JP2000204010A - Dental adhesion kit - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a dental adhesion kit capable of omitting a treatment with an aqueous solution of an acid and a water washing operation, comprising a primer not whitening a bonded part when the primer is bonded to a soft tissue such as gum in the oral cavity and an adhesive. SOLUTION: This dental adhesion kit comprises a primer composition composed of a sulfonic acid group-containing polymerizable polymer such as 2-(meth) acrylamide-2-methylpropanesulfonic acid, a water-soluble polymerizable monomer such as diacetone (meth)acrylamide and water and an adhesive composed of a combination of an acidic phosphoric ester compound containing plural polymerizable unsaturated groups in one molecule such as bis(2- methacryloyloxyethy)hydrogen phosphate and a polymerization initiator.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a dental adhesive kit. Specifically, when filling and restoring in the dental field,
The present invention relates to a kit comprising a combination of a primer composition and an adhesive used for obtaining a high adhesive strength between a filling material and a tooth substance.

[0002]

2. Description of the Related Art A filling restoration material usually called a composite resin is used for restoration of a tooth damaged by caries or the like. Since the composite resin itself does not have adhesiveness, conventionally, in the restoration, the tooth surface is first treated with an aqueous acid solution, then washed and dried, followed by applying a primer, followed by drying, Adhesion between the dentin and the composite resin has been performed. However, such an operation is complicated,
In addition, there is a high possibility that an operation error is made.

[0003] In recent years, a relatively simplified operation in which treatment with an aqueous acid solution and washing with water is omitted, the primer composition is applied directly to the tooth surface and dried, followed by application of an adhesive and light curing. Several systems of methods are provided.

[0004] Examples of such a primer composition which can omit the treatment and washing steps with an acid aqueous solution include, for example, 2
Primer composition using acryloyloxyethyl hydrogen malate (2AEM) (40th J
ADR general meetings and the 24th and 25th general meetings of the Japanese Society of Dental Science and Technology), and a primer composition containing a metal salt and an acidic group-containing polymerizable monomer (JP-A-6-24928) are known.

[0005] However, the 2AEM used in the former primer composition not only has a problem that when it is attached to soft tissue such as gingiva in the oral cavity, it causes whitening of the attached portion, and also uses the primer composition. In such a case, a long processing time of 60 seconds is required. When the primer composition disclosed in JP-A-6-24928 is used, it is necessary to use the primer composition in combination with an adhesive using a specific polymerization initiator. Since the adhesive uses a trialkylboron having a very high polymerization activity as a polymerization initiator, the polymerization initiator and the polymerizable monomer must be mixed immediately before use, and the usable time is short. (Also referred to as an operation allowance time) is relatively short, and there is a problem in operability. Furthermore, since all of these primer compositions need to be stored in two or more parts and mixed immediately before use, from the viewpoint of storage stability,
There is also a problem that the operation becomes complicated.

The present inventor has proposed an adhesive system free from such problems as a primer composition comprising a sulfonic acid group-containing polymerizable monomer, a water-soluble polymerizable monomer, and water, and a polyvalent carboxylic acid group. A dental adhesive kit comprising a combination of an adhesive containing a polyfunctional polymerizable monomer and a polymerization initiator is developed and has already been proposed (JP-A-9-29591).
No. 3).

[0007] The primer composition used in the above-mentioned dental adhesive kit can be stored as a single solution.
It does not whiten even when in contact with the gingiva,
When used in combination with the specific adhesive described above, it is possible to obtain high adhesive strength to both dentin and enamel without the need for pretreatment and washing with an aqueous acid solution.

However, polyfunctional carboxylic acid group-containing polyfunctional polymerizable monomers, which are essential components of the adhesive, are not always easily synthesized or commercially available. Further, many of the polyfunctional carboxylic acid group-containing polyfunctional polymerizable monomers have a high viscosity, and may have a problem in handling property.

[0009]

As described above, Japanese Patent Application Laid-Open No. Hei 9
The dental adhesive kit disclosed in Japanese Patent No. 295913 is excellent as an adhesive system for restoring a composite resin, but a special polymerizable monomer must be used as an adhesive.

According to the present invention, there is provided a method disclosed in JP-A-9-29, without using a polyfunctional polymerizable monomer containing a polycarboxylic acid group.
An object of the present invention is to provide a dental adhesive kit having performance equivalent to that of the dental adhesive kit disclosed in No. 5913.

[0011]

Means for Solving the Problems In order to overcome the above technical problems, the present inventors have intensively studied a polymerizable monomer used for an adhesive used in combination with the primer composition described in the above publication. Was piled up. As a result of examining the performance of many polymerizable monomers as a dental adhesive kit when used as the polymerizable monomer component of the adhesive, an acidic phosphate ester-based polyfunctional polymerizable monomer was used. In the case of the present invention, it was found that the same performance as when a polyfunctional carboxylic acid group-containing polyfunctional polymerizable monomer was used, that is, low harm, high operability and high adhesiveness was obtained, and the present invention Was completed.

That is, the present invention provides (A) a sulfonic acid group-containing polymerizable monomer (hereinafter, also referred to as component A) and (B) a water-soluble polymerizable monomer (hereinafter, also referred to as component B). , And (C) a primer composition containing water (hereinafter, also referred to as C component), and (D) an acidic phosphate ester-based polyfunctional polymerizable monomer (hereinafter, also referred to as D component). And (E)
This is a dental adhesive kit comprising an adhesive containing a polymerization initiator (hereinafter, also referred to as an E component).

In the dental adhesive kit of the present invention, it is essential to use an acidic phosphate ester-based polyfunctional polymerizable monomer as a polymerizable monomer component of the adhesive. In the case where a monofunctional polymerizable monomer is used, the effects of the present invention cannot be obtained. The acidic phosphoric acid ester-based polyfunctional polymerizable monomer is not only excellent in handleability but also commercially available at a low price and in a large amount, and is easily available.

[0014]

BEST MODE FOR CARRYING OUT THE INVENTION The dental adhesive kit of the present invention
It comprises a combination of a primer composition containing the component, the B component and the C component (hereinafter also referred to as the present primer) and an adhesive containing the D component and the E component (hereinafter also referred to as the present adhesive).

Here, the primer is the same as the primer composition used in the dental adhesive kit disclosed in the above-mentioned JP-A-9-295913.

That is, the sulfonic acid group-containing polymerizable monomer (component A), which is one of the essential components of the primer, refers to at least one --SO ₃ H group in one molecule or water as the C component. a group which is generated a -SO ₃ H group react readily with,
It means a polymerizable monomer having at least one polymerizable unsaturated group. The sulfonic acid group-containing polymerizable monomer is not particularly limited as long as it satisfies such a definition, and a known compound can be used.

Examples of typical sulfonic acid group-containing polymerizable monomers include (meth) acrylic acid esters of sulfonic acid represented by the following general formula (1), (2) or (3):
Examples thereof include thioesters, amide derivatives, and vinyl sulfonic acid and styrene sulfonic acid.

[0018]

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In the above formulas, X is O, S or NR ₅ (R ₅
Represents a hydrogen atom or a hydrocarbon group having 1 to 5 carbon atoms), R ₁ represents a hydrogen atom or a methyl group, R ₁ in one molecule
When there are a plurality of R _{1 s} may be different from each other;
R ₂ and R ₃ each independently represent a hydrogen atom or a carbon number of 1 to 5;
Wherein R ₄ is 2 to 6 carbon atoms having 1 to 30 carbon atoms which may have an ether bond and / or an ester bond.
Represents a valent organic residue, n ₁ represents an integer of ₁ to 5, n ₂ represents an integer of ₁ to 5, and n ₁ + n ₂ is 2 to 6.中 In the general formulas (1) to (3), R ₂ and R ₃ are each independently a hydrogen atom or a hydrocarbon group having 1 to 5 carbon atoms, and specific examples thereof include a methyl group, an ethyl group, and a propyl group. , Isopropyl group, butyl group, isobutyl group, sec-butyl group,
tert-butyl group, pentyl group, isopentyl group, neopentyl group, tert-pentyl group and the like.

