JP2021054794A - Low water sensitive ceramic tooth and composite adhesive - Google Patents

Abstract

To provide adhesive compositions that can exert firm adhesive and adhesive durability that can withstand even in harsh oral environments by demonstrating sufficient curability even in moist environments such as in the oral cavity, and on an object to be adhered which has absorbed water.SOLUTION: Provided is an adhesive composition containing: a monomer containing a trifunctional or higher functional (meth)acrylamide group (a); a hydrophilic monomer (b); a hydrophobic monomer (c); a polymerization catalyst (d); an acid anhydride and/or weakly acidic compound (e); and a silane coupling agent (f), the monomer containing the trifunctional or higher functional (meth)acrylamide group (a) being contained in a proportion of 0.1 to 20 wt.%.SELECTED DRAWING: None

Description

The present invention is in the field of dentistry for adhering dental materials such as restoration materials, crown materials, prosthetic materials, preventive materials, abutment construction materials, root canal materials, etc. to ceramics, resins, composite resins, glass ionomer cement, etc. It is an adhesive composition used, and particularly relates to an adhesive composition having excellent operability and adhesive properties.

In recent years, composite resins have dramatically improved long-term durability and mechanical properties, and have also had properties such as sustained release of fluorine and X-ray contrast properties. Composite resins have come to be used for the functional and aesthetic restoration of dental caries in the event of dental caries or in the event of fracture or dropout of a crown restoration. In addition, the use of this composite resin is expanding to applications such as tooth surface coating materials, fee-chassis sealants, orthodontic adhesives, and resin core materials. However, since these composite resins themselves do not have adhesiveness not only to dentin but also to ceramics, it is essential to use various adhesives together. In particular, recently, it has become an issue to firmly adhere to ceramics, resins, composite resins, glass ionomer cements and the like, and to have adhesive durability.

Patent Document 1 and Patent Document 2 describe acidic groups derived from phosphoric acid as an adhesive composition that realizes stronger and more stable adhesiveness while reducing the complexity of operability of the pretreatment material. An adhesive composition containing a polymerizable monomer and a polyvalent metal ion is disclosed.

Japanese Unexamined Patent Publication No. 2008-201726 International Publication No. 2010/010901

In recent years, the range of use of dental composite materials such as dental composite resins has been expanding. However, the conventional adhesive composition has a drawback that it has poor curability in an environment containing water such as in the oral cavity or on a water-absorbed object to be adhered, and therefore sufficient adhesiveness cannot be obtained. Therefore, it exhibits sufficient curability even in a water-containing environment such as the oral cavity or on an object to be adhered that has absorbed water, and has strong adhesiveness and adhesive durability that can withstand even in a harsh oral environment. It is desired to develop an adhesive composition capable of expressing the above.

As a result of diligent research to achieve the above problems, the present inventors have (a) a monomer containing a trifunctional or higher (meth) acrylamide group, (b) a hydrophilic monomer, (c) a hydrophobic monomer, and (d). A monomer containing (e) a polymerization catalyst, (e) an acid anhydride and / or a weakly acidic compound, and (f) a silane coupling agent, and (a) a trifunctional or higher functional (meth) acrylamide group is 0.1. This problem has been solved by providing an adhesive composition contained in a proportion of ~ 20% by weight. The present invention is based on the above findings.

The adhesive composition of the present invention comprises (a) a monomer containing a trifunctional or higher functional (meth) acrylamide group, (b) a hydrophilic monomer, (c) a hydrophobic monomer, (d) a polymerization catalyst, and (e) an acid. Adhesion containing an anhydride and / or a weakly acidic compound, (f) a silane coupling agent, and (a) a monomer containing a trifunctional or higher (meth) acrylamide group in a proportion of 0.1 to 20% by weight. It is a sex composition.

（式中、Ｒは水素原子またはメチル基を表し、互いに同じでも異なってもよい。Ｒ２は、炭素数２〜６のアルキル基であり、互いに同じでも異なってもよい。） In the adhesive composition of the present invention, it is preferable that (a) a monomer containing a trifunctional or higher functional (meth) acrylamide group is represented by the following formula (1).

(In the formula, R represents a hydrogen atom or a methyl group and may be the same or different from each other. R2 is an alkyl group having 2 to 6 carbon atoms and may be the same or different from each other.)

（式中、Ｒは水素原子またはメチル基を表し、互いに同じでも異なってもよい。） In the adhesive composition of the present invention, it is preferable that (a) a monomer containing a trifunctional or higher functional (meth) acrylamide group is represented by the following formula (2).

(In the formula, R represents a hydrogen atom or a methyl group, which may be the same or different from each other.)

In the adhesive composition of the present invention, it is preferable that all Rs in the formula (2) are hydrogen atoms.

The adhesive composition of the present invention preferably does not contain a monomer containing a bifunctional or lower (meth) acrylamide group.

The adhesive composition of the present invention preferably does not contain (g) water and / or (h) an organic solvent.

The adhesive composition of the present invention exhibits sufficient curability even in a water-containing environment such as in the oral cavity or on a water-absorbed object to be adhered, and has strong adhesiveness and a harsh oral environment. It is possible to develop the adhesive durability that can be withstood.

The (a) trifunctional or higher functional (meth) acrylamide group-containing monomer (component (a)) used in the adhesive composition of the present invention is an essential component for improving the adhesiveness, and is an essential component in the molecule. Any monomer containing a trifunctional or higher functional (meth) acrylamide group can be used without any limitation. In the present invention, the component (a) is contained in a proportion of 0.1 to 20% by weight, preferably 1 to 15% by weight, and more preferably 2 to 10% by weight. (A) If the content of the monomer containing a trifunctional or higher (meth) acrylamide group exceeds 20% by weight, the polymerization of other monomers is inhibited, which may adversely affect the adhesive properties. On the other hand, when the content of (a) a monomer containing a trifunctional or higher (meth) acrylamide group is 0.1% by weight or less, no effect is observed in the adhesiveness to the dentin.

