JP2021054788A - Low water sensitive tooth adhesive primer - Google Patents

Abstract

To provide tooth adhesive primers that can exert adhesion to firmly adhere to enamel and dentin and adhesive durability that can withstand even in harsh oral environments, by demonstrating sufficient curability even in moist environments without compromising excellent storage stability in which one-component packaging is also possible.SOLUTION: Provided is a tooth adhesive primer containing: an acid group-containing monomer (a); water (b); a water-soluble organic solvent (c); a polymerization catalyst (d); and a monomer containing a trifunctional or higher functional (meth)acrylamide group (e), the monomer containing the trifunctional or higher functional (meth)acrylamide group (e) being contained in a ratio of 0.1 to 20 pts.wt based on 100 pts.wt of the total components of the tooth adhesive primer excluding (d) and (e).SELECTED DRAWING: None

Description

The present invention relates to a dentin adhesion primer used in the dental field for adhering to biohard tissues (enamel and dentin of natural teeth) and the like. Furthermore, the present invention relates to a dentin adhesive primer used in combination with other adhesive compositions.

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, resulting in defects in the tooth structure due to the onset of caries. Composite resins have come to be used for functional and aesthetic restoration of dental caries in the event of caries or 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 and metals, it is essential to use various adhesives together. Especially for dentin, the adhesive is required to have excellent adhesiveness to both enamel whose main component is an inorganic component such as hydroxyapatite and dentin whose main component is an organic component such as collagen. Has been done.

In recent years, a number of proposals have been made to sufficiently harden the adhesive layer and improve the dentin adhesiveness by combining a primer and a bonding material.
However, the low curability due to the constituents of the primer composition has not been fundamentally improved, and therefore, it is recognized that the adhesive durability to both enamel and dentin is insufficient. Was there.

International Publication No. 2007/135742 describes (a) phosphonic acid group-containing polymerizable monomer, (b) polyvalent carboxylic acid group-containing polymerizable monomer, (c) water, and (d) water-soluble organic solvent. , And (e) a dental adhesive primer composition containing a polymerization catalyst is disclosed.
This dental adhesive primer composition is sufficiently cured after removal of volatile components to exhibit adhesiveness that firmly adheres to enamel and dentin and adhesive durability that can withstand harsh oral environments. To do.
However, moisture proofing is important when applying the dentin adhesive primer, and in cases where it is difficult to prevent moisture proofing, there is a concern that there is a risk of poor adhesion due to the influence of moisture.

International Publication No. 2007/135742

Therefore, the problem to be solved by the present invention is to impair the excellent storage stability that allows a one-component packaging form that is less susceptible to deterioration and deterioration due to hydrolysis of the constituent components due to the temperature of the environment, the acidity of the solution, and the like. It is possible to exhibit sufficient curability even in the state of excessive water, and to develop adhesiveness that firmly adheres to enamel and dentin and adhesive durability that can withstand even in a harsh oral environment. The purpose is to provide a dentin adhesive primer that can be used.

The dentin adhesive primer of the present invention contains (a) an acid group-containing monomer, (b) water, (c) a water-soluble organic solvent, (d) a polymerization catalyst, and (e) a trifunctional or higher (meth) acrylamide group. (E) A monomer containing a trifunctional or higher (meth) acrylamide group, which is a dentin adhesive primer containing a monomer to be added to a total of 100 parts by weight of the components of the dentin adhesive primer excluding (d) and (e). On the other hand, it is a dentin adhesive primer contained in a ratio of 0.1 to 20 parts by weight.

（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 present invention, it is preferable that (e) a monomer containing a trifunctional or higher (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 present invention, it is preferable that (e) a monomer containing a trifunctional or higher (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 present invention, it is preferable that all Rs in the formula (2) are hydrogen atoms.

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

It is preferable that (a) the acid group-containing monomer contains (f) an inorganic acid group-containing monomer and (g) an organic acid group-containing monomer.
In the present invention, it is preferable that the (f) inorganic acid group-containing monomer contains phosphorus and / or sulfur.

In the present invention, the (g) organic acid group-containing monomer is preferably a carboxylic acid group-containing monomer.

The dentin adhesive primer of the present invention is capable of a one-component packaging form that is less susceptible to deterioration and deterioration due to hydrolysis of constituents due to environmental temperature, acidity of solution, etc., without impairing excellent storage stability. It is possible to improve the curability in a state of excessive water content, and to develop adhesiveness that firmly adheres to enamel and dentin and adhesive durability that can withstand even in a harsh oral environment.

The (e) trifunctional or higher functional (meth) acrylamide group-containing monomer (component (e)) used in the dentin adhesive primer of the present invention improves adhesive curability, particularly curability in the presence of water. Any monomer containing a trifunctional or higher functional (meth) acrylamide group in the molecule can be used without any limitation. The ratio of the monomer containing (e) trifunctional or higher (meth) acrylamide group to 100 parts by weight of the total components of the dentin adhesive primer excluding (d) and (e) is 0.1 to 20 parts by weight. It is preferably in the range of 1 to 15 parts by weight, more preferably 2 to 10 parts by weight.

（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 (e) 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。） More specific components (e) include 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, the component (e) is preferably a compound containing a tetrafunctional or higher functional (meth) acrylamide group, more preferably a compound represented by the above formula (1), and the above formula (2). Most preferably, it is a compound represented by. By containing a tetrafunctional or higher functional (meth) acrylamide group, the curability, particularly the curability in the presence of water, can be further improved.