In the general formulas (1) to (3), R ₄ is a divalent to hexavalent organic residue having 1 to 30 carbon atoms which may have an ether bond and / or an ester bond. Is not particularly limited, but preferred examples include the following organic residues.

[0021]

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(However, n ₃ and n ₄ each independently represent 1 to 1
It is an integer of 0. )

[0023]

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[0024]

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(However, m ₁ , m ₂ and m ₃ are each independently an integer of 0 to 10, and m ₁ + m ₂ + m ₃ is 1 or more.) The sulfone represented by the general formula (1) Preferred specific examples of the acid group-containing polymerizable monomer include a compound having the following structure.

[0026]

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[0027]

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[0028]

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(However, R ₁ is as described above.) Preferred specific examples of the sulfonic acid group-containing polymerizable monomer represented by the general formula (2) include compounds having the following structures.

[0030]

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(However, R ₁ is as described above.) Preferred specific examples of the sulfonic acid group-containing polymerizable monomer represented by the general formula (3) include compounds having the following structures.

[0032]

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(However, R ₁ is as described above.) Among the above-mentioned sulfonic acid group-containing polymerizable monomers, the storage stability and the tooth adhesion when the constituent components of the present primer are made into one solution. (Meth) acrylamide derivatives wherein X is NR ₅ are preferably used because
Above all, a (meth) acrylamide derivative represented by the general formula (1) and wherein X is NR ₅ is more preferably used.

Further, among the above (meth) acrylamide derivatives, a (meth) acrylamide derivative in which R ₂ and R ₃ are not hydrogen atoms is preferably used from the viewpoint of storage stability. From the viewpoint of properties and the like, 2- (meth) acrylamido-2-methylpropanesulfonic acid is most preferably used.

Here, R ₅ is a hydrogen atom or a hydrocarbon group having 1 to 5 carbon atoms. Examples of the hydrocarbon group having 1 to 5 carbon atoms are the same as those in the above R ₂ and R ₃ . Is done.

The amount of the above-mentioned sulfonic acid group-containing polymerizable monomer is 10% of the total of all the components constituting the present primer.
When it is 0 wt%, it is preferably 1 to 50 wt%,
More preferably, it is 2 to 30% by weight, most preferably 4 to 20% by weight. If the amount of the sulfonic acid group-containing polymerizable monomer is small, the adhesive strength to enamel tends to decrease, and if it is too large, the adhesive strength to dentin tends to decrease.

The above sulfonic acid group-containing polymerizable monomer may be used as a mixture of a plurality of types as necessary.

The water-soluble polymerizable monomer used as the component B in the present invention means a compound having at least one polymerizable unsaturated group in one molecule and being water-soluble. As the water-soluble polymerizable monomer, existing compounds can be used without limitation as long as they satisfy the above definition. Here, the term "water-soluble" means that 10 g of the compound can be uniformly dissolved in 100 g of water.

Representative water-soluble polymerizable monomers include 2
-Hydroxyethyl methacrylate, 2-hydroxypropyl methacrylate, 3-hydroxypropyl methacrylate, 2,3-dihydroxypropyl methacrylate, 2,3-dihydroxybutyl methacrylate, 2,
4-dihydroxybutyl methacrylate, 2-hydroxymethyl-3-hydroxypropyl methacrylate,
2,3,4-trihydroxybutyl methacrylate,
2,2-bis (hydroxymethyl) -3-hydroxypropyl methacrylate, 2,3,4,5-tetrahydroxypentyl methacrylate, diethylene glycol monomethacrylate, triethylene glycol monomethacrylate, tetraethylene glycol monomethacrylate, pentaethylene glycol monomethacrylate And (meth) acrylic esters of polyhydric alcohols or polyethylene glycols such as acrylates (where the methacryloyl group is replaced with an acryloyl group; the same applies hereinafter); N-methylol methacrylamide, N-methylol acrylamide (Meth) acrylamides of amino alcohols such as (meth) acrylamide, diacetone (meth) acrylamide, N- (meth) acryloylmorpholine, etc. Riruamido like; (meth) acrolein, (meth) acrylonitrile, N- vinylpyrrolidone, and the like.

Among the above water-soluble polymerizable monomers, a polymerizable monomer that can be mixed with water at an arbitrary ratio is preferably used because the primer is easily prepared. In particular, (meth) acrylamides are preferably used because of good storage stability and good dentin adhesion, and (meth) acrylamides in which the carbon atom bonded to the nitrogen atom of the amide has no hydrogen atom are more preferably used. Is done. Furthermore, diacetone (meth) acrylamide is most preferably used in consideration of harmful effects on living bodies.

The amount of the water-soluble polymerizable monomer to be added is preferably 5 to 70 wt%, assuming that the total of all the constituent components constituting the primer is 100 wt%, and 10 to 50 wt%.
The blending amount of wt% is more preferable, and the blending amount of 15 to 40 wt% is most preferable. If the amount is too small, the adhesive strength to dentin tends to be insufficient, while if too large, the adhesive strength to both dentin and enamel tends to be insufficient.

The above-mentioned water-soluble polymerizable monomers can be used by mixing a plurality of kinds as necessary.

The water used as the C component in the primer is preferably substantially free of impurities harmful to storage stability, biocompatibility and adhesiveness. Examples thereof include deionized water and distilled water. No.

The amount of the water used in the present invention is preferably 5 to 90% by weight, more preferably 20 to 80% by weight, assuming that the total of all components constituting the primer is 100% by weight. Most preferred is a loading of ~ 75 wt%. If the amount is too small, the adhesive strength to both dentin and enamel tends to be insufficient, while if too large, the adhesive strength to dentin tends to be insufficient.

It is preferable that the present primer further contains (F) a polyfunctional polymerizable monomer. By blending the polyfunctional polymerizable monomer, the marginal sealing property when the dental adhesive kit of the present invention is used is improved.

The polyfunctional polymerizable monomer (F) is not particularly limited as long as it is a polymerizable monomer having a plurality of polymerizable unsaturated groups in one molecule, and known compounds may be used. Can be.

Specific examples of such compounds include:
2,2-bis (4-methacryloyloxyphenyl) propane, 2,2-bis (4- (3-methacryloyloxy-2-hydroxypropoxy) phenyl) propane,
2,2-bis (4-methacryloyloxyethoxyphenyl) propane, 2,2-bis (4-methacryloyloxydiethoxyphenyl) propane, 2,2-bis (4
-Methacryloyloxytetraethoxyphenyl) propane, 2,2-bis (4-methacryloyloxypentaethoxyphenyl) propane, 2,2-bis (4-methacryloyloxydipropoxyphenyl) propane,
(4-methacryloyloxyethoxyphenyl) -2
(4-methacryloyloxydiethoxyphenyl) propane, 2 (4-methacryloyloxydiethoxyphenyl) -2 (4-methacryloyloxytriethoxyphenyl) propane, 2 (4-methacryloyloxydipropoxyphenyl) -2 (4-methacryloyl Oxytriethoxyphenyl) propane, 2,2-bis (4-methacryloyloxydipropoxyphenyl) propane,
Aromatic difunctional monomers such as 2,2-bis (4-methacryloyloxyisopropoxyphenyl) propane, bis (2-methacryloyloxyethyl) phthalate and acrylates corresponding thereto; ethylene glycol dimethacrylate, diethylene glycol Dimethacrylate, triethylene glycol dimethacrylate, butylene glycol dimethacrylate, neopentyl glycol dimethacrylate, propylene glycol dimethacrylate, 1,3-butanediol dimethacrylate, 1,4-butanediol dimethacrylate, 1,6
-Hexanediol dimethacrylate, glycerin dimethacrylate, di-2-methacryloyloxyethyl-
Aliphatic bifunctional monomers such as 2,2,4-trimethylhexamethylene dicarbamate and their corresponding acrylates, N, N'-methylenebis (meth) acrylamide; trimethylolpropane trimethacrylate, trimethylolethane Trifunctional monomers such as trimethacrylate and acrylates corresponding thereto; tetrafunctional monomers such as pentaerythritol tetramethacrylate and pentaerythritol tetraacrylate, and (meth) acrylamide corresponding thereto. Are also preferably used.