The adhesive composition of the present invention contains (a) a trifunctional or higher (meth) acrylamide group as a monomer containing a (meth) acrylamide group without containing a monomer containing a bifunctional or lower (meth) acrylamide group. It is preferable to contain only the monomer containing. Moreover, it is preferable that the adhesive composition of the present invention does not contain a monomer other than the monomer containing (a) a trifunctional or higher (meth) acrylamide group.

（式中、Ｒは水素原子またはメチル基を表し、互いに同じでも異なってもよい。Ｒ２は、炭素数２〜６のアルキル基であり、互いに同じでも異なってもよい。）

（式中、Ｒ１は水素原子またはメチル基を表す。ｍは２〜４の整数を表す。ｎは２〜４の整数を表す。ｋは０または１を表す。複数のＲ１、ｍは互いに同じであっても異なってもよい。） Specific examples of the component (a) include those represented by the following formulas (1) and the following formula (3).

(In the formula, R represents a hydrogen atom or a methyl group and may be the same or different from each other. R2 is an alkyl group having 2 to 6 carbon atoms and may be the same or different from each other.)

(In the formula, R1 represents a hydrogen atom or a methyl group. M represents an integer of 2 to 4. n represents an integer of 2 to 4. k represents 0 or 1. Multiple R1 and m are the same as each other. It may be different.)

（式中、Ｒは水素原子またはメチル基を表し、互いに同じでも異なってもよい。）

（式中、Ｒは水素原子である。） As a more specific component (a), there are those represented by the following formulas (2) and (4) to (8).

(In the formula, R represents a hydrogen atom or a methyl group, which may be the same or different from each other.)

(In the formula, R is a hydrogen atom.)

Among these, a compound containing a tetrafunctional or higher functional (meth) acrylamide group is preferable, a compound represented by the above formula (1) is more preferable, and a compound represented by the above formula (2) is used. Is most preferable. By containing the compound represented by the above formula (1), the adhesiveness can be sufficiently enhanced.

The adhesive composition of the present invention preferably does not contain a monomer containing a bifunctional or lower (meth) acrylamide group as a monomer containing a (meth) acrylamide group, and preferably contains a trifunctional or lower (meth) acrylamide group. It is more preferable that the monomer contained is not contained, and it is most preferable that the monomer not represented by the formula (1) and containing a (meth) acrylamide group is not contained.

By blending the hydrophilic monomer (b) used in the adhesive composition of the present invention with the adhesive composition, the permeability and wettability to the interface to be adhered are improved, and the adhesiveness is enhanced. The hydrophilic monomer does not correspond to the above component (a), and as long as it is a monomer showing hydrophilicity, it is limited to either monofunctional or polyfunctional regardless of the type of unsaturated group capable of radical polymerization. Can be used without. Examples of the type of radically polymerizable unsaturated group contained in the hydrophilic monomer include a (meth) acryloyl group, a styryl group, a vinyl group, an allyl group and the like, and in particular, a (meth) acryloyl group is contained as an unsaturated group. It is preferable to use a hydrophilic monomer. Further, as long as these hydrophilic monomers exhibit hydrophilicity, they have an acidic group such as a carboxyl group, a phosphoric acid group, a phosphonic acid group and a sulfonic acid group, an alkyl group, a halogen, an amino group, a glycidyl group and a glycidyl group in the molecule. It can also contain other functional groups such as hydroxyl groups.
The term "hydrophilic monomer" as used herein is defined as a monomer having a solubility of 10 parts by weight or more in 100 parts by weight of water at 23 ° C. as a hydrophilic monomer. That is, 10 g of the monomer is added to 100 g of water kept at 23 ° C. in a sample bottle, stirred for 10 minutes, and then left to stand. After 10 minutes, when the mixed mixture was observed in the sample bottle, the monomer in which the mixture was uniformly and translucently dissolved was defined as a hydrophilic monomer.

Specific examples of hydrophilic monomers in which the unsaturated group capable of radically polymerizable is a (meth) acryloyl group include 2-hydroxyethyl (meth) acrylicate, 2-hydroxypropyl (meth) acrylate, and the like. 3-Hydroxypropyl (meth) acrylate, 1,2-dihydroxypropyl (meth) acrylate, 1,3-dihydroxypropyl (meth) acrylate, 2,3-dihydroxypropyl (meth) acrylate, 2-hydroxypropyl-1,3 -Di (meth) acrylate, 3-hydroxypropyl-1,2-di (meth) acrylate, pentaerythritol di (meth) acrylate, 2-trimethylammonium ethyl (meth) acrylic chloride, (meth) acrylamide, 2-hydroxyethyl Examples thereof include (meth) acrylamide and polyethylene glycol di (meth) acrylate (those having 9 or more oxyethylene groups), but the present invention is not limited thereto. These hydrophilic monomers can be used alone or in combination of two or more.

Among these hydrophilic monomers, those having a solubility in 100 parts by weight of water at 23 ° C. of 20 parts by weight or more are preferable, and those having a solubility in 100 parts by weight of water at 23 ° C. of 40 parts by weight or more are used. That is. Specific examples thereof include 2-hydroxyethyl (meth) acrylate, polyethylene glycol di (meth) acrylate (with 9 oxyethylene groups), and polyethylene glycol di (meth) acrylate (number of oxyethylene groups). (14), polyethylene glycol di (meth) acrylate (those with 23 oxyethylene groups) and the like.
The amount of these hydrophilic monomers blended in the adhesive composition is 100 parts by weight of the total weight of the hydrophilic monomer (b) and the hydrophobic monomer (c) contained in the adhesive composition. On the other hand, the range is preferably 5 to 90 parts by weight, more preferably 10 to 60 parts by weight. If it deviates from these ranges, the wettability to the adherend surface to be adhered is lowered, the polymerizability is deteriorated, and the adhesiveness is lowered.