The dentin adhesive primer 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.

The (a) acid group-containing monomer used in the dentin adhesive primer of the present invention is roughly classified into (f) an inorganic acid group-containing monomer and (g) an organic acid group-containing monomer.
(F) The inorganic acid group-containing monomer is not particularly limited as long as it does not correspond to the component (e) and has an inorganic acid group. Specifically, a known inorganic acid group-containing monomer generally used for dental materials can be used. Specific examples of the inorganic acid group contained in the inorganic acid group-containing monomer include, but are not limited to, a phosphoric acid group, a pyrophosphate group, a phosphonic acid group, and a thiophosphate group.

In the present invention, the (f) inorganic acid group-containing monomer preferably contains phosphorus and / or sulfur.

Specific examples of the unsaturated group contained in the inorganic acid group-containing monomer include (meth) acryloyl group, styryl group, vinyl group, allyl group, etc. Among these unsaturated groups, the (meth) acryloyl group is present. It is preferably an inorganic acid group-containing monomer.
Further, these inorganic acid group-containing monomers may also have other functional groups such as an alkyl group, a halogen, an amino group, a glycidyl group and / or a hydroxyl group in the molecule.
A polymer of an inorganic acid group-containing monomer in which a part or all of the acidic groups form a salt with an alkali metal can be used, and a specific inorganic acid group-containing monomer having a (meth) acryloyl group as an unsaturated group can be used. Illustrate in.

Examples of the inorganic acid group-containing monomer having a phosphoric acid group include (meth) acryloyloxymethyldihydrogen phosphate, 2- (meth) acryloyloxyethyl dihydrogen phosphate, and 3- (meth) acryloyloxypropyl dihydrogen phosphate. 4- (Meta) acryloyloxybutyl dihydrogen phosphate, 5- (meth) acryloyloxypentyl dihydrogen phosphate, 6- (meth) acryloyloxyhexyl dihydrogen phosphate, 7- (meth) acryloyloxyheptyl dihydrogen Phosphate, 8- (meth) acryloyloxyoctyl dihydrogen phosphate, 9- (meth) acryloyloxynonyl dihydrogen phosphate, 10- (meth) acryloyloxydecyl dihydrogen phosphate, 11- (meth) acryloyloxyundecyl Dihydrogen phosphate, 12- (meth) acryloyl oxide decyl dihydrogen phosphate, 16- (meth) acryloyloxyhexadecyldihydrogen phosphate, 20- (meth) acryloyloxyecosil dihydrogen phosphate, di (meth) Acryloyloxyethyl hydrogen phosphate, di (meth) acryloyloxybutyl hydrogen phosphate, di (meth) acryloyloxyhexyl hydrogen phosphate, di (meth) acryloyloxyoctylhydrogen phosphate, di (meth) acryloyloxynonyl hydrogen phosphate , Di (meth) acryloyloxydecylhydrogen phosphate, 1,3-di (meth) acryloyloxypropyl-2-dihydrogen phosphate, 2- (meth) acryloyloxyethylphenylhydrogen phosphate, 2- (meth) acryloyl Examples include, but are not limited to, oxyethyl 2'-bromoethyl hydrogen phosphate, (meth) acryloyloxyethylphenylphosphonate, and the like.

Examples of the inorganic acid group-containing monomer having a pyrophosphate group include di [2- (meth) acryloyloxyethyl] pyrophosphate, di [3- (meth) acryloyloxypropyl], and di [4-( Meta) acryloyloxybutyl], dipyrophosphate [5- (meth) acryloyloxypentyl], dipyrophosphate [6- (meth) acryloyloxyhexyl], dipyrophosphate [7- (meth) acryloyloxyheptyl], pyrolin Di [8- (meth) acryloyloxyoctyl], di [9- (meth) acryloyloxynonyl], dipyrophosphate [10- (meth) acryloyloxydecyl], di [12- (meth) pyrophosphate] Acryloyl oxide decyl], tetra pyrophosphate [2- (meth) acryloyloxyethyl], tripylophosphate [2- (meth) acryloyloxyethyl], and the like, but are not limited thereto.

Examples of the inorganic acid group-containing monomer having a thiophosphate group include 2- (meth) acryloyloxyethyl dihydrogenthiophosphate, 3- (meth) acryloyloxypropyldihydrogenthiophosphate, and 4- (meth) acryloyloxy. Butyldihydrogenthiophosphate, 5- (meth) acryloyloxypentyldihydrogenthiophosphate, 6- (meth) acryloyloxyhexyl dihydrogenthiophosphate, 7- (meth) acryloyloxyheptyl dihydrogenthiophosphate, 8 -(Meta) acryloyloxyoctyldihydrogenthiophosphate, 9- (meth) acryloyloxynonyldihydrogenthiophosphate, 10- (meth) acryloyloxydecyldihydrogenthiophosphate and the like, but are limited thereto. It's not something.