Among the above-mentioned polyfunctional polymerizable monomers, it is preferable to use aliphatic difunctional polymerizable monomers or tri- or tetrafunctional polymerizable monomers. Considering that the primer composition is stored in one solution, the use of (meth) acrylamides is preferred.

These polyfunctional polymerizable monomers can be used as a mixture of two or more if necessary.

The compounding amount of the above-mentioned (F) polyfunctional polymerizable monomer is 100 times the sum of all the constituent components constituting the present primer.
When it is set to be wt%, it is preferably 0.1 to 30 wt%, more preferably 0.5 to 20 wt%. If it is less than 0.1 wt%, the effect of improving the marginal sealing properties tends to be not recognized, and if it exceeds 30 wt%, the adhesive strength to dentin tends to decrease.

In the present primer, other than the above-mentioned sulfonic acid group-containing polymerizable monomer, water-soluble polymerizable monomer, water and polyfunctional polymerizable monomer, the primer is required as long as the effects of the present invention are not impaired. Various optional components can be contained in accordance with the above.

Examples of such optional components include a polymerizable monomer containing an acidic group other than a sulfonic acid group, a polymerization inhibitor, inorganic or organic fine particles, a water-soluble organic solvent, a water-insoluble organic solvent, and a water-insoluble monofunctional compound. Examples thereof include a polymerizable monomer, a polymerization initiator, an acid and an acid salt, and an antibacterial agent.

Hereinafter, these optional components will be described.
In the following description, the added amount (blended amount) of each optional component is the sum of all the constituent components constituting the present primer as 1
It is represented by the weight content when it is set to 00 wt%.

In some cases, by admixing an acidic group-containing polymerizable monomer other than sulfonic acid, the adhesion to the dentin, particularly the adhesion to dentin, can be improved.

Examples of such a polymerizable monomer containing an acidic group other than a sulfonic acid group include various kinds of polymerizable monomers such as an acidic phosphate ester-based polyfunctional polymerizable monomer which will be described later as a description of the adhesive. Acidic phosphate ester-based polymerizable monomers; phosphonic acid group-containing polymerizable monomers such as vinylphosphonic acid;
Carboxylic acid group-containing polymerizable monomers such as 1-methacryloxyethyl-1,1-undecanedicarboxylic acid, 4-methacryloxyethyl trimellitic anhydride, N-methacryloylglycine, 2-methacryloxyethyl hydrogen malate and the like. Is mentioned. However, among these polymerizable monomers, there are compounds that cause significant whitening when attached to the gingiva, so such compounds may be omitted from the purpose of the present invention or even if they are added. It is preferred to keep the amount small.

When the primer composition of the present invention is stored, the polymerization inhibitor is added in an amount that does not significantly affect the adhesive strength in order to prevent gelation during storage and improve storage stability. Is preferred. Specific examples of such a polymerization inhibitor include hydroquinone, hydroquinone monomethyl ether, 2,6-ditert-butylphenol, 2,6-ditert-butyl-4-methylphenol, 2,4,6-tritert-butylphenol and the like. Is mentioned. The compounding amount of a general polymerization inhibitor is 10 to 1000 ppm.

By mixing inorganic or organic fine particles, the viscosity and fluidity of the primer composition can be adjusted.

Specific examples of such fine particles include polymer fine particles such as polyethylene, polypropylene, polymethyl (meth) acrylate, polyamides, polyesters, polystyrenes, and silicones; silicon, aluminum, titanium, and zirconium. , Nickel, cobalt, strontium, iron, copper, zinc, tin, magnesium, calcium, potassium, sodium, etc., or a single or complex oxide of these metals, silicon nitride, aluminum nitride, titanium nitride, boron nitride And inorganic fine particles such as carbides such as silicon carbide and boron carbide; and those obtained by treating these inorganic fine particles with a surface treating agent.

At this time, usable surface treatment agents include methyltrimethoxysilane, methyltriethoxysilane,
Methyltrichlorosilane, dimethyldichlorosilane, trimethylchlorosilane, vinyltrimethoxysilane, vinyltriethoxysilane, vinyltrichlorosilane, vinyltriacetoxysilane, vinyltris (β-methoxyethoxy) silane, γ-methacryloxypropyltrimethoxysilane, γ- Methacryloxypropyltris (β-methoxyethoxy) silane, γ-chloropropyltrimethoxysilane, γ-chloropropylmethyldimethoxysilane, γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropylmethyldiethoxysilane, β Silane coupling agents such as (3,4 epoxycyclohexyl) ethyltrimethoxysilane, N-phenyl-γ-aminopropyltrimethoxysilane, hexamethyldisilazane; Le titanate, isopropyl trioctanoyl titanate,
Isopropyl isostearyl diacryl titanate,
Isopropyl tridodecylbenzenesulfonyl titane,
Titanate-based coupling agents such as isopropyldimethacrylisostearoyl titanate and isopropyltricumylphenyltitanate; and aluminum-based coupling agents such as acetoalkoxyaluminum diisopropylate.

Further, polyethylene, polypropylene,
It is also preferable to use fine particles whose surface is coated with a polymer such as polymethyl methacrylate, polyamides, polyesters, polystyrenes, and silicones.

The method for producing the above-mentioned inorganic fine particles is not particularly limited, and existing coprecipitation methods, thermal spraying methods, sol-gel methods, bulk pulverization-classification methods and the like can be used. Existing methods such as spray drying, dry mixing, and wet mixing can be used without limitation. The primary particle system of the fine particles is preferably 0.001 μm to 1 μm, more preferably 0.002 μm to 0.5 μm, in consideration of easy handling of the fine particles and prevention of sedimentation after compounding.

The above-mentioned fine particles may be used by mixing a plurality of particles having different compositions, shapes, manufacturing methods, surface treatment methods and particle systems.

The sulfonic acid group-containing polymerizable monomer (component A) and the water-soluble polymerizable monomer (component B) in this primer are usually soluble in water (component C), and special consideration is required. If not, the primer composition will be uniform. But,
In addition, if the addition of a water-insoluble polyfunctional polymerizable monomer or other water-insoluble optional components causes a considerable decrease in compatibility, or in consideration of storage stability, When it is desired to lower the relative concentration of the polymerizable monomer or water, or to improve the operability during use, a water-soluble organic solvent can be added.