The hydrophobic monomer (c) used in the adhesive composition of the present invention does not correspond to the above (a) and exhibits hydrophobicity, regardless of the type of radically polymerizable unsaturated group. It can be used without any limitation in either monofunctional or polyfunctionality. Examples of the type of radically polymerizable unsaturated group contained in the hydrophobic monomer include (meth) acryloyl group, (meth) acrylicmid group, styryl group, vinyl group, allyl group and the like, and in particular, (meth) acryloyl group and It is preferable to use a hydrophobic monomer having a (meth) acrylicmid group as an unsaturated group. Further, as long as these hydrophobic monomers exhibit hydrophobicity, they include acidic groups such as carboxyl groups, phosphoric acid groups, phosphonic acid groups and sulfonic acid groups, alkyl groups, halogens, amino groups, glycidyl groups and glycidyl groups in the molecule. It can also contain other functional groups such as hydroxyl groups.
The term "hydrophobic monomer" as used herein is defined as a monomer having a solubility in 100 parts by weight of water at 23 ° C. of less than 10 parts by weight as a hydrophobic monomer. That is, 10 g of the monomer is added to 100 g of water kept at 23 ° C. in a sample bottle, stirred for 10 minutes, and then left to stand. After 10 minutes had passed, when the mixture was observed in the sample bottle, the monomer in which the mixture was phase-separated was designated as a hydrophobic monomer.

Specific examples of hydrophobic monomers in which radically polymerizable unsaturated groups are (meth) acryloyl groups include methyl (meth) acrylates and ethyl (meth) acrylates as monofunctional group-containing hydrophobic monomers. , Butyl (meth) acrylate, hexyl (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, glycidyl (meth) acrylate, lauryl (meth) acrylate, cyclohexyl (meth) acrylate, benzyl (meth) acrylate, allyl (meth) acrylate , 2-ethoxyethyl (meth) acrylate, methoxypolyethylene glycol (meth) acrylate, (meth) acrylic acid esters such as isobonyl (meth) acrylate, γ- (meth) acryloyloxypropyltrimethoxysilane, γ- (meth) Examples thereof include silane compounds such as acryloyloxypropyltriethoxysilane and nitrogen-containing compounds such as 2- (N, N-dimethylamino) ethyl (meth) acrylate.

As a hydrophobic monomer containing an aromatic bifunctional group, 2,2-bis (4- (meth) acryloyloxyphenyl) propane, 2,2-bis (4- (3- (meth) acryloyloxy-2-hydroxy) Propoxy) phenyl) propane, 2,2-bis (4- (meth) acryloyloxyethoxyphenyl) propane, 2,2-bis (4- (meth) acryloyloxydiethoxyphenyl) propane, 2,2-bis (4) -(Meta) acryloyloxytetraethoxyphenyl) propane, 2,2-bis (4- (meth) acryloyloxypentaethoxyphenyl) propane, 2,2-bis (4- (meth) acryloyloxydipropoxyphenyl) propane, 2 (4- (meth) acryloyloxyethoxyphenyl) -2 (4- (meth) acryloyloxydiethoxyphenyl) propane, 2 (4- (meth) acryloyloxydiethoxyphenyl) -2 (4- (meth) acryloyl) Oxytriethoxyphenyl) propane, 2 (4- (meth) acryloyloxydipropoxyphenyl) -2 (4- (meth) acryloyloxytriethoxyphenyl) propane, 2,2-bis (4- (meth) acryloyloxydi) Examples thereof include propoxyphenyl) propane, 2,2-bis (4- (meth) acryloyloxyisopropoxyphenyl) propane and the like.

As the hydrophobic monomer containing an aliphatic difunctional group, ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, butylene glycol di (meth) acrylate, neopentyl glycol di ( Meta) acrylate, propylene glycol di (meth) acrylate, 1,3-butanediol di (meth) acrylate, 1,4-butanediol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, di- Examples thereof include 2- (meth) acryloyloxyethyl-2,2,4-trimethylhexamethylene dicarbamate.

Examples of the hydrophobic monomer containing an aliphatic trifunctional group include trimethylolpropane tri (meth) acrylate, trimethylolethanetri (meth) acrylate, and trimethylolpropane tri (meth) acrylate.
Examples of the hydrophobic monomer containing an aliphatic tetrafunctional group include pentaerythritol tetra (meth) acrylate and pentaerythritol tetraacrylate.

Further, specifically, as a urethane-based hydrophobic monomer, it has a hydroxyl group such as 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, and 3-chloro-2-hydroxypropyl (meth) acrylate. Derived from an adduct of a monomer with a diisocyanate compound such as methylcyclohexane diisocyanate, methylenebis (4-cyclohexylisocyanate), hexamethylene diisocyanate, trimethylhexamethylene diisocyanate, isophorone diisocyanate, diisocyanate methylmethylbenzene, 4,4-diphenylmethane diisocyanate. Examples thereof include di (meth) acrylate having a bifunctional or trifunctional or higher polymerizable group and having a urethane bond. Further, as long as it contains a (meth) acrylate group, not only a monomer having a short main chain but also an oligomer having a long main chain, a prepolymer, a polymer and the like can be used without any limitation.
The hydrophobic monomers described above are not limited to these, and can be used alone or in combination of two or more.