The (f) inorganic acid group-containing monomer particularly preferable in the present invention is, for example, an inorganic acid group-containing monomer having a phosphonic acid group. An inorganic acid group-containing monomer having a phosphonic acid group (phosphonic acid group-containing monomer) is at least one (-PO (OH) ₂ ) or phosphonic acid monoester group (-PO (OH) OH) directly linked to a carbon atom in the molecule. ) (OR)) and a monomer having at least one polymerizable unsaturated group.
That is, any functional group having any functional group in the molecule can be used without any limitation as long as it satisfies these conditions. In addition, the phosphonic acid group-containing monomer includes the number of phosphonic acid groups or phosphonic acid monoester groups in the molecule, the types of radically polymerizable unsaturated groups such as (meth) acryloyl group, styryl group, vinyl group, and allyl group. The number is not particularly limited.
By containing a phosphonic acid group-containing monomer in the dentin adhesion primer of the present invention, excellent dentin adhesion performance can be exhibited particularly with respect to enamel. In addition, since the phosphonic acid group-containing monomer is not bonded to an oxygen atom by an ester bond, it is not easily hydrolyzed in the molecule even in an acidic atmosphere in which water coexists, and has excellent storage stability. There is. Therefore, the packaging form can be not only a two-component packaging form divided into two, but also a one-component packaging form.

Among these phosphonic acid group-containing monomers, the general formula (I): which is excellent in dentin adhesion and storage stability:

[In the formula, R ¹ represents a hydrogen atom or a methyl group, R ² represents an alkylene group having 5 to 10 carbon atoms, and R ³ represents an alkylene group having 1 to 6 carbon atoms. ], It is preferable to use the phosphonic acid group-containing monomer.
Specific examples of the phosphonic acid group-containing monomer represented by the general formula (I) include, but are not limited to, the following compounds.

Among these phosphonic acid group-containing monomers, 6- (meth) acryloyloxyhexyl phosphonoacetate, 6- (meth) acryloyloxyhexyl-3-phosphonopropionate, 10- (meth) acryloyloxydecyl-3-3. It is more preferable to use phosphonoacetate, 10- (meth) acryloyloxydecylphosphonopropionate, 5- (meth) acryloyloxypentyl-3-phosphonopropionate and the like.

These inorganic acid group-containing monomers can be used alone or in combination of two or more.

The content of these (f) inorganic acid group-containing monomers can be appropriately selected depending on the intended use or purpose of use of the dentin adhesive primer and the method of use, but the dentin except for (d) and (e). It is preferably in the range of 0.1 to 40.0 parts by weight with respect to 100 parts by weight of the total components of the adhesive primer.
If the content of these inorganic acid group-containing monomers exceeds 40.0 parts by weight, the curability due to the polymerizable property is lowered, which adversely affects the adhesive properties. On the other hand, when the content of the inorganic acid group-containing monomer is less than 0.1 parts by weight, no effect is observed in the adhesiveness to the enamel.

Although the inorganic acid group-containing monomers have been shown above, the present invention is not limited to these, and these inorganic acid group-containing monomers can be used alone or in combination of two or more. Further, as these inorganic acid group-containing monomers, not only monomers having a short main chain but also oligomers having a long main chain, prepolymers, polymers and the like can be used without any limitation.
Derivatives of inorganic acid group-containing monomers such as metal salts, ammonium salts, and acid chlorides in which the acidic groups of these inorganic acid group-containing monomers are partially neutralized also adversely affect the adhesion to various adherends. It can be used as long as it is not given.

The (g) organic acid group-containing monomer used in the dentin adhesive primer of the present invention is not particularly limited as long as it does not correspond to the component (e) and has an organic acid group. Specifically, a known organic acid group-containing monomer generally used for dental materials can be used. Specific examples of the organic acid group contained in the organic acid group-containing monomer include a carboxyl group, a sulfonic acid group, a sulfinic acid group, a phenol group, an enol group, a thiophenol group, an oxime group, an aromatic sulfoamide group, and a primary nitro. Examples include, but are not limited to, groups, secondary amide groups, hydroxyl groups and the like.

In the present invention, the (g) organic acid group-containing monomer is preferably a carboxylic acid group-containing monomer.

Specific examples of the unsaturated group contained in the organic acid group-containing monomer include a (meth) acryloyl group, a styryl group, a vinyl group, an allyl group, etc. Among these unsaturated groups, the (meth) acryloyl group is present. It is preferably an organic acid group-containing monomer.
Further, these organic acid group-containing monomers may also have other functional groups such as an alkyl group, a halogen, an amino group, a glycidyl group and / or a hydroxyl group in the molecule.
A polymer of an organic acid group-containing monomer in which a part or all of the acidic groups form a salt with an alkali metal can be used, and an organic acid group-containing monomer having a (meth) acryloyl group as an unsaturated group can be specifically used. Illustrate to.

Examples of the acidic group-containing monomer having a monocarboxylic acid group include (meth) acrylic acid, 2-chloro (meth) acrylic acid, 3-chloro (meth) acrylic acid, 2-cyano (meth) acrylic acid, and N-. (Meta) acryloyl-p-aminobenzoic acid, N- (meth) acryloyl-5-aminosalicylic acid, 2- (meth) acryloyloxybenzoic acid, p-vinylbenzoic acid, 5- (meth) acryloylaminopentylcarboxylic acid, etc. However, the present invention is not limited to these.

Examples of the acidic group-containing monomer having a sulfonic acid group include 2- (meth) acrylamide-2-methylpropanesulfonic acid, styrenesulfonic acid, 2-sulfoethyl (meth) acrylicate, and 4- (meth) acryloyloxybenzene. Examples thereof include, but are not limited to, sulfonic acid, 3- (meth) acryloyloxypropane sulfonic acid.