Specific examples of such a water-soluble organic solvent include methanol, ethanol, 1-propanol, 2-
Propanol, 1-butanol, 2-butanol, 2-
Methyl-1-propanol, 2-methyl-2-propanol, 2-methyl-2-butanol, 2-propene-1
-Ol, 2-propyn-1-ol, 1,2-ethanediol, 1,2-propanediol, 1,3-propanediol, 1,3-butanediol, 1,4-butanediol, 2,3- Butanediol, 1,5-pentanediol, hexylene glycol, glycerol, 1,
2,6-hexanetriol, trimethylolpropane, diethylene glycol, triethylene glycol,
Tetraethylene glycol, propylene glycol, dipropylene glycol, tripropylene glycol, 2
-Methoxyethanol, 2-ethoxyethanol, 2-
(Methoxyethoxy) ethanol, 2- (ethoxyethoxy) ethanol, triethylene glycol monomethyl ether, triethylene glycol monoethyl ether, 2-isopropoxyethanol, 2-butoxyethanol, 1-methoxy-2-propanol, 1-ethoxy- 2-propanol, dipropylene glycol monomethyl ether, tripropylene glycol monomethyl ether, 1,3-dioxolan, tetrahydrofuran,
Dioxane, propylene oxide, dimethoxymethane, 1,2-dimethoxyethane, 1,2-diethoxyethane, bis (2-methoxyethyl) ether, bis (2
Alcohol compounds or ether compounds such as -ethoxyethyl) ether; ketone compounds such as acetone and methyl ethyl ketone; phosphoric ester compounds such as hexamethylphosphoric triamide; acid amide compounds such as dimethylformamide and dimethylacetamide. And carboxylic acid compounds such as acetic acid and propionic acid, and sulfur oxide compounds such as dimethyl sulfoxide and sulfolane.

Among these water-soluble organic solvents, it is preferable to use those having a boiling point of 100 ° C. or less because they are easily dried after being applied to the tooth surface. The use of propanol or acetone is more preferred. In addition, when storage stability is considered, it is preferable to use ether compounds which do not easily react with other components.

In addition, a water-insoluble organic solvent can be blended in view of the effect of improving the storage stability by reducing the concentration and the effect of improving the solubility of various components. Such water-insoluble organic solvents include, for example, hexane, heptane,
Octane, toluene, dichloromethane, chloroform,
Examples thereof include carbon tetrachloride, dichloroethane, trichloroethane, pentanone, hexanone, ethyl formate, propyl formate, butyl formate, ethyl acetate, propyl acetate, butyl acetate, vinyl acetate, and diethyl ether.

It is also possible to mix a water-insoluble monofunctional polymerizable monomer in consideration of tooth adhesion and adhesive durability. Specific examples of such a water-insoluble monofunctional polymerizable monomer include methyl methacrylate, ethyl methacrylate, tetrahydrofurfuryl methacrylate, 2-ethylhexyl methacrylate, glycidyl methacrylate, and acrylates of these.

Examples of the polymerization initiator include organic peroxides, amine compounds, sulfinates, borates, organometallic polymerization initiators, and photo-intensifiers, which are specifically exemplified in the section of adhesives described later. Sensitizers, photopolymerization accelerators, dyes, and photoacid generators can be added alone or in combination as needed.

The addition of these polymerization initiators is preferred because it has the effect of improving the tooth adhesion and the adhesion durability.

It is also possible to promote the demineralization of the dentin by adding a non-polymerizable acid, and to improve the adhesion to the dentin, especially the enamel adhesion. Such non-polymerizable acids include:
Inorganic acids such as hydrochloric acid, nitric acid, sulfuric acid, phosphoric acid, and perchloric acid; organic carboxylic acids such as formic acid, acetic acid, citric acid, malonic acid, maleic acid, and oxalic acid; methanesulfonic acid, ethanesulfonic acid, propanesulfonic acid, and butane Sulfonic acid, benzenesulfonic acid, toluenesulfonic acid, xylenesulfonic acid, dodecylbenzenesulfonic acid, chlorobenzenesulfonic acid, bromobenzenesulfonic acid, biphenylsulfonic acid, naphthalenesulfonic acid, anthracenesulfonic acid, phenolsulfonic acid, naphtholsulfonic acid, sulfosulfonic acid Non-polymerizable sulfonic acids such as acetic acid, sulfobenzoic acid, sulfosalicylic acid, anthraquinonesulfonic acid, benzenedisulfonic acid, naphthalenedisulfonic acid, naphtholdisulfonic acid, and biphenyldisulfonic acid.

Further, by adding a metal salt, it is possible to improve the adhesiveness when using a chemically polymerizable adhesive.
Such metal salts include magnesium, aluminum, calcium, iron, cobalt, nickel, copper, zinc,
Examples include hydrochloride, hydrofluoride, sulfate, nitrate, phosphate, acetate, citrate, oxalate, and EDTA salt of polyvalent metals such as strontium, tin, and barium.

Further, a coloring matter can be blended as a coloring material.

The method of preparing the primer is not particularly limited, and the above-mentioned components may be weighed, placed in a container, stirred, mixed, and made into a uniform solution.

The packaging form of the primer may be appropriately determined in consideration of storage stability, and is not particularly limited. For example, when an easily hydrolyzable component is contained, the easily hydrolyzable compound, water, and a compound that serves as a hydrolysis catalyst such as a sulfonic acid group-containing polymerizable monomer may be used in any combination. It may be divided into two and mixed immediately before use. When only a hardly hydrolyzable compound such as a (meth) acrylamide derivative is contained as a polymerizable monomer, it is possible to prepare one liquid from the beginning.

The fact that the present primer does not whiten the gingiva when adhered to the gingiva is disclosed in Japanese Patent Application Laid-Open No. 9-295913.
No. 1 in the publication.

In the dental adhesive kit of the present invention, it is necessary to use the present primer in combination with the above-mentioned present adhesive.

The adhesive contains an acidic phosphate ester-based polyfunctional polymerizable monomer (component D) as an essential component.
In the case where the D component is not contained in the adhesive, the inventors of the present invention have studied so far, as described in JP-A-9-295913.
Unless a polyfunctional carboxylic acid group-containing polyfunctional polymerizable monomer disclosed in Japanese Patent Application Laid-Open Publication No. H10-157, is used, a strong adhesive force enough to practically withstand strong stress in the oral cavity cannot be obtained.

The acidic phosphate ester-based polyfunctional polymerizable monomer as the component D means an acidic phosphate ester having a plurality of polymerizable unsaturated groups in one molecule. The acidic phosphoric acid ester-based polyfunctional polymerizable monomer is not particularly limited as long as it satisfies such a definition, and a known compound can be used. Here, the acidic phosphate ester means not only a monoester or a diester of phosphoric acid,
All of those having a structure which easily reacts with water to generate a free P-OH group, such as an anhydride or an acid halide, are collectively referred to.

Examples of such compounds include compounds represented by the following general formulas (4), (5) and (6).

[0080]

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(In each formula, R ₁ represents a hydrogen atom or a methyl group, and R _{1 in} one molecule may be different from each other;
R _5, R ₆ each independently d - represents a divalent to hexavalent organic residue ether bond and / or 1 to 30 carbon atoms which may have an ester bond, R ₇ is e - ether bond and / Or a trivalent to hexavalent organic residue having 1 to 30 carbon atoms which may have an ester bond, wherein R ₈ has 1 to 30 carbon atoms having no polymerizable unsaturated group.
Wherein n ₅ and n _{6 each} represent an integer of 1 to 5, n ₅ + n ₆ is 2 or more, and n ₇ represents an integer of 2 to 5. In the general formula (4), R ₅ and R ₆ are each a group of 2 to 6 carbon atoms having 1 to 30 carbon atoms which may have an ether bond and / or an ester bond.
Is a valent organic residue, and its structure is not particularly limited.
Specifically same as R ₄ exemplified in the paragraph of the sulfonic acid group-containing polymerizable monomers are exemplified.

Preferred specific examples of the acidic phosphoric acid ester-based polyfunctional polymerizable monomer represented by the general formula (4) are as follows.