Among these hydrophobic monomers, those having a solubility in 100 parts by weight of water at 23 ° C. are preferably less than 5 parts by weight, and more preferably, the solubility in 100 parts by weight of water at 23 ° C. is less than 1 part by weight. These include 2,2-bis (4- (3-methacryloyloxy-2-hydroxypropoxy) phenyl) propane (Bis-GMA) and 2,2-bis (4-methacryloyloxyethoxyphenyl) propane (D-2. 6E), di (methacryloyloxy) -2,2,4-trimethylhexamethylenediurethane (UDMA), triethylene glycol dimethacrylate (TEGDMA), neopentyl glycol dimethacrylate, trimethylpropantrimethacrylate and the like are preferably used. ..
The amount of these hydrophobic monomers blended in the adhesive composition is 100 parts by weight of the total weight of the hydrophilic monomer (b) and the hydrophobic monomer (c) contained in the adhesive composition. On the other hand, the range is preferably 10 to 95 parts by weight, and more preferably 40 to 90 parts by weight. If it deviates from these ranges, the wettability to the adherend surface to be adhered is lowered, the polymerizability is deteriorated, and the adhesiveness is lowered.
In the present invention, the hydrophilic monomer component (b) and the hydrophobic monomer component (c) are contained in a total amount of 30.0 to 99.5% by weight, preferably 50. It is contained in a proportion of 0 to 97.5% by weight.

The (d) polymerization catalyst used in the adhesive composition of the present invention is not particularly limited, and a known radical generator can be used without any limitation. Generally, the types of polymerization catalysts are those that start polymerization by mixing immediately before use (chemical polymerization catalyst), those that start polymerization by heating or heating (thermal polymerization catalyst), and those that start polymerization by light irradiation (radiation of light). It is roughly classified into (photopolymerization catalyst), and any of them can be used alone or in combination of two or more.

Examples of the above-mentioned chemical polymerization catalyst include a redox-type polymerization catalyst system consisting of an organic peroxide / amine compound or an organic peroxide / amine compound / sulfinate, an organic peroxide / amine compound / borate compound, oxygen and water. Examples thereof include polymerization catalyst systems such as organic boron compounds, perborates, permanganates, and persulfates that react with and initiate polymerization, and sulfinates, borate compounds, and barbituric acids are also water and /. Alternatively, the polymerization can be started by coexisting with a monomer having an acidic group.

Specific examples of organic peroxides include benzoyl peroxide, parachlorobenzoyl peroxide, 2,4-dichlorobenzoyl peroxide, acetyl peroxide, lauroyl peroxide, tertiary butyl peroxide, cumene hydroperoxide, 2 , 5-Dimethylhexane, 2,5-Dihydroperoxide, methylethylketone peroxide, tertiary butylperoxybenzoade and the like, but are not limited thereto. In addition, the above organic peroxides can be used alone or in combination of several kinds.

As the amine compound, a secondary or tertiary amine in which an amine group is bonded to an aryl group is preferable, and specifically, N, N-dimethyl-p-toluidine, N, N-dimethylaniline, N-β- Hydroxyethyl-aniline, N, N-di (β-hydroxyethyl) -aniline, N, N-di (β-hydroxyethyl) -p-toluidine, N-methyl-aniline, N-methyl-p-toluidine, etc. However, it is not limited to this. Further, the above amine compounds may be used alone or in combination of several kinds.

Specific examples of sulfinates include, but are not limited to, sodium benzenesulfinate, lithium benzenesulfinate, sodium p-toluenesulfinate, and the like. In addition, the above sulfinates can be used alone or in combination of several kinds.
Specific examples of the borate compound include sodium and lithium salts of trialkylphenyl boron and trialkyl (p-fluorophenyl) boron (alkyl groups are n-butyl group, n-octyl group, n-dodecyl group, etc.). Examples thereof include, but are not limited to, potassium salt, magnesium salt, tetrabutylammonium salt, and tetramethylammonium salt. Further, the above borate compounds may be used alone or in combination of several kinds.
Specific examples of barbituric acids include barbituric acid, 1,3-dimethylbarbituric acid, 1,3-diphenylbarbituric acid, 1,5-dimethylbarbituric acid, 5-butylbarbituric acid, 5-. Ethyl barbituric acid, 5-isopropyl barbituric acid, 5-cyclohexyl barbituric acid, 1,3,5-trimethylbarbituric acid, 1,3-dimethyl-5-ethyl barbituric acid, 1,3-dimethyl-n -Butyl barbituric acid, 1,3-dimethyl-5-isobutyl barbituric acid, 1,3-dimethyl-barbituric acid, 1,3-dimethyl-5-cyclopentyl barbituric acid, 1,3-dimethyl-5- Cyclohexyl barbituric acid, 1,3-dimethyl-5-phenylbarbituric acid, 1-cyclohexyl-5-ethylbarbituric acid, 1-benzyl-5-phenylbarbituric acid and thiobarbituric acids, and salts thereof ( Alkali metals or alkaline earth metals are particularly preferred), for example sodium 5-butylbarbiturates, sodium 1,3,5-trimethylbarbiturates, calcium 1,3,5-trimethylbarbiturates and 1-cyclohexyl. Examples include, but are not limited to, -5-ethylbarbiturate sodium. In addition, the above barbituric acids can be used alone or in combination of several kinds.

When the adhesive composition of the present invention is used alone, it is necessary to include these chemical polymerization catalysts in at least two or more packaging forms. Further, when the adhesive composition of the present invention is used together with other treatment materials, the adhesive composition of the present invention is used so that the chemical polymerization starts when the adhesive composition comes into contact with the other treatment materials. It can also be included in both the product and other treated materials.
Among these chemical polymerization catalysts, sulfinates, barbituric acids, organic peroxides-tertiary amines and the like are preferably used alone or in combination, and more preferably organic peroxides-tertiary amines. Organic peroxides-tertiary amines-barbituric acids and organic peroxides-tertiary amines-sulfinates are used.
These chemical polymerization catalysts are preferably contained in the range of 0.1 to 15.0% by weight, more preferably in the range of 0.1 to 10.0% by weight.

Examples of the photopolymerization catalyst include those consisting of a system containing only a photosensitizer, those consisting of a combination of a photosensitizer / a photopolymerization accelerator, and the like.
Further, the above-mentioned photosensitizers are roughly classified into those which start polymerization by ultraviolet rays and those which start polymerization by visible light.