The (g) organic acid group-containing monomer particularly preferable in the present invention is, for example, a polyvalent carboxylic acid group-containing monomer. The polyvalent carboxylic acid group-containing monomer is a group having at least two or more carboxylic acid groups in the molecule, or a group which easily reacts with water to generate two or more carboxylic acid groups, and at least one polymerizable unsaturated group. Means a monomer with.
That is, any functional group that satisfies these conditions can be used without any limitation. Further, the polyvalent carboxylic acid group-containing monomer is not particularly limited in the type and number of radically polymerizable unsaturated groups such as (meth) acryloyl group, styryl group, vinyl group and allyl group contained in the molecule. By containing a polyvalent carboxylic acid group-containing monomer in the dentin adhesion primer of the present invention, excellent dentin adhesion performance can be exhibited for dentin.

Specific examples of the polyvalent carboxylic acid group-containing monomer are aconitic acid, mesaconic acid, maleic acid, maleic anhydride, itaconic acid, itaconic anhydride, fumaric acid, glutaconic acid, citraconic acid, utraconic acid, 1,4-. Di (meth) acryloyloxyethyl pyromellitic acid, 6- (meth) acryloyloxynaphthalene-1,2,6-tricarboxylic acid, 1-butene 1,2,4-tricarboxylic acid, 3-butene 1,2,3- Tricarboxylic acid, 4- (meth) acryloyloxyethyl trimellitic acid and its anhydride, 4- (meth) acryloyloxybutyltrimellitic acid and its anhydride, β- (meth) acryloyloxyethyl hydrogen succinate, β- (meth) acryloyloxyethyl hydrogen maleate, 11- (meth) acryloyloxy-1,1-undecandicarboxylic acid, 4- (meth) acryloyloxyethoxycarbonylphthalic acid, 4- (meth) acryloyloxybutyl Oxycarbonylphthalic acid, 4- (meth) acryloyloxyhexyloxycarbonylphthalic acid, 4- (meth) acryloyloxyoctyloxycarbonylphthalic acid, 4- (meth) acryloyloxydecyloxycarbonylphthalic acid and their acid anhydrides, 6- (meth) acryloyloxy-1,1-hexanedicarboxylic acid, 8- (meth) acryloyloxy-1,1-octanedicarboxylic acid, 10- (meth) acryloyloxy-1,1-decandicarboxylic acid, 11- (Meta) Acryloyloxy-1,1-undecandicarboxylic acid and the like can be mentioned, but the present invention is not limited thereto. These polyvalent carboxylic acid group-containing polymerizable monomers can be used alone or in combination of two or more. Among these polyvalent carboxylic acid group-containing monomers, it is more preferable to use 4-methacryloyloxyethyl trimellitic acid and its anhydride, 4-acryloyloxyethyltrimellitic acid and its anhydride, and the like.

The content of these (g) organic acid group-containing monomers can be appropriately selected depending on the intended use or purpose of use of the dentin adhesive primer and the method of use, but the dentin except for (d) and (e). It is preferably in the range of 0.1 to 40.0 parts by weight with respect to 100 parts by weight of the total components of the adhesive primer.
If the content of these organic acid group-containing monomers exceeds 40.0 parts by weight, the curability due to the polymerizable property is lowered, which adversely affects the adhesive properties. On the other hand, when the content of the organic acid group-containing monomer is less than 0.1 parts by weight, no effect is observed in the adhesiveness to dentin.

Although the organic acid group-containing monomers have been shown above, the present invention is not limited to these, and these organic acid group-containing monomers can be used alone or in combination of two or more. Further, as these organic acid group-containing monomers, not only monomers having a short main chain but also oligomers having a long main chain, prepolymers, polymers and the like can be used without any limitation.
Derivatives of organic acid group-containing monomers such as metal salts, ammonium salts or acidified compounds in which the acidic groups of these organic acid group-containing monomers are partially neutralized also adversely affect the adhesion to various adherends. It can be used as long as it is not given.

The content of the (a) acid group-containing monomer in the present invention can be appropriately selected depending on the intended use or purpose of use of the dentin adhesive primer and the method of use, but the dentin except for (d) and (e). It is preferably in the range of 0.2 to 80.0 parts by weight with respect to 100 parts by weight of the total components of the adhesive primer.

Further, when the dentin adhesive primer of the present invention further enhances the adhesiveness to the dentin, or when imparting the adhesiveness to various adherends containing noble metals and the like, a polymerizable monomer containing a sulfur atom in the molecule. , Silane compounds can be included alone or in combination, respectively.

In order to impart adhesiveness to a noble metal to the dentin adhesive primer of the present invention, it is also effective for the present invention to use a monomer containing a sulfur atom in the molecule. Any monomer containing a sulfur atom in the molecule can be used regardless of the type and number of unsaturated groups and the presence or absence of other functional groups.
Specific examples of a monomer containing a sulfur atom in a molecule having a (meth) acryloyl group as an unsaturated group include a (meth) acrylate having a triazinethiol group, a (meth) acrylate having a mercapto group, and a polysulfide group. (Meta) acrylate, (meth) acrylate having a thiophosphate group, (meth) acrylate having a disulfide cyclic group, (meth) acrylate having a mercaptodiathiazole group, (meth) acrylate having a thiouracil group, having a thiirane group. Examples thereof include (meth) acrylate, but the present invention is not limited to this. Monomers containing a sulfur atom in these molecules can be used alone or in combination of two or more.