[0083]

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(However, R ₁ is as described above.) In the general formula (5), R ₈ is a monovalent organic residue having 1 to 30 carbon atoms and having no polymerizable unsaturated group. . As the organic residue, specifically, in addition to those exemplified as R _{2 in} the section of the sulfonic acid group-containing polymerizable monomer, an octyl group,
A decyl group, an undecyl group, a dodecyl group, an octadecyl group, a phenyl group, a naphthyl group, a benzyl group, and those substituted with a halogen atom, a hydroxyl group, an amino group, a carboxyl group and the like can be mentioned.

In the general formulas (5) and (6), R ₇ represents a trivalent to hexavalent organic residue having 1 to 30 carbon atoms which may have an ether bond and / or an ester bond; The structure is not particularly limited, and specific examples thereof include those having a valence of 3 to 6 among R ₄ exemplified in the section of the sulfonic acid group-containing polymerizable monomer.

Preferred specific examples of the acidic phosphoric acid ester-based polyfunctional polymerizable monomer represented by the general formula (5) are as follows.

[0087]

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(However, R ₁ is as described above.) Preferred specific examples of the acidic phosphoric acid ester-based polyfunctional polymerizable monomer represented by the general formula (6) are as follows. is there.

[0089]

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(Provided that R ₁ is as described above) Among the above-mentioned acidic phosphate ester-based polyfunctional polymerizable monomers, the compound represented by the above general formula (4) is preferable. In particular, from the viewpoint of easy availability and synthesis and tooth adhesion, among the compounds represented by the general formula (4), R ₅ and R ₆
Are the same, and compounds in which n ₅ and n ₆ are equal are more preferably used.

These acidic phosphate ester-based polyfunctional polymerizable monomers can be used in combination as necessary.

In addition to the acidic phosphoric acid ester-based polyfunctional polymerizable monomer, the adhesive used in the present invention may further include various other polymerizable monomers for controlling its operability and various physical properties. The body can be included as an optional ingredient. In that case, the acidic phosphate ester-based polyfunctional polymerizable monomer is the total of the acidic phosphate ester-based polyfunctional polymerizable monomer and the polymerizable monomer contained as other optional components. (Hereinafter, also referred to as all polymerizable monomers.) In 100 parts by weight,
It is preferably contained at least 10 parts by weight, more preferably at least 20 parts by weight.

Other polymerizable monomers which can be blended as the optional components include the same sulfonic acid group-containing polymerizable monomers and water-soluble polymerizable monomers as specifically exemplified in the section of the present primer. Monomer, water-insoluble monofunctional polymerizable monomer, aromatic difunctional monomer, aliphatic difunctional monomer, trifunctional monomer, tetrafunctional monomer, non-functional A water-soluble monofunctional monomer or the like can be used.

Further, 11-methacryloyloxy-
1,1-undecanedicarboxylic acid and 4-methacryloyloxyethyl trimellitate anhydride, 2-
Polymerizable monomers having a carboxyl group such as (meth) acryloyloxyethyl hydrogen malate, 2- (meth) acryloyloxyethyl hydrogen succinate and N- (meth) acryloylglycine;
2-methacryloyloxyethyl phenyl hydrogen phosphate or 2-methacryloyloxyethyl
It is also possible to use an acidic phosphate ester-type monofunctional polymerizable monomer having one polymerizable unsaturated group and an acidic phosphate ester structure in one molecule such as dihydrogen phosphate.

These polymerizable monomers can be used as a mixture of two or more as necessary.

The adhesive used in the present invention contains, as the E component, a polymerization initiator for polymerizing and curing the polymerizable monomer such as the D component. As the polymerization initiator, known ones are used without any particular limitation.

Such a polymerization initiator is usually one in which the constituents of the adhesive are divided into two or more parts and the polymerization is started by mixing immediately before use (chemical polymerization initiator);
They are roughly classified into those that initiate polymerization by light irradiation (photopolymerization initiators).

As the chemical polymerization initiator, organic peroxides /
Amine compound or organic peroxide / amine compound / sulfinate, organic peroxide / amine compound / borate,
Redox-type polymerization initiators composed of barbituric acids / copper ion-forming compounds / halogen ion-forming compounds, and organic metal-type polymerization initiators that initiate polymerization by reacting with oxygen or water, and further include sulfinic acid salts and The borates can also initiate polymerization by reaction with an acidic compound.

Examples of the organic peroxide include t-butyl hydroperoxide, cumene hydroperoxide, di-t-butyl peroxide, dicumyl peroxide, acetyl peroxide, lauroyl peroxide, benzoyl peroxide and the like.

The amine compound is preferably a secondary or tertiary amine having an amino group bonded to an aryl group.
Specifically, N, N-dimethyl-p-toluidine, N, N-dimethylaniline, N- (2-hydroxyethyl) aniline, N, N-di (2-hydroxyethyl) -p-toluidine, N -Methylaniline, N-methyl-p-toluidine and the like are preferred.

Examples of the above sulfinates include sodium benzenesulfinate, lithium benzenesulfinate, sodium p-toluenesulfinate, lithium p-toluenesulfinate, potassium p-toluenesulfinate, sodium m-nitrobenzenesulfinate,
Sodium p-fluorobenzenesulfinate and the like. Examples of borates include trialkylphenylboron, trialkyl (p-chlorophenyl) boron, trialkyl (p-fluorophenyl) boron, and trialkyl (3,5-bistrifluoromethyl). ) Phenylboron, dialkyldiphenylboron, dialkyldi (p-chlorophenyl) boron, dialkyldi (p-fluorophenyl) boron, dialkyldi (3,5-bistrifluoromethyl) phenylboron, monoalkyltriphenylboron, monoalkyltri (p- Chlorophenyl) boron,
Sodium salt of monoalkyltri (p-fluorophenyl) boron, monoalkyltri (3,5-bistrifluoromethyl) phenylboron (alkyl group is n-butyl group, n-octyl group, n-dodecyl group, etc.), lithium salt,
Potassium salt, magnesium salt, tetrabutylammonium salt, tetramethylammonium salt and the like can be mentioned.

Examples of the barbituric acids include 5-methylbarbituric acid, 5-ethylbarbituric acid, 5-propyl barbituric acid, 5-butyl barbituric acid, 5,5-diethyl barbituric acid, and 1,5-diethyl barbituric acid. Barbituric acid, 1-ethyl-5-methylbarbituric acid, 1-ethyl-5-isobutyl barbituric acid, 1,3-diethyl-5-butyl barbituric acid, 1-cyclohexyl-5-methyl barbituric acid, 1-cyclohexyl-5-ethylbarbituric acid,
1-cyclohexyl-5-octylbarbituric acid, 1-
Cyclohexyl-5-hexyl barbituric acid, 5-butyl-1-cyclohexyl barbituric acid, 1-benzyl-
5-phenylbarbituric acid and the like.

Examples of the copper ion-forming compound include copper acetylacetone, cupric acetate, copper oleate, and copper chloride. Examples of the halogen ion-forming compound include dilauryl dimethyl ammonium chloride, dilauryl dimethyl ammonium bromide, and lauryl dimethyl. Benzylammonium chloride and the like.

Further, examples of the organometallic polymerization initiator include:
Boron compounds such as triphenylborane, tributylborane, and tributylborane partial oxide are exemplified.

Examples of the photopolymerization initiator include those comprising only a photosensitizer, those comprising a photosensitizer / a photopolymerization accelerator, dyes / photoacid generators / sulfinates, and dyes / photoacid generators / And those made of borate.

