JP2002187907A - Dental chemical polymerization catalyst - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a dental chemical polymerization catalyst which has high chemical stability, is easy to handle, has high activity, is not easily inhibited by polymerization, and does not cause coloring or discoloration of a cured product. A dental curable composition that can be used as an adhesive or a restorative material using such a chemical polymerization catalyst is provided. SOLUTION: A dental chemical polymerization catalyst comprising an acidic compound, an organic peroxide such as cumene hydroperoxide, and an aryl borate compound such as sodium tetraphenylboron, and a dental hardening comprising the dental chemical polymerization catalyst Composition.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a dental chemical polymerization catalyst used in the field of dental care, a dental adhesive composition using the dental chemical polymerization catalyst, and a use of the dental curable composition. .

[0002]

2. Description of the Related Art A method of curing a polymerizable monomer with a polymerization catalyst is widely used in the field of dentistry. Examples of such a method include dental cements, dental adhesives, and composites. Resins, room temperature polymerization resins for dental use, dental pretreatment materials, and the like.

[0003] In these materials, polymerization catalysts are properly used in accordance with the composition, purpose of use and required performance. As the polymerization catalyst, there are a photopolymerization catalyst and a chemical polymerization catalyst, but when the curable composition contains a large amount of fillers or the like that are difficult to transmit light, or when used in applications where light irradiation is difficult. Requires the use of a chemical polymerization catalyst. Also,
In dental adhesives and pretreatment materials, it is often necessary to use a chemical polymerization catalyst depending on the type of dental material to be bonded. Furthermore, when a photopolymerization catalyst is used, it is necessary to irradiate light using a dedicated device, and use of a chemical polymerization catalyst may be desired from the viewpoint of simplification of operation.

For example, when restoring a tooth damaged by dental caries or an accident, a dental composite restoration material (dental prosthesis material) such as a composite resin or a compomer is directly filled into the cavity of the tooth. In the restoration method (direct restoration method) in which curing is performed later, a bonding material mainly composed of a polymerizable monomer containing an acid group-containing polymerizable monomer is used as an adhesive (adhesive material for dental direct restoration). As such bonding materials, excellent bonding materials which do not require a pre-treatment operation normally required have been developed (Japanese Patent Application Laid-Open Nos. 9-263604 and 10).
However, since the bonding material uses a specific photopolymerization catalyst, it is not only necessary to omit the light irradiation operation to simplify the bonding operation, but also to use the bonding material. Is used in combination with a chemically polymerized dental restorative material, the unreacted acidic group-containing polymerizable monomer in the bonding material is generally used as a chemical polymerization catalyst component of the dental restorative material. It reacts with the amine component in the organic peroxide / tertiary amine-based catalyst used, resulting in insufficient adhesive strength. Therefore, the dental restoration material used in combination is limited to the photo-curing type. There is a problem that it is done.

[0005] In a restoring method (indirect restoring method) in which a dental restorative material such as an inlay or a crown prepared in advance outside the mouth using a metal, a ceramic material or the like is bonded to a tooth, an acidic group-containing polymerizable monomer is used. Adhesive dental cements such as adhesive resin cements and resin-reinforced ionomer cements containing polymerizable monomers containing monomeric monomers and organic or inorganic fillers as main components have been used as adhesives. In some cases, a large amount of filler is contained, or a light-impermeable metal material or the like is used. Therefore, a chemical polymerization catalyst that can be polymerized at room temperature in a dark place must be used.

Various proposals have been made for chemical polymerization catalysts. For example, a system using a trialkylboron or a partial oxide thereof (JP-A-57-108102)
Japanese Patent Application Laid-Open No. 51-92883, a system comprising a combination of an organic peroxide and a cobalt salt or a manganese salt, a system comprising a combination of an organic peroxide and a tertiary amine, and the like. A redox-type room temperature polymerization initiator such as a system comprising a combination of hydrogen peroxide and an Fe ²⁺ compound, a system comprising barbituric acid, a Cu ²⁺ compound and a Cl ^- compound (JP-A-5-295013), and aryl Aryl such as a system comprising a combination of a borate compound and an acidic compound (JP-A-9-309811) and a system comprising a combination of an arylborate compound, an acidic compound and a transition metal compound (JP-A-9-227325). Currently, chemical polymerization catalysts and the like using borate compounds are known, and some of them have been put to practical use.

[0007]

However, the above-mentioned system using trialkylboron or its partial oxide is an excellent chemical polymerization catalyst having a very high activity, but is extremely unstable chemically, It is necessary to store it separately from other components and store it, and to collect an appropriate amount immediately before use and mix it with other monomer components, which has the disadvantage that the operation becomes complicated.

Further, of the above, the chemical polymerization catalyst comprising a combination of an organic peroxide and a tertiary amine, and the barbituric acid-based chemical polymerization catalyst are preferred in view of their low harmful effects on living organisms and their easy availability. Although these are most commonly used in the field of dental materials, the following problems have been pointed out.