In order to impart adhesiveness to ceramics, composite resins and the like to the dentin adhesive primer of the present invention, it is also effective to use an organosilane compound having at least one polymerizable unsaturated group in the molecule. Any organosilane compound having a polymerizable unsaturated group in the molecule can be used regardless of the type and number of unsaturated groups and the presence or absence of other functional groups. Specific examples of the organosilane compound having a polymerizable unsaturated group include vinyltrimethoxysilane, vinyltriethoxysilane, vinyltrichlorosilane, vinyl (β-methoxyethoxy) silane, and γ-methacryloxypropyltrimethoxysilane. However, it is not limited to this. These organosilane compounds can be used alone or in combination of two or more.

In order to impart adhesiveness to ceramics, composite resins and the like to the dentin adhesive primer of the present invention, it is also effective to use an organosilane compound having at least one polymerizable unsaturated group in the molecule. Any organosilane compound having a polymerizable unsaturated group in the molecule can be used regardless of the type and number of unsaturated groups and the presence or absence of other functional groups. Specific examples of the organosilane compound having a polymerizable unsaturated group include vinyltrimethoxysilane, vinyltriethoxysilane, vinyltrichlorosilane, vinyl (β-methoxyethoxy) silane, and γ-methacryloxypropyltrimethoxysilane. However, it is not limited to this. These organosilane compounds can be used alone or in combination of two or more.

(B) Water contained as an essential component in the dentin adhesion primer of the present invention is (a) such as (f) an inorganic acid group-containing monomer and (g) an organic acid group-containing monomer contained in the dentin adhesion primer. ) It has a function of activating the acidic group of the acid group-containing monomer, promoting the decalcification action on the tooth substance, and promoting the penetration into the tooth substance. Therefore, water can be used without any limitation as long as it does not contain impurities that adversely affect storage stability, biocompatibility, polymerizable property, dentin adhesiveness and the like. It is preferable to use distilled water or ion-exchanged water.
The content of water can be appropriately selected according to the intended use or purpose of use and the method of use of the dentin adhesive primer of the present invention, but the total components of the dentin adhesive primer excluding (d) and (e). It is preferably in the range of 0.1 to 80.0 parts by weight with respect to 100 parts by weight. If the water content exceeds 80.0 parts by weight, the composition cannot maintain a uniform state and separates, which adversely affects the storage stability. On the other hand, if the water content is less than 0.1 parts by weight, sufficient adhesiveness cannot be obtained for various adherends including dentin.

The (c) water-soluble organic solvent contained as an essential component in the dentin adhesion primer of the present invention includes (f) an inorganic acid group-containing monomer and (g) an organic acid group-containing monomer contained in the dentin adhesion primer. It has a role as a dissolution accelerator that dissolves various monomers, water, polymerization catalysts and other compounding components in an arbitrary ratio, and also has a function of promoting the penetration of the dentin adhesive primer into the dentin. is there. In addition, the liquid viscosity of the dentin adhesive primer can be lowered, and operability such as dropping from a container or applying to a portion to be adhered can be improved.
Specific examples of this water-soluble organic solvent include alcohols such as methanol, ethanol, 1-propanol, 2-propanol and 1-butanol, triethylene glycol monomethyl ether, triethylene glycol monoethyl ether and dipropylene glycol. Examples thereof include ether compounds such as monomethyl ether, tetrahydrofuran and dimethoxyethane, and water-soluble organic solvents such as ketone compounds such as acetone and methyl ethyl ketone, but the solvent is not limited thereto and can be used without any limitation. In addition, these water-soluble organic solvents can be used alone or in combination of several kinds. Among these water-soluble organic solvents, methanol, ethanol, 1-propanol, 2-propanol, acetone and the like having excellent compatibility with water are preferable, and acetone and ethanol are more preferable.

The content of the organic solvent can be appropriately selected depending on the intended use or purpose of use and the method of use of the dentin adhesive primer of the present invention, but preferably, the dentin adhesive primer other than (d) and (e) is used. The range is 0.1 to 80.0 parts by weight with respect to 100 parts by weight of the total components. When the content of the organic solvent exceeds 80.0 parts by weight, the adhesiveness to the dentin is lowered. On the other hand, if the content of the organic solvent is less than 0.1 parts by weight, the composition cannot maintain a uniform state and separates, which adversely affects the storage stability.