Specific examples of photosensitizers that can be used as photopolymerization catalysts include benzyl, camphorquinone, α-naphthyl, acetnaphthene, p, p'-dimethoxybenzyl, p, p'-dichlorobenzylacetyl, pentandione, Α-Diketones such as 1,2-phenanthrenquinone, 1,4-phenylanthrenquinone, 3,4-phenanthrenquinone, 9,10-phenanthrenquinone, naphthoquinone, benzoin, benzoinmethyl ether, benzoinalkyl ether such as benzoin ethyl ether, etc. Classes, thioxanthone, 2-chlorothioxanthone, 2-methylthioxanthone, 2-isopropylthioxanthone, 2-methoxythioxanthone, 2-hydroxythioxanthone, 2,4-dipropylthioxanthone, 2,4-diisopropylthioxanthone and other thioxanthones, benzophenone, acetoin Benzophenones such as benzophenone, p-chlorobenzophenone, p-methoxybenzophenone, 2,4,6-trimethylbenzoyldiphenylphosphine oxide, bis (2,6-dimethoxybenzoyl) -2,4,4-trimethylpentylphosphine oxide Acylphosphine oxides such as 2-benzyl-dimethylamino-1- (4-morpholinophenyl) -butanone-1, 2-benzyl-diethylamino-1- (4-morpholinophenyl) -propanone-1 and the like. Ketals such as α-aminoacetophenones, benzyl dimethyl ketal, benzyl diethyl ketal, benzyl (2-methoxyethyl ketal), bis (cyclopentadienyl) -bis [2,6-difluoro-3- (1-pyrrolill)) Phenyl] -titanium, bis (cyclopentadienyl) -bis (pentanfluorophenyl) -titanium, bis (cyclopentadienyl) -bis (2,3,5,6-tetrafluoro-4-disyloxyphenyl)- Benzyls such as titanium can be mentioned, but the present invention is not limited to this. In addition, the above photosensitizer may be used alone or in combination of several kinds.

Specific examples of photopolymerization accelerators that can be used as photopolymerization catalysts include N, N-dimethylaniline, N, N-diethylaniline, N, N-di-n-butylaniline, and N, N-dibenzyl. Aniline, N, N-dimethyl-p-toluidine, N, N-dimethyl-m-toluidine, N, N-diethyl-p-toluidine, p-bromo-N, N-dimethylaniline, m-chloro-N, N -Dimethylaniline, p-dimethylaminobenzaldehyde, p-dimethylaminoacetophenone, p-dimethylaminobenzoic acid, p-dimethylaminobenzoic acid ethyl ester, p-dimethylaminobenzoic acid aminoester, N, N-dimethylanthra Nilic acid methyl ester, N, N-dihydroxyethylaniline, N, N-dihydroxyethyl-p-toluidine, p-dimethylaminophenyl alcohol, p-dimethylaminostyrene, N, N-dimethyl-3,5-xylidine, 4-Dimethylaminopyridine, N, N-dimethyl-α-naphthylamine, N, N-dimethyl-β-naphthylamine, tributylamine, tripropylamine, triethylamine, N-methyldiethanolamine, N-ethyldiethanolamine, N, N-dimethyl Hexylamine, N, N-dimethyldodecylamine, N, N-dimethylstearylamine, N, N-dimethylaminoethyl methacrylate, N, N-diethylaminoethyl methacrylate, 2,2'-(n-butylimino) diethanol and the like. Tertiary amines, secondary amines such as N-phenylglycine, 5-butylbarbituric acid, 1-benzyl-5-phenylbarbituric acid, 1,3,5-trimethylbarbituric acid, 1,3,5 -Barbituric acids such as sodium 1,3,5-trimethylbarbiturate, dibutyltin diacetate, dibutyltin dilaurate, dioctyltin dilaurate, dioctyl tin diversate, dioctyl tinbis (isooctyl mercaptoacetate) Ester) salts, tin compounds such as tetramethyl-1,3-diacetoxydistanoxane, aldehyde compounds such as lauryl aldehyde and terephthalaldehyde, dodecyl mercaptan, 2-mercaptobenzoxazole, 1-decanthyl, thiosartyl acid and the like. Examples include, but are not limited to, sulfur-containing compounds of. .. Further, the above photopolymerization accelerator may be used alone or in combination of several kinds.

Further, in order to improve the photopolymerization promoting ability, in addition to the above photopolymerization accelerator, citric acid, malic acid, tartaric acid, glycolic acid, gluconic acid, α-oxyisobutyric acid, 2-hydroxypropanoic acid, 3-hydroxypropane. It is effective to add oxycarboxylic acids such as acid, 3-hydroxybutanoic acid, 4-hydroxybutanoic acid and dimethylolpropionic acid.

Further, when the photopolymerization catalyst is used, there is no particular limitation even if it is in one packaging form or in two or more divided packaging forms. Among these photopolymerization catalysts, a combination of α-diketone and a tertiary amine or α-diketone and a tin compound is preferable, and camphorquinone and an amino group such as p-N, N-dimethylaminobenzoate are more preferable. Is a combination of aromatic tertiary amines directly linked to the benzene ring or aliphatic tertiary amines having a double bond in the molecule such as N, N-dimethylaminoethyl methacrylate, as well as camphorquinone and dibutyltin dilaurate. It is a combination of tin compounds such as dioctyltin dilaurate. The content of these photopolymerization catalysts is preferably in the range of 0.1 to 15.0% by weight, more preferably in the range of 0.1 to 10.0% by weight. Most preferably, it is contained in the range of 0.1 to 8.0% by weight.

Further, as the thermal polymerization catalyst by heating or heating, azo compounds such as azobisisobutyronitrile, methyl azobisisobutyrate, and azobiscyanovaleric acid are preferably used in addition to the above organic peroxides, but the present invention is limited to this. It is not something that is done. Further, these thermal polymerization catalysts can be used alone or in combination of several kinds.
Further, depending on the intended use, Bronsted acid or Lewis acid can be obtained by light irradiation with sensitizing pigments such as coumarin, cyanine, and thiazine, halomethyl group-substituted-s-triazine derivatives, and diphenyliodonium salt compounds. The produced photoacid generator, quaternary ammonium halides, transition metal compounds and the like can also be appropriately used.