That is, in the case of a chemical polymerization catalyst comprising a combination of an organic peroxide and a tertiary amine, problems such as coloring and discoloration of the cured product due to oxidation of the amine compound, oxygen and acidic components (acid components are It has been pointed out that polymerization inhibition by tertiary amine to form a quaternary salt having no reducing ability is large. For example, when the above-mentioned problem of coloring and discoloration is applied to a dental restorative material represented by a composite resin, a color shift from a natural tooth is caused to cause an aesthetic problem, and the problem of polymerization inhibition is caused by an acidic group-containing polymer. This means that it cannot be used for dental adhesives and the like containing a hydrophilic monomer as an essential component. Further, in the case of barbituric acid-based chemical polymerization catalysts, problems such as difficulty in controlling the curing time and poor storage stability have been pointed out.

The chemical polymerization catalyst using the above-mentioned aryl borate is easy to handle, does not cause coloring and discoloration of the cured product, and is excellent in storage stability. There is a demand for high activation.

As described above, a dental chemical polymerization catalyst which has high chemical stability of the catalyst itself, is easy to handle, has high activity, is not easily inhibited by polymerization, and does not cause the cured product to be colored or discolored. Not known so far. Therefore, an object of the present invention is to provide a dental chemical polymerization catalyst having such excellent characteristics.

[0012]

Means for Solving the Problems The present inventors have made intensive studies to achieve the above object. As a result, when an aryl borate compound and an acidic compound are used in combination with a specific oxidizing agent, the polymerization activity is significantly increased, and further, a dental curable composition using such a chemical polymerization catalyst is The inventors have found that they have excellent characteristics as various adhesives, pretreatment materials, and restoration materials, and have completed the present invention.

That is, a first aspect of the present invention is a dental chemical polymerization catalyst comprising an aryl borate compound, an acidic compound, and an organic peroxide and substantially free of an amine compound as a catalyst component. .

Since the dental chemical polymerization catalyst of the present invention does not substantially contain an amine compound, the cured product is not colored or discolored, and is easy to handle.
It is characterized in that the polymerization activity is high even in the presence of oxygen and acidic compounds, and that a proper operation margin time can be secured. Among the dental chemical polymerization catalysts of the present invention, those containing a metal compound that promotes the decomposition of organic peroxides have the feature that the polymerization activity is particularly high. Further, those containing an acidic group-containing polymerizable monomer as an acidic compound, when used as a polymerization catalyst for a dental curable composition containing such a polymerizable monomer as an essential component, other acidic compounds may be used. There is no need to add a compound, and acidic compounds are not eluted from the cured product obtained after use.

Although the present invention is not restricted by logic, in the dental chemical polymerization catalyst of the present invention, the aryl borate compound is decomposed by an acidic compound to form an aryl borane compound. The compound itself is not only oxidized by oxygen present in the atmosphere to produce polymerizable radicals, but also oxidized by organic peroxides, resulting in more oxygen inside the curable composition with less oxygen. Since the radicals are generated, it is considered that they act as highly active chemical polymerization catalysts. Further, by further containing a metal compound that promotes decomposition of the organic peroxide, the oxidation of the arylborane compound by the organic peroxide is promoted, so that it is considered that the arylborane compound acts as a more active chemical polymerization catalyst.

[0016] A second aspect of the present invention is a dental curable composition comprising a polymerizable monomer and the above-mentioned dental chemical polymerization catalyst of the present invention. The dental curable composition of the present invention is characterized in that it is polymerized at room temperature even in a dark place to give an excellent cured product. Further, the dental adhesive composition of the present invention further containing a photopolymerization initiator is a so-called dual cure type curable composition, and has a feature that it has a wide clinical application range.

In the third aspect of the present invention, 100 parts by weight of a polymerizable monomer containing a polymerizable monomer having an acidic group, 0.01 to 10 parts by weight of an aryl borate compound, 0.1 part by weight of an organic peroxide. A dental curable composition comprising the curable dental composition of the present invention containing 0.1 to 10 parts by weight, and 1 to 20 parts by weight of a polyvalent metal ion-eluting filler and / or 2 to 30 parts by weight of water. It is a repair adhesive. The dental direct restoration adhesive (bonding material) of the present invention provides a high adhesive strength to both dentin and enamel without performing a pretreatment operation on the tooth material, and performs a light irradiation operation in application. This is an excellent feature not found in conventional bonding materials, which is not required in conventional bonding materials, and is used for both photo-curable and chemically-curable dental restorative materials.

In the fourth aspect of the present invention, 100 parts by weight of a polymerizable monomer containing a polymerizable monomer having an acidic group, 0.01 to 10 parts by weight of an aryl borate compound, 0.1 parts by weight of an organic peroxide. An adhesive for indirect restoration of dental material, comprising the dental curable composition of the present invention containing 01 to 10 parts by weight and 50 to 900 parts by weight of a filler. The adhesive material for dental indirect restoration of the present invention has a feature of high adhesiveness to both enamel and dentin.