The (d) polymerization catalyst contained as an essential component in the dentin adhesive primer of the present invention is not particularly limited, and a known radical generator can be used without any limitation. The types of polymerization catalysts are generally 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. 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 specific examples thereof include N, N-dimethyl-p-toluidine, N, N-dimethylaniline, and 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 dentin adhesive primer of the present invention is used alone, it is necessary to divide and include these chemical polymerization catalysts in at least two or more packaging forms. When the dentin adhesion primer of the present invention is used together with other compositions, the dentin adhesion of the present invention is used so that the chemical polymerization starts when the dentin adhesion primer comes into contact with the other composition. It can also be included in both the primer and the other composition, respectively.
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 to 15.0 parts by weight, more preferably 0. It is contained in the range of 1 to 10.0 parts 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 photosensitizer is roughly classified into one in which polymerization is initiated by ultraviolet rays and one in which polymerization is initiated 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 parts by weight, more preferably 0, based on 100 parts by weight of the total components of the dentin adhesive primer excluding (d) and (e). It should be contained in the range of 1 to 10.0 parts by weight. Most preferably, it is contained in the range of 0.1 to 8.0 parts 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. It is not limited. 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 dentin adhesive primer of the present invention can contain (h) a hydrophobic monomer. (H) As the hydrophobic monomer, radical polymerization is possible as long as it is a monomer exhibiting hydrophobicity, except for the monomer containing the component (e), the component (a) and the bifunctional or lower (meth) acrylamide group. Regardless of the type of saturated group, it can be used without any limitation in either monofunctionality 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. 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 the hydrophobic monomer in which the unsaturated group capable of radical polymerization is a (meth) acryloyl group among the hydrophobic monomers will be exemplified.
Examples of the monofunctional group-containing hydrophobic monomer include methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, hexyl (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, glycidyl (meth) acrylate, and lauryl. (Meta) such as (meth) acrylate, cyclohexyl (meth) acrylate, benzyl (meth) acrylate, allyl (meth) acrylate, 2-ethoxyethyl (meth) acrylate, methoxypolyethylene glycol (meth) acrylate, isobonyl (meth) acrylate, etc. Acrylate esters, silane compounds such as γ- (meth) acryloyloxypropyltrimethoxysilane, γ- (meth) acryloyloxypropyltriethoxysilane, 2- (N, N-dimethylamino) ethyl (meth) acrylate, etc. Examples of the nitrogen-containing compound and the like.

As the hydrophobic monomer containing an aromatic bifunctional group, 2,2-bis (4- (meth) acryloyloxyphenyl) propane, 2,2-bis (4- (3- (meth) acryloyloxy-2-) Hydroxypropoxy) 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) Acryloyloxytriethoxyphenyl) propane, 2 (4- (meth) acryloyloxydipropoxyphenyl) -2 (4- (meth) acryloyloxytriethoxyphenyl) propane, 2,2-bis (4- (meth) acryloyloxy) Dipropoxyphenyl) propane, 2,2-bis (4- (meth) acryloyloxyisopropoxyphenyl) propane and the like can be mentioned.

Examples of the aliphatic bifunctional monomer-containing hydrophobic monomer include ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, butylene glycol di (meth) acrylate, and 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.

Specific examples of the urethane-based hydrophobic monomer include hydroxyl groups such as 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, and 3-chloro-2-hydroxypropyl (meth) acrylate. Derived from an adduct of the monomer having a diisocyanate 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. Specifically, 2,2-bis (4- (3-methacryloyloxy-2-hydroxypropoxy) phenyl) propane (Bis-GMA), 2,2-bis (4-methacryloyloxyethoxyphenyl) propane (D-2.6) It is preferable to use E), di (methacryloyloxy) -2,2,4-trimethylhexamethylenediurethane (UDMA), triethylene glycol dimethacrylate (TEGDMA), neopentyl glycol dimethacrylate, trimethylpropantrimethacrylate and the like. ..
The amount of these hydrophobic monomers blended in the dentin adhesive primer is 1.0 to 50.0 with respect to 100 parts by weight of the total components of the dentin adhesive primer excluding (d) and (e). The range of parts by weight is preferable, and the range is more preferably 1.0 to 30.0 parts by weight. If it deviates from these ranges, the wettability to the adherend surface to be adhered is lowered, and the curability due to the polymerizable property is lowered, resulting in a deterioration in the adhesive properties.

It is preferable that the dentin adhesive primer of the present invention does not contain a hydrophilic monomer that is easily compatible with water. The hydrophilic monomer can make the hydrophobic component and the hydrophilic component contained in the dentin adhesive primer compatible with each other at an arbitrary ratio, and improve the permeability and wettability to the interface to be adhered to enhance the adhesiveness. effective. However, on the other hand, since the dentin adhesive primer is in an acidic atmosphere, the hydrophilic monomer is susceptible to deterioration and alteration due to hydrolysis, which may cause a decrease in adhesiveness. Further, the hydrophilic monomer is originally poor in curability, and even when it is cured, it has a high affinity with water, so that it causes hydrolysis, and there are problems in adhesive durability.
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, when 10 g of a monomer is added to 100 g of water kept at 23 ° C. in a sample bottle, and the mixture is mixed and stirred for 10 minutes and left to stand, the monomer in which the mixture is uniformly transparent or translucent in the sample bottle is hydrophilic. It was used as a 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, it is preferable not to include those having a solubility of 20 parts by weight or more in 100 parts by weight of water at 23 ° C., and more preferably 40 parts by weight or more of solubility in 100 parts by weight of water at 23 ° C. It does not include what 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.

(I) Filler is added to the dentin adhesive primer for the purpose of thickening the dentin adhesive primer of the present invention to improve operability or imparting mechanical strength to the adhesive interface layer to improve the adhesiveness. Can include. The filler is not particularly limited, and a known dental filler can be used. For example, an inorganic filler and / or an organic filler and / or an organic-inorganic composite filler and the like can be mentioned, and these can be used without any limitation even if one kind or a combination of several kinds is used.
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. Further, the particle size of these fillers is not particularly limited, but those in the range of 0.001 to 10 μm are preferable, and more preferably in the range of 0.01 to 5 μm from the viewpoint of problems such as sedimentation and separation.
Among these 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 blended in the dentin adhesive primer. It is effective for the present invention because it acts as a thickener. 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 these ultrafine particles are intentionally aggregated is used.