The (f) silane coupling agent used in the adhesive composition of the present invention is not particularly limited, but specifically, methyltrimethoxysilane, methyltriethoxysilane, methyltrichlorosilane, dimethyldichlorosilane, and trimethylchlorosilane. , Hexamethyldisilazane, vinyltrimethoxysilane, vinyltriethoxysilane, vinyltrichlorosilane, vinyltriacetoxysilane, vinyltris (β-methoxyethoxy) silane, γ-methacryloyloxypropyltrimethoxysilane, γ-methacryloyloxypropyltris ( β-methoxyethoxy) silane, γ-chloropropyltrimethoxysilane, γ-chloropropylmethyldimethoxysilane, γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropylmethyldiethoxysilane, β- (3,4) -Epoxycyclohexyl) ethyltrimethoxysilane, N-phenyl-γ-aminopropyltrimethoxysilane, hexamethyldisilazane and the like are preferably used, and particularly preferably methyltrichlorosilane, dimethyldichlorosilane, γ-methacryloyloxypropyltri. Methoxysilane and hexamethyldisilazane are used. The blending amount of the silane coupling agent is preferably 1-8% by weight rather than 0.1-15% by weight.

Of the (e) acid anhydride and / or weakly acidic compound used in the adhesive composition of the present invention, the weakly acidic compound may be a weakly acidic compound having a pH of 2 or more, but a carboxylic acid-based compound is preferable. More preferably, it is only a carboxylic acid-based compound. As the carboxylic acid-based compound, tartaric acid, malic acid, citric acid, maleic acid, itaconic acid, and aconitic acid are preferable. In particular, citric acid, maleic acid, and itaconic acid anhydrides are preferable. The weakly acidic compound is more preferably an acid anhydride.

Of the (e) acid anhydrides and / or weakly acidic compounds used in the adhesive composition of the present invention, the acid anhydrides are not only acid anhydrides of organic acids such as carboxylic acids, but also sulfuric acid, nitric acid and phosphorus. Acid anhydrides of inorganic acids such as acids can also be used. Specific inorganic acid acid anhydrides are disulfuric acid (pyrosulfuric acid) as sulfuric acid anhydride, trifluoromethanesulfonic acid anhydride as sulfonic acid anhydride, dinitrous pentoxide as nitrate anhydride, and phosphoric acid anhydride. Pyrophosphoric acid (diphosphoric acid) and diphosphorus pentoxide (tetraphosphorus pentoxide) can be used as an anhydride, and diphosphorus trioxide can be used as an anhydride of phosphite.

It is preferably an acid anhydride having a pH of 2 or more, and even in the acid anhydride, a carboxylic acid-based compound is preferable, and it is more preferable that only a carboxylic acid-based compound is used. As the carboxylic acid-based compound, a compound of tartaric acid, malic acid, citric acid, maleic acid, itaconic acid, and aconitic acid is preferable. In particular, citric acid, maleic acid, and itaconic acid anhydrides are preferable. The acid anhydride preferably contains an acid anhydride of a carboxylic acid, sulfuric acid, nitric acid, or phosphoric acid.

(E) The blending amount of the acid anhydride and / or the weakly acidic compound is 0.1-5% by weight, more preferably 0.1-2% by weight.

When water and an organic solvent are present in the adhesive composition, they inhibit the polymerization of the polymerizable component contained in the adhesive composition and cause deterioration of adhesiveness and mechanical properties. Therefore, the adhesive composition of the present invention preferably does not contain (g) water and (h) an organic solvent, particularly when it does not contain an acidic group-containing monomer. When the adhesive composition of the present invention contains (g) water and / or (h) an organic solvent, after application to the site where the adhesive composition is to be repaired, a gun or the like before and / or during the polymerization process. It is necessary to dry it sufficiently to volatilize the water and the organic solvent.

The adhesive composition of the present invention can include (i) a filler. Examples of the filler include those known as dental fillers, such as inorganic fillers and / or organic fillers and / or organic-inorganic composite fillers, which can be used without limitation even if one or several kinds are combined. .. Further, the shape of these fillers may be any particle shape such as spherical, needle-shaped, plate-shaped, crushed-shaped, and scaly-shaped, and is not particularly limited.

Specific examples of inorganic fillers include quartz, amorphous silica, aluminum silicate, aluminum oxide, and various glasses that do not contain elements with X-ray blocking ability (glass by melting method, synthetic glass by Zolgel method, ki). (Including glass produced by phase reaction), calcium carbonate, talc, kaolin, clay, mica, aluminum sulfate, calcium sulfate, calcium phosphate, hydroxyapatite, silicon nitride, aluminum titrated, silicon carbide, boron carbide, calcium hydroxide And so on. The average particle size of these inorganic fillers is not particularly limited, but is preferably in the range of 0.001 to 10 μm, and more preferably in the range of 0.01 to 5 μm. Among the above-mentioned inorganic fillers, aerosil produced by the vapor phase method, which is ultrafine particles, or silica-zirconia oxide particles produced from a solution such as a sol-gel reaction, which is an ultrafine silica composite particle, is contained in the adhesive composition. It is effective for the present invention because it acts as a thickener when blended. Specific examples of Aerosil include Aerosil 200, Aerosil OX50, Aerosil R972, Aerosil R974, Aerosil R8200, Aerosil R711, Aerosil DT4, aluminum oxide C, titanium dioxide P25 and the like.
Further, there is no problem even if a cohesive inorganic filler or the like in which the filler containing the ultrafine particles is intentionally aggregated is used.