Further, the fifth present invention relates to a method for preparing the total polymerizable monomer 1
A dental composite restoration material comprising the dental curable composition of the present invention, which contains 50 to 900 parts by weight of a filler with respect to 00 parts by weight. What is a dental composite restoration material?
It is a material for performing restoration as a prosthesis by dissimilar materials such as a filler and a cured monomer, which can be combined to provide a high-strength cured body without coloring or discoloration. By using this, it is possible to perform restoration with high aesthetics and reliability.

Further, a sixth aspect of the present invention is characterized in that the dental curable composition of the present invention comprises an acidic group-containing polymerizable monomer, an aryl borate compound, an organic peroxide, and water. It is a dental pretreatment material. The dental pretreatment material of the present invention provides high adhesive strength to both enamel and dentin in a single operation even when both light and chemically polymerized adhesives are used, and is safe. It has the feature of being expensive.

[0021]

DETAILED DESCRIPTION OF THE INVENTION The dental chemical polymerization catalyst of the present invention comprises:
It comprises an aryl borate compound, an acidic compound, and an organic peroxide, and is characterized by substantially not containing an amine compound as a catalyst component.

Here, the phrase "substantially free of an amine compound as a catalyst component" means that an amount of the amine is such that the acidic compound which is a component of the chemical polymerization catalyst is neutralized and the chemical polymerization catalyst does not substantially function. For example, in a polymerizable composition containing the chemical polymerization catalyst of the present invention, a trace amount (for example, 0.1% by weight or less based on the acidic compound) of an amine compound is used for purposes other than the chemical polymerization catalyst. If included, it is acceptable. When an amine compound exceeding the amount shown above is contained as a catalyst component, the initial coloring of the obtained cured product increases due to the oxidation of the amine compound, and furthermore, the coloring resistance is reduced, which causes an aesthetic problem. Not only occurs,
Since the acidic compound which is one component of the chemical polymerization catalyst of the present invention is neutralized, the polymerization activity is reduced. further,
An odor peculiar to the amine compound may be generated, and a problem such as discomfort to the patient may occur.

The aryl borate compound used in the chemical polymerization catalyst of the present invention contains at least one boron-containing compound in the molecule.
It is not particularly limited as long as it has an aryl bond,
The following general formula (1)

[0024]

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[0025] (wherein, R _1, R _2, and R ₃ are each independently an alkyl group, an aryl group, an aralkyl group, an alkenyl group, these groups may have a substituent; R ₄ And R ₅ are each independently a hydrogen atom, a halogen atom, an alkyl group which may have a substituent, or a phenyl group which may have a substituent; L ⁺ is a metal cation, a quaternary ammonium Ions, quaternary pyridinium ions, quaternary quinolinium ions, or phosphonium ions.) Can be used.

In dental practice, materials utilizing the curing reaction of a chemical polymerization catalyst system are generally used by mixing or kneading the products which are separately packaged with the catalyst system immediately before use. However, a borate compound having no boron-aryl bond has extremely poor storage stability, easily reacts with oxygen in the air and decomposes, so that the borate compound easily deteriorates even in a separately packaged state. In addition, there is a problem that the curing reaction proceeds during mixing or kneading, and the operation margin time is shortened, so that it becomes practically difficult to use.

Specific examples of the aryl borate compound represented by the above formula (1) include borate compounds having one aryl group per molecule, such as trialkylphenylboron and trialkyl (p-chlorophenyl) borane. , Trialkyl (p-fluorophenyl) boron,
Trialkyl (3,5-bistrifluoromethyl) phenylboron, trialkyl [3,5-bis (1,1,1
1,3,3,3-hexafluoro-2-methoxy-2-
Propyl) phenyl] boron, trialkyl (p-nitrophenyl) boron, trialkyl (m-nitrophenyl) boron, trialkyl (p-butylphenyl) boron, trialkyl (m-butylphenyl) boron, trialkyl (p -Butyloxyphenyl) boron, trialkyl (m-butyloxyphenyl) boron, trialkyl (p-octyloxyphenyl) boron, trialkyl (m-octyloxyphenyl) boron (alkyl group is n-butyl group, n- Octyl group, n-dodecyl group, etc.) sodium, lithium, potassium, magnesium, tetrabutylammonium, tetramethylammonium, tetraethylammonium, tributylamine, triethanolamine, methylpyridinium, ethylpyridinium Jiniumu salt, butyl pyridinium salt, methyl quinolinium salt, ethyl quinolinium salt and butyl quinolinium salt.