Further, in the dentin adhesive primer, polymerization of an ultraviolet absorber such as 2-hydroxy-4-methylbenzophenone, hydroquinone, hydroquinone monomethyl ether, 2,5-di-terriary butyl-4-methylphenol, etc. 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 dentin adhesive primer of the present invention is not particularly limited, and is not limited to use alone, but also has other compositions such as an etching material, a primer, a bonding material, a self-etching primer, a ceramic primer, a metal primer, and a noble metal primer. It can be used in combination with an object as appropriate.

The dentin adhesive primer of the present invention is characterized by being excellent in storage stability due to the composition of the components contained in the composition. Therefore, it can be made into one packaging form. Further, depending on the ratio of components to be blended in the dentin adhesive primer of the present invention, the type of polymerization catalyst, the method of use, the purpose of use, etc., two or more packaging forms can be formed and can be appropriately selected.

Hereinafter, the present invention will be specifically described with reference to Examples and Comparative Examples, but the present invention is not limited to these Examples.
The test method for evaluating the performance of the dentin adhesive primer prepared in the following examples is as follows.

(1) Tooth property adhesion test Evaluation purpose:
Evaluation of dentin adhesion to enamel and dentin using various dentin adhesion primers.
Evaluation method:
After slaughter, the removed central incisors of the mandibular mandible are frozen and stored within 24 hours, thawed, and then the roots are removed and the crowns are cut to prepare cow tooth fragments. Embed the piece in epoxy resin. Under water injection, the embedded cow tooth is washed with water by exposing the enamel or dentin with # 600 water-resistant abrasive paper, and dried by blowing dry air for 5 seconds. A double-sided tape with a hole of 4 mm in diameter is applied to the exposed enamel or dentin to define the adhesive surface. Adhesion treatment is performed on the specified adhesive surface by the adhesive technique specified in Examples or Comparative Examples. After that, a plastic mold (inner diameter 4 mm, height 2 mm) is fixed to the bonded surface, and a photopolymerization type composite resin (Beauty Fill, manufactured by Shofu Inc.) is filled inside the mold, and a photopolymerization irradiator (photopolymerization irradiator) ( Grip Light II (manufactured by Shofu Inc.) is used to irradiate light for 30 seconds to cure. After curing, the mold is removed and used as an adhesive test piece. After immersing this adhesion test piece in 37 ° C distilled water for 24 hours, a dentin adhesion test based on shear adhesion strength at a crosshead speed of 1 mm / min using an Instron universal testing machine (Instron 5567, manufactured by Instron). I do.

(2) Tooth adhesive durability test Evaluation purpose:
Evaluation of dentin adhesion durability to enamel and dentin using various dentin adhesion primers.
Evaluation method:
After preparing an adhesive test piece in the same manner as in the dentin adhesiveness test, the adhesiveness test piece is immersed in 37 ° C. distilled water for 24 hours. After that, 2000 cycles of thermal cycles of alternately immersing in constant temperature water tanks at 4 ° C. and 60 ° C. for 1 minute each are carried out. After the completion of the thermal cycle, this adhesion test piece is subjected to a dentin adhesion test based on shear adhesion strength at a crosshead speed of 1 mm / min using an Instron universal testing machine (Instron 5567, manufactured by Instron).

(3) Storage stability test Evaluation purpose:
The prepared various dentin adhesion primers were stored in an environment of 50 ° C. for 2 weeks, and the dentin adhesion to enamel and dentin using the composition was evaluated.
Evaluation method:
The dentin adhesiveness test is performed by the shear adhesive strength by the same method as the dentin adhesiveness test.

The abbreviations of the materials used for preparing each dentin adhesive primer in the examples and comparative examples of the present invention are as follows.
Bis-GMA: 2,2-bis (4- (3-methacryloyloxy-2-hydroxypropoxy) phenyl) propane
UDMA: Di (methacryloyloxy) -2,2,4-trimethylhexamethylenediurethane
TEGDMA: Triethylene glycol dimethacrylate
HEMA: 2-Hydroxyethyl methacrylate
CQ: Camphorquinone
BPO: Pennzoil Peroxide
DEPT: N, N-di (β-hydroxyethyl) -p-toluidine
DMB: Dimethylaminobenzoic acid
MHPA: 6-methacryloyloxyhexyl phosphonoacetate
MHPP: 6-methacryloyloxyhexyl-3-phosphonopropionate
META: 4-methacryloyloxyethyl trimellitic acid anhydride
MET: 4-methacryloyloxyethyl trimellitic acid
AETA: 4-acryloyloxyethyl trimellitic anhydride
AET: 4-acryloyloxyethyl trimellitic acid
FAM-401 (manufactured by FUJIFILM Corporation): Monomer containing (meth) acrylamide group
FAM-201 (manufactured by FUJIFILM Corporation): Monomer containing (meth) acrylamide group

A. Preparation of primer composition [Preparation of one-component primer composition (compositions 1 to 8)]
One-component primer compositions (compositions 1 to 8) were prepared with the compositions shown in Table 1, and used in Examples and Comparative Examples.

B. Preparation of Bonding Material Composition [Preparation of Photopolymerizable One-Liquid Bonding Material Composition (Compositions A and B)]
Photopolymerizable one-component bonding material compositions (compositions A and B) were prepared with the compositions shown in Table 2, respectively, and used in Examples and Comparative Examples.