Further, the organic filler can be used without any limitation as long as it can be obtained by polymerizing a monomer having an unsaturated group, and the type thereof is not particularly limited. Specific examples of organic fillers include unsaturated aromatics such as polymethylmethacrylate, styrene, α-methylstyrene, styrene halide, and divinylbenzene, unsaturated esters such as vinyl acetate and vinyl propionate, and acrylonitrile. Examples thereof include those obtained by polymerizing unsaturated nitriles, monomers such as butadiene and isoprene alone, or copolymerizing several kinds. Particularly preferably, it is obtained by polymerizing various monomers already known in the dental field. The method for producing the organic filler is not particularly limited, and any method such as emulsion polymerization, suspension polymerization or dispersion polymerization of the monomer may be used, or a method of pulverizing a pre-produced polymer bulk may be used. The average particle size of these organic fillers is preferably in the range of 0.1 to 200 μm. It is more preferably 0.5 to 150 μm, still more preferably 1 to 100 μm.

Further, an organic-inorganic composite filler containing inorganic particles in the organic polymer can also be used. The inorganic filler contained in the organic polymer is not particularly limited, and known ones can be used. For example, an inorganic filler that can be used as the above-mentioned filler can be used. The method for producing the organic-inorganic composite filler is not particularly limited, and any method can be adopted. For example, a method of microencapsulating or grafting the surface of an inorganic filler with an organic substance, a method of radically polymerizing the surface of an inorganic filler after introducing a polymerizable functional group or a polymerizable initiator group, or a polymer containing a previously generated inorganic filler. Examples thereof include a method of crushing the bulk.
The average particle size of these organic-inorganic composite fillers is preferably in the range of 0.1 to 100 μm. It is more preferably 1 to 50 μm, still more preferably 0.2 to 30 μm.

A surface treatment agent and / or a surface treatment method for each filler surface such as an inorganic filler, an organic filler, and an organic-inorganic composite filler, which are fillers, for the purpose of improving wettability with various monomers and water or for other purposes. Can also be used in the adhesive composition of the present invention by subjecting the surface to the adhesive composition.
Specific examples of surface treatment agents that can be used for surface treatment include surfactants, fatty acids, organic acids, inorganic acids, silane coupling agents, titanate coupling agents, polysiloxanes, and the like. It is not limited. Further, the surface treatment method that can be used for the surface treatment is not particularly limited, and a known method can be used. Further, the surface treatment agent and / or the surface treatment method can be used alone or in combination, respectively.
There is no limitation even if the surface of the filler is surface-treated with a special surface treatment agent and / or a special surface treatment method for the purpose of making these fillers multifunctional.
The blending amount of these fillers in the adhesive composition can be arbitrarily set according to the requirements for the material properties required for the adhesive composition.

Further, in the adhesive composition, polymerization of an ultraviolet absorber such as 2-hydroxy-4-methylbenzophenone, hydroquinone, hydroquinone monomethyl ether, 2,5-diter-shari-butyl-4-methylphenol and the like is prohibited. Ingredients such as an agent, a discoloration inhibitor, an antibacterial material, a coloring pigment, and other conventionally known additives can be arbitrarily added as needed.

The method of use in the adhesive composition of the present invention is not particularly limited, and is not limited to use alone, but other treatments such as etching materials, primers, bonding materials, self-etching primers, ceramic primers, metal primers, and precious metal primers. It can be used in combination with a material, a bonding material, or the like as appropriate.

The packaging form of the adhesive composition of the present invention is not particularly limited, and depends on the storage stability of the adhesive composition, the proportion of components blended in the adhesive composition, the type of polymerization catalyst, the method of use, the purpose of use, and the like. A single package or a plurality of packages of two or more can be appropriately selected according to the intended use without any limitation.

The adhesive composition of the present invention may contain an X-ray contrast glass filler. Specific examples of elements having X-ray blocking ability that can be contained in the X-ray contrast glass filler are chromium, iron, and zinc in the 4th period of the periodic table, and strontium, yttrium, and zirconium in the 5th period of the periodic table. , Tin and tellurium, elements such as barium, lantern, yttrium, tantalum, tungsten, and bismus in the sixth period of the periodic table, but are not limited thereto. Among these, strontium, barium, lanthanum, zirconium, titanium and the like can be mentioned as an element having a preferable X-ray blocking ability contained in the X-ray contrast-enhancing glass filler.

Hereinafter, the present invention will be described in more detail and concretely by way of examples, but the present invention is not limited thereto.
[Sample preparation]
Adhesive: B was prepared according to a conventional method using the following components according to the formulation shown in Table 1.
(Adhesive: B1 to B7)
-Silane coupling agent: methyltrichlorosilane, γ-methacryloyloxypropyltrimethoxysilane-acid anhydride and / or weakly acidic compound: maleic anhydride, maleic anhydride, pyrophosphate-monomer containing (meth) acrylamide group: FAM-401 (manufactured by Fujifilm Co., Ltd.), FAM-201 (manufactured by Fujifilm Co., Ltd.)
Polymerizable monomer: 2-hydroxyethyl methacrylate (HEMA), 2,2-bis (4- (3-methacryloyloxy-2-hydroxypropoxy) phenyl) propane (Bis-GMA), di (methacryloyloxy) -2,2,4-trimethylhexamethylenediurethane (UDMA), 4- (meth) acryloyloxybutyltrimellitic acid anhydride (4MABT)
-Polymerization catalyst (photopolymerization initiator): camphorquinone and ethyl p-N, N-dimethylaminobenzoate