As borate compounds having two aryl groups in one molecule, dialkyldiphenylboron, dialkyldi (p-chlorophenyl) boron, dialkyldi (p-fluorophenyl) boron, dialkyldi (3,5-bistrifluoromethyl) ) Phenylboron, dialkyldi [3,5-bis (1,1,1,3,
3,3-hexafluoro-2-methoxy-2-propyl) phenyl] boron, dialkyl (p-nitrophenyl) boron, dialkyldi (m-nitrophenyl) boron, dialkyldi (p-butylphenyl) boron, dialkyldi (m- Butylphenyl) boron, dialkyldi (p-butyloxyphenyl) boron, dialkyldi (m-butyloxyphenyl) boron, dialkyldi (p-octyloxyphenyl) boron, dialkyldi (m-octyloxyphenyl) boron (alkyl group is n- Butyl group, n-octyl group, n-dodecyl group, etc.) sodium salt, lithium salt, potassium salt, magnesium salt, tetrabutylammonium salt, tetramethylammonium salt, tetraethylammonium salt, tributylamine salt, triethanol Min salts, methyl pyridinium salt, ethyl pyridinium salt, butyl pyridinium salt, methyl quinolinium salt, ethyl quinolinium salt and butyl quinolinium salt.

Further, as borate compounds having three aryl groups in one molecule, monoalkyltriphenylboron, monoalkyltris (p-chlorophenyl) boron, monoalkyltris (p-fluorophenyl) boron, monoalkyltrisboron (3,5-bistrifluoromethyl) phenylboron, monoalkyltris [3,5
-Bis (1,1,1,3,3,3-hexafluoro-2
-Methoxy-2-propyl) phenyl] boron, monoalkyltris (p-nitrophenyl) boron, monoalkyltris (m-nitrophenyl) boron, monoalkyltris (p-butylphenyl) boron, monoalkyltris (m- Butylphenyl) boron, monoalkyltris (p-butyloxyphenyl) boron, monoalkyltris (m-butyloxyphenyl) boron, monoalkyltris (p-octyloxyphenyl) boron,
Monoalkyltris (m-octyloxyphenyl) boron (alkyl group is n-butyl group, n-octyl group, n
-Dodecyl group, etc.) sodium salt, lithium salt, potassium salt, magnesium salt, tetrabutylammonium salt,
Tetramethylammonium salt, tetraethylammonium salt, tributylamine salt, triethanolamine salt,
Examples thereof include a methylpyridinium salt, an ethylpyridinium salt, a butylpyridinium salt, a methylquinolinium salt, an ethylquinolinium salt, and a butylquinolinium salt.

As borate compounds having four aryl groups in one molecule, tetraphenylboron, tetrakis (p-chlorophenyl) boron, tetrakis (p
-Fluorophenyl) boron, tetrakis (3,5-bistrifluoromethyl) phenylboron, tetrakis [3,5-bis (1,1,1,3,3,3-hexafluoro-2-methoxy-2-propyl) Phenyl] boron, tetrakis (p-nitrophenyl) boron, tetrakis (m-nitrophenyl) boron, tetrakis (p-
Butylphenyl) boron, tetrakis (m-butylphenyl) boron, tetrakis (p-butyloxyphenyl) boron, tetrakis (m-butyloxyphenyl)
Boron, tetrakis (p-octyloxyphenyl) boron, tetrakis (m-octyloxyphenyl) boron (alkyl group is n-butyl group, n-octyl group, n-
Sodium, lithium, potassium, magnesium, tetrabutylammonium, tetramethylammonium, tetraethylammonium, tributylamine, triethanolamine, methylpyridinium, ethylpyridinium, butylpyridinium Salt, methylquinolinium salt, ethylquinolinium salt, butylquinolinium salt and the like can be mentioned.

Among these, in consideration of storage stability, it is preferable to use a borate compound having three or four aryl groups in one molecule, and more preferably, four borate compounds because of easy handling and availability. A borate compound having an aryl group of is most preferred. These aryl borate compounds can be used alone or in combination of two or more.

As the acidic compound used in the dental chemical polymerization catalyst of the present invention, inorganic acids and organic acids generally known as Bronsted acids are used without any limitation. Typical examples of inorganic acids include hydrochloric acid, sulfuric acid, nitric acid, and phosphoric acid. Representative organic acids include carboxylic acids such as acetic acid, propionic acid, maleic acid, fumaric acid, phthalic acid, benzoic acid, trichloroacetic acid, trifluoroacetic acid, citric acid and trimellitic acid, and p-toluenesulfonic acid. And sulfonic acids such as benzenesulfonic acid, methanesulfonic acid and trifluoromethanesulfonic acid, and phosphoric acids such as methylphosphonic acid, phenylphosphonic acid, dimethylphosphinic acid and diphenylphosphinic acid. Further, in addition to phenols and thiols, solid acids such as acidic ion exchange resins and acidic alumina are also exemplified as suitable acids. Furthermore, as the acidic compound, an acidic group-containing polymerizable monomer containing a polymerizable group may be used.In this case, the acidic compound itself is also a polymerizable monomer, and Curing is preferable because there is no fear of elution of acidic components and the like.