[Preparation of dual polymerizable two-component bonding material composition (compositions C and D)]
Dual polymerization type two-component bonding material compositions (compositions C and D) were prepared with the compositions shown in Table 3, respectively, and used in Examples and Comparative Examples.

C. Evaluation of dentin adhesion [Examples 1 to 5]
A two-step type adhesive system consisting of a combination of one-component primer compositions 1 to 5 and a photopolymerizable one-component bonding material composition A or B (primer application / leaving for 10 seconds / drying / bonding material application / 10 seconds). Adhesion treatment by light irradiation) was performed.
Then, after a filling operation of a photopolymerizable composite resin (Beauty Fill, manufactured by Shofu Inc.), a dentin adhesion test, a dentin adhesion durability test and a storage stability test were carried out. The results of each are shown in Table 4.

As shown in Table 4, the adhesive system consisting of the one-component primer compositions 1 to 5 has excellent dentin adhesion to enamel and dentin (after immersion in water at 37 ° C. for 24 hours). Admitted. In addition, even in the adhesive durability after 2000 thermal cycles, both enamel and dentin have excellent adhesive durability without lowering the adhesive strength as compared with the dentin adhesive after immersion in water at 37 ° C. for 24 hours. It was confirmed that Furthermore, the one-component primer compositions 1 to 5 maintain the initial dentin adhesiveness (after immersion in water at 37 ° C. for 24 hours) without being deteriorated or deteriorated by hydrolysis even under storage conditions of 50 ° C. for 2 weeks. The primer was also excellent in storage stability.

[Comparative Examples 1 to 3]
One-component primer composition 6 containing 0.1 to 10 parts by weight of the component (e) with respect to 100 parts by weight of the total components of the dentin adhesive primer excluding the component (d) and the component (e). Adhesion treatment by a two-step type adhesive system (primer application / leaving for 10 seconds / drying / bonding material application / light irradiation for 10 seconds) consisting of a combination of ~ 8 and a photopolymerization type one-component bonding material composition A or B. Then, the same various tests as in Examples 1 to 5 were carried out. The results of each are shown in Table 4.

As shown in Table 4, 0.1 to 10 parts by weight of the component (e) is not included in the total of 100 parts by weight of the components of the dentin adhesive primer excluding the component (d) and the component (e). The adhesive system using the one-component primer compositions 6 to 8 is a component of the dentin adhesive primer excluding the component (d) and the component (e) in all of the dentin adhesiveness, the adhesive durability and the storage stability. Adhesion of dentin and enamel as compared to an adhesion system using liquid primer compositions 1-5 containing 0.1 to 20 parts by weight of component (e) relative to 100 parts by weight of It was found that the strength was low.

[Examples 6 to 7]
By a two-step type adhesive system (primer application / leaving for 10 seconds / drying / mixing and coating equal amounts of bonding material) consisting of a combination of a dual polymerization type two-component bonding material composition C or D and a one-component primer composition 2. Adhesion treatment was performed.
Then, after a filling operation of a photopolymerizable composite resin (Beauty Fill, manufactured by Shofu Inc.), a dentin adhesion test, a dentin adhesion durability test and a storage stability test were carried out. The results are shown in Table 4.

As shown in Table 4, the one-component primer composition 2 has excellent dentin adhesion to enamel and dentin even in an adhesion system composed of a dual polymerization type bonding material (after immersion in water at 37 ° C. for 24 hours). Was found to have. In addition, even in the adhesive durability after 2000 thermal cycles, both enamel and dentin have excellent adhesive durability without lowering the adhesive strength as compared with the dentin adhesive after immersion in water at 37 ° C. for 24 hours. It was confirmed that Furthermore, the one-component primer composition 2 maintains the initial dentin adhesiveness (after immersion in water at 37 ° C. for 24 hours) without being deteriorated or deteriorated by hydrolysis even under storage conditions of 50 ° C. for 2 weeks. Excellent storage stability was also observed.

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 a dentin adhesive primer and is an industrially used invention.

Claims (7)

(A) Acid group-containing monomer,
(B) Water,
(C) Water-soluble organic solvent,
A dentin adhesive primer containing (d) a polymerization catalyst and (e) a monomer containing a trifunctional or higher (meth) acrylamide group.
(E) Ratio of 0.1 to 20 parts by weight of the trifunctional or higher functional (meth) acrylamide group-containing monomer to 100 parts by weight of the total components of the dentin adhesive primer excluding (d) and (e). Contains dentin adhesive primer in. (E) The dentin adhesive primer 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.) (E) The dentin adhesive primer 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 dentin adhesive primer according to claim 3, wherein all R in the formula (2) are hydrogen atoms. The dentin adhesive primer according to any one of claims 1 to 4, which does not contain a monomer containing a bifunctional or less (meth) acrylamide group. Claims 1 to 5 in which (a) an acid group-containing monomer contains (f) an inorganic acid group-containing monomer and (g) an organic acid group-containing monomer, and (f) an inorganic acid group-containing monomer contains phosphorus and / or sulfur. One of the dentin adhesive primers. Any of 1 to 6 in which (a) the acid group-containing monomer contains (f) an inorganic acid group-containing monomer and (g) an organic acid group-containing monomer, and (g) the organic acid group-containing monomer is a carboxylic acid group-containing monomer. The dentin adhesive primer.