Examples of the photosensitizer include camphorquinone, benzyl, α-naphthyl, acetonaphthene, naphthoquinone, p, p′-dimethoxybenzyl, p, p′-dichlorobenzylacetyl, 1,2-phenanthrenequinone,
Α-diketones such as 1,4-phenanthrenequinone, 3,4-phenanthrenequinone, 9,10-phenanthrenequinone, thioxanthones such as 2,4-diethylthioxanthone, 2-benzyl-dimethylamino-1- (4
-Morpholinophenyl) -butanone-1,2-benzyl-diethylamino-1- (4-morpholinophenyl) -butanone-1,2-benzyl-dimethylamino-
1- (4-morpholinophenyl) -propanone-1,
2-benzyl-diethylamino-1- (4-morpholinophenyl) -propanone-1, 2-benzyl-dimethylamino-1- (4-morpholinophenyl) -pentanone-1, 2-benzyl-diethylamino-1- ( 4-
Α-aminoacetophenones such as morpholinophenyl) -pentanone-1, bis- (2,6-dichlorobenzoyl) phenylphosphine oxide, bis- (2,6
-Dichlorobenzoyl) -2,5-dimethylphenylphosphine oxide, bis- (2,6-dichlorobenzoyl) -4-propylphenylphosphine oxide,
Bis- (2,6-dichlorobenzoyl) -1-naphthylphosphine oxide, bis- (2,6-dimethoxybenzoyl) phenylphosphine oxide, bis-
(2,6-dimethoxybenzoyl) -2,4,4, -trimethylpentylphosphine oxide, bis- (2,
6-dimethoxybenzoyl) -2,5-dimethylphenylphosphine oxide, bis- (2,4,6-trimethylbenzoyl) phenylphosphine oxide, bis- (2,5,6-trimethylbenzoyl) -2,4,4
And bisacylphosphine oxides such as trimethylpentylphosphine oxide.

As the above-mentioned photopolymerization accelerator, tributylamine, tripropylamine, triethylamine, N-methyldiethanolamine, N-ethyldiethanolamine, N, N-dimethylhexylamine, N, N-dimethyldodecylamine, N, N-dimethyl Stearylamine, 2,2 '-(n-butylimino) diethanol 2-
(Dimethylamino) ethyl (meth) acrylate, 2-
(Diethylamino) ethyl (meth) acrylate, N-
Aliphatic tertiary amines such as (3-dimethylaminopropyl) methacrylamide, N, N-dimethylaniline,
N, N-diethylaniline, N, N-di-n-butylaniline, N, N-dibenzylaniline, N, N-dimethyl-p-toluidine, N, N-diethyl-p-toluidine, N, N- Dimethyl-m-toluidine, p-bromo-
N, N-dimethylaniline, m-chloro-N, N-dimethylaniline, N, N-dihydroxyethylaniline,
N, N-dihydroxyethyl-p-toluidine, p-dimethylaminophenethyl alcohol, p-dimethylaminostilpene, N, N-dimethyl-3,5-xylidine, 4-dimethylaminopyridine, N, N-dimethyl-
α-naphthylamine, N, N-dimethyl-β-naphthylamine, p-dimethylaminobenzaldehyde, p-dimethylaminoacetophenone, p-dimethylaminobenzoic acid, p-dimethylaminobenzoic acid ethyl ester, p
And aromatic tertiary amines such as -dimethylaminobenzoic acid amyl ester and N, N-dimethylanthranilic acid methyl ester.

Specific examples of suitably used dyes include 3-thienoylcoumarin, 3- (4-methoxybenzoyl) coumarin, 3-benzoylcoumarin, and 3- (4
-Cyanobenzoyl) coumarin, 3-thienoyl-7-
Methoxycoumarin, 7-methoxy-3- (4-methoxybenzoyl) coumarin, 3-benzoyl-7-methoxycoumarin, 3- (4-cyanobenzoyl) -7-methoxycoumarin, 5,7-dimethoxy-3- (4 -Methoxybenzoyl) coumarin, 3-benzoyl-5,7-dimethoxycoumarin, 3- (4-cyanobenzoyl) -5.
7-dimethoxycoumarin, 3-acetyl-7-dimethylaminocoumarin, 7-diethylamino-3-thienoylcoumarin, 7-diethylamino-3- (4-methoxybenzoyl) coumarin, 3-benzoyl-7-diethylaminocoumarin, 7- Diethylamino-3- (4-cyanobenzoyl) coumarin, 7-diethylamino-3- (4
-Dimethylaminobenzoyl) coumarin, 3-cinnamoyl-7-diethylaminocoumarin, 3- (p-diethylaminocinnamoyl) -7-diethylaminocoumarin, 3-acetyl-7-diethylaminocoumarin, 3-
Carboxy-7-diethylaminocoumarin, 3- (4-
(Carboxybenzoyl) -7-diethylaminocoumarin, 3,3′-carbonylbiscoumarin, 3,3′-carbonylbis (7-diethylamino) coumarin, 2,
3,6,7-tetrahydro-1,1,7,7-tetramethyl-10- (benzothiazoyl) -11-oxo-1
H, 5H, 11H,-[1] benzopyrano [6,7,8
-Ij] quinolidine, 3,3′-carbonylbis (5,
7-) Dimethoxy-3,3'-biscoumarin, 3-
(2′-benzimidazoyl) -7-diethylaminocoumarin, 3- (2′-benzoxazoyl) -7-diethylaminocoumarin, 3- (5′-phenylthiadiazoyl) -7-diethylaminocoumarin, 3- ( 2'-benzthiazoyl) -7-diethylaminocoumarin, 3,
3'-carbonylbis (4-cyano-7-diethylamino) coumarin and the like can be mentioned.

As the above-mentioned photoacid generator, 2,4,6-tris (trichloromethyl) -s-triazine, 2,4,4
6-tris (tribromomethyl) -s-triazine, 2
-Methyl-4,6-bis (trichloromethyl) -s-triazine, 2-methyl-4,6-bis (tribromomethyl) -s-triazine, 2-phenyl-4,6-bis (trichloromethyl)- s-triazine, 2- (p-methoxyphenyl) -4,6-bis (trichloromethyl)
-S-triazine, 2- (p-methylthiophenyl)-
4,6-bis (trichloromethyl) -s-triazine,
2- (p-chlorophenyl) -4,6-bis (trichloromethyl) -s-triazine, 2- (2,4-dichlorophenyl) -4,6-bis (trichloromethyl) -s-
Triazine, 2- (p-bromophenyl) -4,6-bis (trichloromethyl) -s-triazine, 2- (p-
Tolyl) -4,6-bis (trichloromethyl) -s-triazine, 2- (p-methoxyphenyl) -4,6-bis (trichloromethyl) -s-triazine, 2-n-propyl-4,6- Bis (trichloromethyl) -s-triazine, 2- (α, α, β-trichloroethyl) -4,
6-bis (trichloromethyl) -s-triazine, 2-
Styryl-4,6-bis (trichloromethyl) -s-triazine, 2- (p-methoxystyryl) -4,6-bis (trichloromethyl) -s-triazine, 2- (o-
Methoxystyryl-4,6-bis (trichloromethyl)
-S-triazine, 2- (p-butoxystyryl)-
4,6-bis (trichloromethyl) -s-triazine,
2- (3,4-dimethoxystyryl) -4,6-bis (trichloromethyl) -s-triazine, 2- (3
Halomethyl-substituted-s-triazine derivatives such as 4,5-trimethoxystyryl) -4,6-bis (trichloromethyl) -s-triazine, diphenyliodonium, bis (p-chlorophenyl) iodonium, ditolyliodonium, Bis (p-tert-butylphenyl) iodonium, bis (m-nitrophenyl) iodonium, p-tert-butylphenylphenyliodonium, methoxyphenylphenyliodonium, p-
Examples include chlorides such as octyloxyphenylphenyliodonium, bromides, diphenyliodonium salt compounds such as tetrafluoroborate, hexafluorophosphate, hexafluoroarsenate, hexafluoroantimonate, and trifluoromethanesulfonate.

The sulfinates and borates are
Those specifically exemplified in the section of the chemical polymerization type polymerization initiator can be similarly used.