Such an acidic group-containing polymerizable monomer includes at least one acidic group and at least one acidic group in one molecule.
There is no particular limitation as long as it is a polymerizable monomer having two polymerizable unsaturated groups, and a known compound can be used. Here, the acidic group refers to a phosphinico group {= P (= O) OH}, a phosphono group {-P (= O) (OH) ₂ }, a carboxyl group {-C (= O) OH}, a sulfo group (- (SO ₃ H) or an organic group having an acid anhydride skeleton {—C (＝ O) —O—C (＝ O) —} or the like, which means an acidic group in an aqueous solution.
The polymerizable unsaturated group means an unsaturated group having radical polymerization ability such as a vinyl group, an allyl group, an acryloyl group, a methacryloyl group, an acrylamide group, and a methacrylamide group.

As the acidic group-containing polymerizable monomer, a compound represented by the following formula (2) or (3) can be suitably used.

[0035]

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In the formula, R ₆ and R ₆ ′ each independently represent a hydrogen atom or a methyl group, and W and W ′ each independently represent an oxycarbonyl group (—COO—), an iminocarbonyl group (—CONH—) Or a phenylene group (-
C ₆ H ₄ -) represents, R ₇ and R ₇ 'represents an organic residue of bond or an ether bond and / or ester bond having 1 to 30 carbon atoms may also be divalent to hexavalent, which have, , W,
When W ′ is an oxycarbonyl group or an iminocarbonyl group, R ₇ is not a bond, X and X ′ are a monovalent or divalent acidic group, and m and m ′ are each independently 1 to 4 And m + n represents the valence of R ₇ ,
m ′ + n ′ represents the valence of R ₇ ′.中 In the general formulas (2) and (3), the structure is not particularly limited as long as X and X ′ are acidic groups according to the above definition, but preferred specific examples are as follows.

[0037]

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In the general formulas (2) and (3), the structure of R ₇ is not particularly limited, and may have a bond or a known ether bond and / or ester bond. A hexavalent organic residue having 1 to 30 carbon atoms may be employed, and specific examples are as follows. Note that R ₇
Is a state in which the group W and the group X are directly bonded. When W is an oxycarbonyl group or an iminocarbonyl group, R ₇ is not a bond.

[0039]

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(Wherein m1, m2 and m3 are each independently an integer of 0 to 10, and m1 + m2 + m3
Is 1 or more. Preferred specific examples of the acidic group-containing polymerizable monomer represented by the general formulas (2) and (3) are as follows.

[0041]

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[0042]

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Wherein R ₆ is a hydrogen atom or a methyl group, and l, m and n are each independently an integer of 0 to 2. In the formula, the compounds at the bottom are l, m , And n are often obtained as different compounds,
The sum of l, m, and n in the mixture averages 3.5. )

[0044]

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[0045]

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(However, R ₆ is a hydrogen atom or a methyl group.) In addition, vinylphosphonic acids, acrylic acid, methacrylic acid, and vinylsulfonic acids are also included in the acidic group-containing polymerizable monomer.

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

Among the acidic group-containing polymerizable monomers specifically exemplified above, the phosphinico group {= P (= O) OH} and the phosphono group {-P It is particularly preferable to use those having (（O) (OH) ₂ } and a carboxyl group {—C (＝ O) OH}.

The amount of the acidic compound used in the dental chemical polymerization catalyst of the present invention is not particularly limited. However, from the viewpoint of polymerization activity and curability, 0.1 to 100 mol, particularly 0.5 mol, is preferably used per 1 mol of the aryl borate compound. Preferably, it is 50 mol.

The dental chemical polymerization catalyst of the present invention contains an organic peroxide as an oxidizing agent. Known compounds can be used as these organic peroxides without limitation.

Representative organic peroxides usable in the present invention are classified into ketone peroxide, peroxyketal, hydroperoxide, diaryl peroxide, peroxyester, diacyl peroxide, and peroxydicarbonate. Various organic peroxides can be mentioned, and specific examples of these organic peroxides include the following.

That is, as the ketone peroxides,
Examples include methyl ethyl ketone peroxide, cyclohexanone peroxide, methylcyclohexanone peroxide, methyl acetoacetate peroxide, and acetylacetone peroxide.

Further, as peroxyketals,
1,1-bis (t-hexylperoxy) 3,3,5-
Trimethylcyclohexane, 1,1-bis (t-hexylperoxy) cyclohexane, 1,1-bis (t-butylperoxy) 3,3,5-trimethylcyclohexane, 1,1-bis (t-butylperoxy) Cyclohexane, 1,1-bis (t-butylperoxy) cyclododecane, 2,2-bis (t-butylperoxy) butane, n-butyl 4,4-bis (t-butylperoxy) valerate, 2, 2-bis (4,4-di-t-butylperoxycyclohexyl) propane.

