glycol dimethacrylate instead, and one solution of Agent D were used. The same operation as in Example 4 was performed using the same. The results are shown in Table 2.

[Table 2] The compositions of the metals in [Table 2] are as follows. Gear cutter Para 12: Gold-palladium alloy Tiger gold two-metal alloy Atocast: Nickel-chromium alloy All manufactured by Nippon Ryodan Kogyo Co., Ltd. (Effects of the invention) 4 which is a compound of the present invention (A) - formula (■) - vinylbenzoic acid, (B) - an α-amino acid or a derivative thereof which is a compound of the formula (1), (C) a compound selected from acrylic compounds, styrene, divinylbenzene, and (D) a free radical generator and/or light. The adhesive composed of a composition containing a sensitizer and/or (E) a free radical generation promoter is a metal,
Strong adhesion to porcelain or teeth. This is due to the addition of α-amino acids or α-amino acid derivatives, which eliminates the need for treatment with strong acids, which were previously used due to insufficient adhesive strength, and is particularly labor-saving in dental treatment. It also has the effect of preventing tooth surface dissolution loss due to acid, and can be said to be an extremely excellent adhesive.

Claims (4)

[Claims] (1) (A) General formula (I), ▲Mathematical formulas, chemical formulas, tables, etc.▼ [In the formula, R_1 is hydrogen or a methyl group, R_2 is hydrogen,
An alkyl group having 1 to 5 carbon atoms that may be substituted with a halogen, an alkylene oxide group having 2 to 4 carbon atoms that may be substituted with a halogen, or -(CH_2CH_2O )−
(B) General formula (II) ▲ Numerical formula, chemical formula, table, etc. are available ▼ (II) [In the formula, R_1 is hydrogen, methyl group, isopropyl group, isobutyl group, sec-butyl group, benzyl group or p-
hydroxybenzyl group, R_2 represents hydrogen, phenyl group or tolyl group, R_3 represents hydrogen, methacryloxy group, methacryloxyethyl group or 2-hydroxy-3-methacryloxypropyl group], an aliphatic or aromatic nucleus represented by (C) a compound selected from acrylic compounds, styrene, dipinylbenzene, and (D) a free radical generator that generates free radicals and/or absorbs visible light, ultraviolet rays, etc. (E) containing a photosensitizer that generates free radicals, or (E) promoting free radical generation of the free radical generator and/or photosensitizer shown in (D) above. The composition ratio of (A), (B), (C), (D), and (E) is (A) 0.1 to 10% by weight and (B) 0.1 to 10% by weight. weight%
, (C) 70 to 99% by weight, (D) 0.1 to 5% by weight,
(E) An adhesive composition that is 0.1 to 5% by weight. (2) The adhesive composition according to claim 1, which is a dental adhesive. (3) The adhesive composition according to claim 1 or 2, wherein the combination of the free radical generator (D) and the promoter (E) is a redox polymerization catalyst. (4) (A) General formula (I), ▲Mathematical formulas, chemical formulas, tables, etc.▼ [In the formula, R_1 is hydrogen or a methyl group, R_2 is hydrogen,
An alkyl group having 1 to 5 carbon atoms that may be substituted with a halogen, an alkylene oxide group having 2 to 4 carbon atoms that may be substituted with a halogen, or -(CH_3CH_2O )−
(B) General formula (II) ▲ Numerical formulas, chemical formulas, tables, etc. are available ▼ (II) [In the formula, R_1 is hydrogen, methyl group, Isopropyl group, isobutyl group, sec-butyl group, benzyl group or p-
hydroxybenzyl group, R_2 represents hydrogen, phenyl group or tolyl group, R_3 represents hydrogen, methacryloxy group, methacryloxyethyl group or 2-hydroxy-3-methacryloxypropyl group], an aliphatic or aromatic nucleus represented by (C) an acrylic compound, styrene,
2 mixed with a compound selected from dipinylbenzene.
One side of the seed mixture contains (D) a mixture component mixed with a free radical generator and/or a photosensitizer, and the other side contains (E) a free radical generation promoter and/or photosensitizer. 2. The adhesive composition according to claim 1, which comprises a two-component system including a mixture component in which an adhesive is mixed.