These polymerization initiators can be used in combination as needed.

Among the above-mentioned polymerization initiators, it is preferable to use a photopolymerization initiator which enables the present adhesive to be stored in one liquid. Considering the polymerization rate and the polymerization rate, a photosensitizer / photopolymerization accelerator is preferred. The use of a combination of agents is more preferred, and the use of a combination of α-diketones / aromatic tertiary amines or bisacylphosphine oxides / aromatic tertiary amines is most preferred.

The amount of the polymerization initiator to be added is not particularly limited as long as the effect is exhibited.
With respect to 100 parts by weight of the total polymerizable monomer in the adhesive, 0.0
The addition is preferably 1 to 30 parts by weight, more preferably 0.05 to 10 parts by weight, and most preferably 0.5 to 5 parts by weight.

The adhesive used in the present invention may contain, if necessary, hydroquinone, hydroquinone monomethyl ether, 2,6-
Polymerization inhibitors such as di-tert-butylphenol and 2,6-di-tert-butyl-4-methylphenol
It is preferable to add 0 to 5000 ppm.

It is preferable to add a filler to the adhesive of the present invention, if necessary. By adding a filler, it becomes possible to improve mechanical strength, control viscosity and fluidity, and the like.

Specific examples of such fillers include:
In the description of the present primer, inorganic fine particles such as polymer fine particles, metal oxides, metal nitrides, and metal carbides specifically exemplified as optional components in the description of the primer, and surface-treated inorganic fine particles thereof are exemplified.

In addition, the viscosity of the adhesive is generally relatively high, so that the possibility of filler settling is reduced.
Particles having a larger particle diameter than the fine particles can be used, and particles of the polymer or the inorganic compound having a particle size of 1 to 200 μm can also be used.

Further, organic or inorganic particles are dispersed in a polymerizable monomer, and a particle-dispersed polymer obtained by polymerizing the particles is pulverized to have a size of 200 μm or less. It is also suitable.

The filler described above has the composition, shape,
It is also possible to use a plurality of different production methods, different surface treatment methods, and different particle systems.

The addition amount of these fillers is not particularly limited as long as the effects of the present invention are not impaired, but the addition of not more than 300 parts by weight based on 100 parts by weight of the total polymerizable monomer is not limited. Preferably, addition of 100 parts by weight or less is more preferable, and addition of 30 parts by weight or less is further preferable.

[0121] The dental adhesive kit of the present invention is preferably prepared from the viewpoint that both the primer and the adhesive can be made into one liquid.
The A component is a (meth) acrylamide derivative in which X is NR ₅ in the general formula (1), the B component is a (meth) acrylamide derivative, and the D component is represented by the general formula (4). It is preferred that the compound is a compound and the component E is a combination with the present adhesive which is a photopolymerization initiator.

Among them, from the viewpoints of storage stability and polymerizability, the component A is a (meth) acrylamide derivative in which X is NR ₅ and R ₂ and R ₃ are not hydrogen atoms in the general formula (1), The primer in which the B component is a (meth) acrylamide in which the carbon atom to which the nitrogen atom of the amide is bonded does not have a hydrogen atom, that is, is not directly bonded to a hydrogen atom, and the D component is in the general formula (4) R ₅ and R ₆
Are the same and n ₅ and n ₆ are the same,
Particularly preferred are those whose components consist of a combination with the present adhesive which is a combination of a photosensitizer / photopolymerization accelerator.

Further, in view of the marginal sealing property, in the above-mentioned preferred dental adhesive kit of the present invention and particularly preferred dental adhesive kit of the present invention, the primer further comprises (F) a polyfunctional polymerizable monomer. Which contain bi- or tetrafunctional (meth) acrylamides is preferred.

The method for preparing the present adhesive is not particularly limited, and the above-mentioned acidic phosphoric acid ester-based polyfunctional polymerizable monomer, a polymerization initiator, and optional components to be blended if necessary are added to the desired components. What is necessary is just to weigh out in a ratio, mix by stirring, and make it uniform.

When using the dental adhesive kit of the present invention, the same operation as that of a conventional dental adhesive may be performed, and specifically, a treatment required for dental treatment such as removal of dental caries and the like. Apply this primer to the tooth where
After leaving for several tens of seconds, remove the volatile components in the primer by air blowing, then apply this adhesive on it, cure the adhesive by irradiating light if necessary, and then fill the composite resin according to the standard method Should be performed.

[0126]

EXAMPLES Hereinafter, the present invention will be described specifically with reference to Examples and Comparative Examples, but the present invention is not limited thereto. The abbreviations, abbreviations, methods of measuring adhesive strength, methods of evaluating harm to living organisms, and compositions of adhesives shown in the examples are as follows.

(1) Abbreviations and abbreviations [Sulfonic acid group-containing polymerizable monomer] • AMPS: 2-acrylamide-2-methylpropanesulfonic acid • MMPS: 2-methacrylamide-2-methylpropanesulfonic acid • SPN: 3-methacryloyloxypropanesulfonic acid [water-soluble polymerizable monomer]-DAAM: diacetone acrylamide-HEMA: 2-hydroxyethyl methacrylate [polyfunctional polymerizable monomer]-3G: triethylene glycol dimethacrylate [polymerization BHT: 2,6-ditert-butyl-4-methylphenol HQME: hydroquinone monomethyl ether [acidic phosphate ester polyfunctional polymerizable monomer] PM2: bis (2-methacryloyloxyethyl) Hydrogen phosphate ・ PM2- C6: bis (6-methacryloyloxyhexyl) hydrogen phosphate PM2-Cl: bis (1-chloromethyl-2-methacryloyloxyethyl) hydrogen phosphate PM2-21: the following compound

[0128]

Embedded image

[Polymerization initiator] CQ: camphorquinone BAPO: bis (2,4,6-trimethylbenzoyl) phenylphosphine oxide DMBE: ethyl N, N-dimethyl-p-aminobenzoate DMA: N, N-dimethyl-p-aminoacetophenone [monofunctional acidic phosphoric acid ester-based polymerizable monomer] PM1: 2-methacryloyloxyethyl dihydrogen phosphate Phenyl-P: 2-methacryloyloxyethyl phenyl hydrogen phosphate [ Other polymerizable monomers] Bis-GMA: the following compound

[0130]

Embedded image

D-2.6E: a mixture of the following compounds:

[0132]

Embedded image

(However, the average of n ₈ + n ₉ is 2.6.) (2) Adhesion of enamel and dentin The bovine anterior teeth are removed within 24 hours after sacrifice, and water is injected under # 80.
The enamel or dentin plane was cut out so as to be parallel to the lips with water-resistant abrasive paper. Next, compressed air is blown onto these surfaces for about 10 seconds to dry them.
A double-sided tape with a hole of mm was fixed and the adhesion area was defined. A thin coat of the primer composition is applied to the dressing surface,
After leaving for 2 seconds, compressed air was blown for about 5 seconds to dry. Next, an adhesive was applied, and light was irradiated for 20 seconds with a visible light irradiator (Power Light, manufactured by Tokuyama Corporation) to cure the adhesive. Subsequently, a dental wax having a hole having a thickness of about 1 mm and an inner diameter of 8 mm was fixed on the circular hole so as to have the same center, thereby forming a simulated cavity. There, dental composite resin (Palphite Light Posteria, Inc.)
(Manufactured by Tokuyama Co., Ltd.) and irradiated with light for 30 seconds using a visible light irradiator to produce an adhesion test piece.

After immersing the adhesive test piece in water at 37 ° C. for 24 hours, a tensile tester (Autograph AD500) was used.
0, manufactured by Shimadzu Corporation) with a crosshead speed of 10
It was pulled at a rate of mm / min, and the tensile adhesive strength between the tooth and the composite resin was measured.