The hydroperoxides include P-menthane hydroperoxide, diisopropylbenzene hydroperoxide, 1,1,3,3
-Tetramethylbutyl hydroperoxide, cumene hydroperoxide, t-hexyl hydroperoxide and t-butyl hydroperoxide. Examples of the dialkyl peroxide include α, α-bis (t-butylperoxy) diisopropylbenzene,
Dicumyl peroxide, 2,5-dimethyl-2,5-
Bis (t-butylperoxy) hexane, t-butylcumyl peroxide, di-t-butylperoxide,
2,5-dimethyl-2,5-bis (t-butylperoxy) hexyne-3 and the like.

The diacyl peroxides include isobutyryl peroxide, 2,4-dichlorobenzoyl peroxide, 3,5,5-trimethylhexanoyl peroxide, octanoyl peroxide, lauroyl peroxide, and stearyl peroxide. Succinic acid peroxide, m-toluoylbenzoyl peroxide, benzoyl peroxide and the like.

The peroxydicarbonates include di-n-propylperoxydicarbonate, diisopropylperoxydicarbonate, bis (4-t-
(Butylcyclohexyl) peroxydicarbonate, di-2-ethoxyethylperoxydicarbonate, di-2-ethylhexylperoxydicarbonate, di-2
-Methoxybutyl peroxydicarbonate, di (3-
Methyl-3-methoxybutyl) peroxydicarbonate.

Further, as peroxyesters,
α, α-bis (neodecanoylperoxy) diisopropylbenzene, cumylperoxyneodecanoate,
1,1,3,3-tetramethylbutyl peroxy neodecanoate, 1-cyclohexyl-1-methylethyl peroxy neodecanoate, t-hexyl peroxy neodecanoate, t-butyl peroxy neodecanoate Noate, t-hexylperoxypivalate, t-butylperoxypivalate, 1,1,3,3-tetramethylbutylperoxy-2-ethylhexanoate, 2,5-
Dimethyl-2,5-bis (2-ethylhexanoylperoxy) hexane, 1-cyclohexyl-1-methylethylperoxy-2-ethylhexanoate, t-hexylperoxy-2-ethylhexanoate, t- Butylperoxy 2-ethylhexanoate, t-butylperoxyisobutyrate, t-hexylperoxyisopropyl monocarbonate, t-butylperoxymaleic acid, t-butylperoxy 3,5,5-trimethylhexa Noate, t-butyl peroxy laurate, 2,5-dimethyl-2,5-bis (m-toluoyl peroxy) hexane, t-butyl peroxyisopropyl monocarbonate, t-butyl peroxy 2-ethylhexyl mono Carbonate, t-hexylperoxybenzoate, 2 5-dimethyl-2,5-bis (benzoylperoxy) hexane, t-butylperoxyacetate, t-butylperoxy-m-toluoylbenzoate, t-butylperoxybenzoate, bis (t-butylperoxy) Isophthalate and the like.

Other than these, t-butyltrimethylsilyl peroxide, 3,3 ', 4,4'-tetra (t-butylperoxycarbonyl) benzophenone and the like can be preferably used.

These organic peroxides may be appropriately selected and used depending on the type and amount of the aryl borate compound or acidic compound used in combination, and may be used alone or in combination of two or more. From the viewpoint of polymerization activity, it is particularly preferable to use ketone peroxides, peroxyesters, or diacyl peroxides. Further, among these, the 10-hour half-life temperature is 60 ° C. from the viewpoint of storage stability when the curable composition is used.
It is preferable to use the above organic peroxides.

The amount of the organic peroxide to be used in the dental chemical polymerization catalyst of the present invention is not particularly limited. However, from the viewpoint of polymerization activity, 0.1 to 1 mol of the aryl borate compound is used.
Suitably, it is 10 mol, especially 0.5 to 5 mol.

In order to further increase the polymerization activity in the dental chemical polymerization catalyst of the present invention, it is preferable to add a metal compound which promotes the decomposition of the organic peroxide used (hereinafter simply referred to as a decomposition accelerator). It is suitable. When an amine compound is added to a compound having an action of decomposing an organic peroxide, an acidic compound which is one of the catalyst components is neutralized, and the polymerization activity is reduced.

The decomposition accelerator that can be used in the present invention is not particularly limited as long as it is a metal compound and has an action of accelerating the decomposition of the organic peroxide when it coexists with the arylborane compound. Specific examples of the decomposition accelerator having such an action include vanadium compounds such as vanadium oxide (V), vanadium oxide acetylacetonate, sodium vanadate, and vanadium oxytrichloride;
Iron (III) chloride, iron (III) acetylacetonate, iron compounds such as iron (III) naphthenate, iron (III) citrate, copper (II) chloride, copper (II) citrate, copper (II) acetyl Acetonate, copper stearate (I
Copper compounds such as I), molybdenum compounds such as molybdenum oxide (VI) and molybdenum oxide acetylacetonate, manganese compounds such as manganese oxide (IV) and manganese naphthenate, cobalt naphthenate and cobalt (III) acetylacetonate Cobalt compounds, tungsten oxides (VI), tungsten compounds such as sodium tungstate, silicotungstic acid, dibutyltin oxide (I
V) and the like, and metal alkoxides such as titanium tetrabutoxide and aluminum tributoxide. Although the amount of the decomposition accelerator used is not particularly limited, from the viewpoint of polymerization activity, it may be 0.0 to 1 mol of the organic peroxide.
It is preferably from 01 to 1 mol, particularly preferably from 0.05 to 0.1 mol.