[Lithium disilicate glass ceramics]
(Preparation of adherent and adherent)
Molded from lithium disilicate glass ceramics (manufactured by Shofu Co., Ltd.) using a CAD / CAM system or press system, fired as instructed, washed in water and stored in water for 1 week, and then lithium disilicate glass. A ceramics bonded body and a lithium disilicate-based glass ceramics bonded body were used. The shape and dimensions of the lithium disilicate-based glass-ceramics adherent (large) were cylindrical with a diameter of 2 cm and a thickness of 1 cm. The shape and dimensions of the lithium disilicate-based glass-ceramic adhesive (small) were cylindrical with a diameter of 0.5 cm and a thickness of 1 cm.
(Preparation of adhesive test piece)
Any of the adhesives B1 to B7 after sandblasting (0.2 MPa, 1 second) with alumina (50 μm) on the lithium disilicate glass-ceramic adhesive (large) and the lithium disilicate glass-ceramic adhesive (small). After applying Kano to the lithium disilicate glass ceramics adhesive (small), press-weld it to the lithium disilicate glass ceramics adhesive (large) → remove excess adhesive → leave it for 15 minutes to cure and bond A test piece was prepared. (Number of test bodies N = 5)

[Ceramics]
(Preparation of adherent and adherent)
It was built and fired as instructed using "Vintage LD" (manufactured by Shofu Inc.), washed with water and stored in water for 1 week, and then used as a porcelain adherend and a porcelain adhesive. The shape and dimensions of the porcelain adherend (large) were cylindrical with a diameter of 2 cm and a thickness of 1 cm. The shape and dimensions of the porcelain adhesive (small) were cylindrical with a diameter of 0.5 cm and a thickness of 1 cm.
(Preparation of adhesive test piece)
After sandblasting (0.2 MPa, 1 second) of alumina (50 μm) on the porcelain adhesive (large) and porcelain adhesive (small), one of the adhesives B1 to B7 is applied to the porcelain adhesive (small). After the coating, it was pressure-welded to a porcelain adherend (large) → removal of excess adhesive → left for 15 minutes to cure to prepare an adhesive test piece. (Number of test bodies N = 5)

[Composite]
(Preparation of adherent)
The resin disc material "Shofu Disc HC" (manufactured by Shofu Inc.) was cut using a CAD / CAM system, washed with water and stored in water for 1 week, and then used as a composite resin adhered body. The shape and dimensions of the composite resin adhered body were cylindrical with a diameter of 2 cm and a thickness of 1 cm.
(Preparation of adhesive test piece)
Any of the adhesives B1 to B7 was applied to the composite resin adhered body and irradiated with light for 30 seconds (Grip Light 2: manufactured by Shofu Co., Ltd.). The adhesive surface is defined using a jig with a diameter of 0.5 cm, and after filling the composite resin (Light Fill 2: manufactured by Shofu Co., Ltd.), light irradiation (Grip Light 2: manufactured by Shofu Co., Ltd.) is performed for 30 seconds to cure the composite resin. To prepare an adhesive test piece. (Number of test bodies N = 5)

[Adhesion test method]
-Initial adhesion test: The adhesion test was performed after immersing the adhesion test piece in water at 37 ° C for 24 hours.
-Durable adhesion test: After immersing the adhesion test piece in water at 37 ° C for 24 hours, a thermal cycle test was performed under the following conditions to perform an adhesion test. The conditions of the thermal cycle were 5 ° C and 50 ° C, respectively, and the immersion for 1 minute was repeated 10,000 times.
-Shelves life test: After preparing dental primers, 5 cc each was collected in a closed container, stored in a cool and dark place at 23 ° C. for 1 year, and then the initial adhesion test and thermal cycle test were performed.
The adhesion test was carried out under atmospheric pressure at 23 ° C.

Examples 1-6 (adhesion between lithium disilicate-based glass ceramics), 7-12 (adhesion of composite resin to composite resin adherend), 13-18 (pottery) using the dental adhesive of the present invention. Regarding (adhesion between materials), although the materials and methods for adhesion are different, it was confirmed that the adhesive strength was stable in both the initial adhesion test and the durability adhesion test regardless of the presence or absence of the "shelf life test".
On the other hand, in Comparative Examples 1-6 using a dental primer containing no component (a), although the materials and methods for adhesion are different, both the initial adhesion test and the durability adhesion test have a constant adhesive strength in "without shelf life test". It was recognized that there was. However, although the adhesive test piece could be produced in the "with shelf life test", it was found that the adhesive had already fallen off at the initial adhesion test stage.

In the present specification, when the components of the invention are described as either singular or plural, or even if they are described without limitation to either singular or plural, they should be understood separately in the context. Except for, the component may be either singular or plural.
Although the present invention has been described with reference to the drawings and detailed embodiments, it should be understood by those skilled in the art that various modifications or modifications can be made based on the matters disclosed herein. Is. Therefore, it is intended that the scope of the embodiments of the present invention will include any modification or modification.

It relates to an adhesive composition used in the dental field, and is an industrially used invention.

Claims (6)

(A) Monomer containing a trifunctional or higher functional (meth) acrylamide group,
(B) Hydrophilic monomer,
(C) Hydrophobic monomer,
(D) Polymerization catalyst,
(E) Acid anhydrides and / or weakly acidic compounds, and
(F) Contains a silane coupling agent
(A) An adhesive composition containing a monomer containing a trifunctional or higher (meth) acrylamide group in a proportion of 0.1 to 20% by weight. (A) The adhesive composition according to claim 1, wherein the monomer containing a trifunctional or higher functional (meth) acrylamide group is represented by the following formula (1).

(In the formula, R represents a hydrogen atom or a methyl group and may be the same or different from each other. R2 is an alkyl group having 2 to 6 carbon atoms and may be the same or different from each other.) (A) The adhesive composition according to claim 2, wherein the monomer containing a trifunctional or higher functional (meth) acrylamide group is represented by the following formula (2).

(In the formula, R represents a hydrogen atom or a methyl group, which may be the same or different from each other.) The adhesive composition according to claim 3, wherein all R in the formula (2) are hydrogen atoms. The adhesive composition according to any one of claims 1 to 4, which does not contain a monomer containing a bifunctional or lower (meth) acrylamide group. The adhesive composition according to any one of claims 1 to 5, which does not contain (g) water and / or (h) an organic solvent.