The tensile strength of four pieces per test was measured by the above method, and the average value was defined as the adhesive strength.

(3) Marginal sealing property The bovine anterior teeth were removed within 24 hours after sacrifice, and under water injection, # 80
The enamel plane was cut out with water-resistant abrasive paper 0 so as to be parallel to the lips. Next, under water injection, using a carborundum point (HP35, manufactured by Shofu Co., Ltd.), the inner system was 4.5 mm to 5 mm.
A cavity was formed that extended to dentin with a depth of 4 mm to 5 mm. The primer composition was thinly applied in the cavity, allowed to stand for 20 seconds, and then dried by blowing compressed air for about 5 seconds. Next, an adhesive was applied, and light was irradiated for 20 seconds with a visible light irradiator (Power Light, manufactured by Tokuyama Corporation) to cure the adhesive. Further, a dental composite resin (Palphique Esterite, manufactured by Tokuyama Corporation) was filled thereon, and light was irradiated with a visible light irradiator for 30 seconds to produce a marginal sealing test piece.

After the adhesive test piece was immersed in water at 37 ° C. for 24 hours, it was polished using an # 800 emery paper to remove excess composite resin, and the root portion was immediately polymerized with resin (TOXOH). Cure Fast, Inc.
(Made by Tokuyama). This was alternately immersed in a dye aqueous solution (0.1% basic fuchsin, manufactured by Tokyo Kasei Co., Ltd.) at 4 ° C. and 60 ° C. for 60 times for 1 minute each. After immersion, the test piece was ground with # 120 emery paper so that a cross section from the cervical direction to the crown direction could be seen, and the state of dye penetration into the interface between the dentin and the filled composite resin was observed. ,evaluated. The evaluation was performed by observing a total of 12 cross-sections of six test pieces, six at the cervical part side and six at the crown part side, and counted the number of 12 minutes to see if the dye had penetrated. That is, the larger the number, the better the marginal sealing properties.

(4) Preparation of Primers The primers A to E were each stirred and mixed with the composition shown in the following table to obtain a uniform liquid. The primer was prepared immediately before use.

[0139]

[Table 1]

(5) Preparation of Adhesive The adhesive described in each of the examples was prepared by shading under light shielding.
The mixture was stirred and mixed to obtain a viscous liquid.

Example 1 A mixture of polymerizable monomers consisting of 5.0 g of PM2, 2.1 g of BisGMA, 1.4 g of 3G and 1.5 g of HEMA was added to 0.05 g of CQ and 0.1 g of DMBE. Was mixed to prepare an adhesive. Primer A
An adhesion test was performed on the tooth surface treated with the adhesive using this adhesive. As a result, both dentin and enamel 2
High adhesive strength of 1 MPa or more was obtained.

Examples 2 to 5 The tooth surfaces treated with the primer A according to the method of Example 1 were evaluated using an adhesive having the composition shown in Table 2. Table 2 shows the composition of the adhesive and the results.

[0143]

[Table 2]

Comparative Examples 1 to 4 The tooth surfaces treated with the primer A according to the method of Example 1 were evaluated using an adhesive having the composition shown in Table 2. Table 2 shows the composition of the adhesive and the results. At this time,
Tests on enamel were not performed due to the significantly poor adhesion to dentin.

In Examples 1 to 5, PM2 was used as the (A) acidic phosphoric acid ester-based polyfunctional polymerizable monomer in the adhesive, and the types of other components and the mixing ratio of each component were changed. The result of the case. In each case, dentin and enamel exhibited good adhesive strength, and were clear as compared with Comparative Examples 1 to 4 using PM1 or phenyl-P, which is a monofunctional acidic phosphate polymerizable monomer. Showed good adhesive strength.

Examples 6 to 12 Adhesives having the compositions shown in Table 3 were prepared, and an adhesion test was performed on tooth surfaces treated with the primers B, C or D using these adhesives. Table 3 shows the results.

[0147]

[Table 3]

Comparative Examples 5 and 6 According to the method of Example 6, an adhesion test was performed on tooth surfaces treated with the primer B or D using these adhesives. Table 3 shows the results.

Examples 1 and 5 to 8 and Examples 9 to
Numeral 12 represents the results obtained when the type of the primer used was changed. By using the present primer and the present adhesive in combination, a high adhesive strength can be obtained for both dentin and enamel. On the other hand, Comparative Examples 5 and 6
The results obtained when phenyl-P, which is a monofunctional acidic phosphoric acid ester-based polymerizable monomer, was used instead of the acidic phosphoric acid ester-based polyfunctional polymerizable monomer as a component. No high adhesion was obtained when used in combination with.

Examples 13 to 16 Tooth surfaces treated with primer A according to the method of Example 1
The evaluation was performed using an adhesive having a composition shown in Table 4. Table 4 shows the composition of the adhesive and the results.

[0151]

[Table 4]

Comparative Example 7 The tooth surface treated with the primer A according to the method of Example 1 was evaluated using an adhesive having the composition shown in Table 4. Table 4 shows the composition of the adhesive and the results.

Examples 13 to 16 show the results when the type of the acidic phosphate ester-based polyfunctional polymerizable monomer used as the D component of the adhesive was changed. In each case, it showed high adhesive strength to both dentin and enamel.

Comparative Example 7 shows the result when an adhesive containing no acidic phosphate ester-based polyfunctional polymerizable monomer was used, and the adhesive strength to dentin was remarkably low. Examples 17 and 18 From a mixture of polymerizable monomers consisting of 5.0 g PM2, 2.1 g BisGMA, 1.4 g 3G and 1.5 g HEMA from 0.05 g CQ and 0.1 g DMBE Was mixed to prepare an adhesive. Primer B
Alternatively, a margin sealing test was performed using E and this adhesive.
Table 5 shows the results.

[0155]

[Table 5]

Comparative Example 8 An adhesive shown in Table 5 was prepared according to the method of Example 17, and a marginal sealing test was performed. Table 5 shows the results.

Examples 17 and 18 both exhibited better edge sealing properties than Comparative Example 8 using an adhesive containing no acidic phosphate ester-based polyfunctional polymerizable monomer component. Furthermore, in Example 18 using the primer E containing the polyfunctional polymerizable monomer, better edge sealing properties were shown as compared with Example 17 using the primer B not containing the polyfunctional polymerizable monomer.

[0158]

[Effect] As a system for composite resin restoration,
By using the dental adhesive kit of the present invention in which an adhesive containing a primer acidic phosphoric acid ester-based polyfunctional polymerizable monomer having low harm, such as whitening of gums, is treated with an aqueous acid solution and washed with water. And high adhesion can be obtained without using a special compound such as a polyvalent carboxylic acid group-containing polymerizable monomer.

Furthermore, by selecting the chemical structure of the components to be used, both the primer composition and the adhesive can be stored in one solution.

 ──────────────────────────────────────────────────続 き Continued on the front page F term (reference) 4C089 AA10 BB05 BC02 BC03 BC06 BC08 BC12 BD02 BD03 BD06 BD10 BD11 4J038 FA012 FA152 FA161 GA03 GA13 HA156 KA04 PA07 PA17 PB01 4J040 FA011 FA121 FA122 GA15 GA25 GA27 HA126 JB07 KA14 MA15 NA03

Claims (2)

[Claims] (A) a sulfonic acid group-containing polymerizable monomer,
(B) a primer composition containing a water-soluble polymerizable monomer and (C) water, (D) an acidic phosphate ester-based polyfunctional polymerizable monomer, and (E) a polymerization initiator. A dental adhesive kit comprising an adhesive material. 2. The dental adhesive kit according to claim 1, further comprising (F) a polyfunctional polymerizable monomer in the primer composition.