Since the dental chemical polymerization catalyst of the present invention does not substantially contain an amine compound, it does not cause coloring or discoloration of the cured product, is easy to handle, has high polymerization activity, and has an appropriate operation margin. Since time can be secured, it can be suitably used as a polymerization catalyst for a dental curable composition containing various polymerizable monomers. At this time, as the polymerizable monomer, a known polymerizable monomer that can be used in combination with a conventional dental chemical polymerization catalyst in the dental field can be used without limitation, but from the viewpoint of curing speed, (meth) acrylate-based It is preferred to use monomers.

Specific examples of preferably used (meth) acrylate polymerizable monomers include methyl (meth) acrylate, ethyl (meth) acrylate, and butyl (meth) acrylate.
Acrylate, glycidyl (meth) acrylate, 2-
Such as cyanomethyl (meth) acrylate, benzyl methacrylate, polyethylene glycol mono (meth) acrylate, allyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, and glyceryl mono (meth) acrylate Mono (meth) acrylate monomers; ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, nonaethylene glycol di (meth) acrylate, propylene glycol di (meth) acrylate, Dipropylene glycol di (meth)
Acrylate, 2,2'-bis [4- (meth) acryloyloxyethoxyphenyl] propane, 2,2'-bis [4- (meth) acryloyloxyethoxyethoxyphenyl] propane, 2,2'-bis [4- (Meth) acryloyloxyethoxyethoxyethoxyethoxyethoxyphenyl] propane, 2,2′-bis {4- [3
-(Meth) acryloyloxy-2-hydroxypropoxy] phenyl} propane, 1,4-butanediol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, 1,9-nonanediol di (meth) Acrylate, trimethylolpropane tri (meth) acrylate, neopentyl glycol di (meth)
Examples thereof include polyfunctional (meth) acrylate monomers such as acrylate, urethane (meth) acrylate, and epoxy (meth) acrylate. These (meth) acrylate monomers can be used alone or in combination of two or more.

In the dental curable composition of the present invention,
In addition to the (meth) acrylate-based monomer, a polymerizable monomer other than the (meth) acrylate-based monomer may be used for adjusting the viscosity of the curable composition or adjusting other physical properties. It is also possible to mix and polymerize. However, the mixing ratio of the (meth) acrylate monomer to all polymerizable monomers is 50% by weight or more, preferably 6% by weight.
It is preferably 0% by weight or more. If it is less than 50% by weight, it tends to be difficult to obtain a curing speed required in dental clinic.

Examples of other polymerizable monomers that can be used in the present invention include styrene such as styrene, p-chlorostyrene, p-hydroxystyrene, divinylbenzene and α-methylstyrene or α-methylstyrene derivatives; fumaric acid Fumaric acid ester compounds such as monomethyl, diethyl fumarate and diphenyl fumarate; diallyl phthalate;
Allyl compounds such as diallyl terephthalate, diallyl carbonate, and allyl diglycol carbonate; diglycerol polyglycidyl ether, pentaerythritol polyglycidyl ether, 1,4-bis (2,3-epoxypropoxyperfluoroisopropyl) cyclohexane, sorbitol polyglycidyl ether, Trimethylolpropane polyglycidyl ether, resorcin diglycidyl ether, 1,6-hexanediol diglycidyl ether, polyethylene glycol diglycidyl ether, phenylglycidyl ether, p-ter
t-butylphenyl glycidyl ether, adipic acid diglycidyl ether, o-phthalic acid diglycidyl ether, dibromophenyl glycidyl ether, 1,2,2
7,8-diepoxyoctane, 4,4′-bis (2,3
-Epoxypropoxyperfluoroisopropyl) diphenyl ether, 3,4-epoxycyclohexylmethyl-3 ', 4'-epoxycyclohexanecarboxylate, 3,4-epoxycyclohexyloxirane, ethylene glycol-bis (3,4-epoxycyclohexanecarboxylate) Epoxy compounds such as 3-ethyl-3-hydroxymethyloxetane, 3-ethyl-3
-(Phenoxymethyl) oxetane, 3-ethyl-3-
(Naphthoxymethyl) oxetane, di [1-ethyl (3
-Oxetanyl)] methyl ether, 3-ethyl-3-
(2-ethylhexyloxymethyl) oxetane, 1,4
Oxetane compounds such as -bis {[(3-ethyl-3-oxetanyl) methoxy] methyl} benzene; vinyl-
2-chloroethyl ether, vinyl-n-butyl ether, triethylene glycol divinyl ether, 1,4
-Vinyl ether compounds such as cyclohexane dimethanol divinyl ether, trimethylolethane trivinyl ether and vinyl glycidyl ether. Among the other polymerizable monomers described above, epoxy compounds, oxetane compounds, and vinyl ether compounds are cations capable of initiating polymerization with an acidic compound that is one component of the dental chemical polymerization catalyst of the present invention. It is a polymerizable monomer. Further, the other polymerizable monomers may be used alone or in combination of two or more.

The amount ratio of the polymerizable monomer in the curable composition of the present invention to the dental chemical polymerization catalyst of the present invention is not particularly limited as long as the ratio is sufficient to cure the polymerizable monomer. However, generally, the amount of the dental chemical polymerization catalyst of the present invention is 0.01 to 20 parts by weight, particularly 0.1 to 10 parts by weight, based on 100 parts by weight of all polymerizable monomers. Is preferred.

In the dental curable composition of the present invention containing the polymerizable monomer and the dental polymerization catalyst of the present invention, the composition and the cured product thereof are in a range which does not deteriorate the physical properties of the composition. In addition to the dental chemical polymerization catalyst of the present invention, another chemical polymerization catalyst (thermal polymerization catalyst) or a photopolymerization catalyst using ultraviolet light or visible light (hereinafter, also simply referred to simply as other polymerization catalyst) is added. You may. When used in combination with a photopolymerization catalyst, a so-called dual cure type curable composition capable of both chemical curing and photocuring can be obtained.

The other polymerization catalyst to be used in combination is not particularly limited, but preferred examples of the thermal polymerization catalyst include azo compounds such as azobisisobutyronitrile.

Further, preferably used ultraviolet or visible light polymerization catalysts include diacetyl, acetylbenzoyl, benzyl, 2,3-pentadione, 2,3-octadione, 4,4′-dimethoxybenzyl, 4,4 ′. Α-diketones such as -oxybenzyl, camphorquinone, 9,10-phenanthrenequinone and acenaphthenequinone;
Benzoin alkyl ethers such as benzoin methyl ether, benzoin ethyl ether and benzoin propyl ether; 2,4-diethoxythioxanthone;
Thioxanthone derivatives such as chlorothioxanthone and methylthioxanthone; benzophenone derivatives such as benzophenone, pp'-dimethylaminobenzophenone, p, p'-methoxybenzophenone; 2,4,6-trimethylbenzoyldiphenylphosphine oxide, bis ( 2,6-dimethoxybenzoyl) -2,4,4-trimethylpentylphosphine oxide, bis (2,4,
Acylphosphine oxide derivatives such as 6-trimethylbenzoyl) phenylphosphine oxide, and an arylborate compound which is an essential component of the present invention, in which a dye and a photoacid generator are combined, that is, aryl borate / dye / photoacid generator A system consisting of Among these, particularly preferred are α-diketone and acylphosphine oxide-based photopolymerization initiators, and a system in which a dye and a photoacid generator are combined, in which case both chemical curing and photocuring are possible. It is possible to prepare a so-called dual cure type curable composition.

The α-diketone is preferably camphorquinone or benzyl, and the acylphosphone oxide is 2,4,6-trimethylbenzoyldiphenylphosphine oxide or bis (2,6-dimethoxybenzoyl) -2,4. Preferred are 2,4-trimethylpentylphosphine oxide and bis (2,4,6-trimethylbenzoyl) phenylphosphine oxide.

As the dye used for the aryl borate / dye / photoacid generator-based photopolymerization initiator, a coumarin-based dye can be mentioned. As particularly preferred coumarin-based dyes, those having a maximum absorption wavelength in the visible light range of 400 to 500 nm are preferred because of their high sensitivity to irradiators generally used for dental applications. Specific examples of typical coumarin dyes include 3-thienoyl coumarin and 3,3′-carbonylbis (7-diethylamino).
Coumarin, 3,3'-carbonylbis (4-cyano-7
-Diethylaminocoumarin and the like.

The above-mentioned photoacid generators generate Bronsted acid or Lewis acid upon irradiation with light, and any known photoacid generators can be used as long as they can be decomposed under visible light irradiation by a dye to generate an acid. Can be used. As the photoacid generator, a halomethyl group-substituted-s-triazine derivative or a diphenyliodonium salt compound is particularly preferable because the photoacid generator performs energy transfer with the coumarin-based dye and generates an acid with high efficiency under irradiation with visible light. It is.

The following are specific examples of typical halomethyl group-substituted -s-triazine derivatives: 2,4,6-tris (trichloromethyl) -s-triazine, 2-methyl-
4,6-bis (trichloromethyl) -s-triazine,
2- (2,4-dichlorophenyl) -4,6-bis (trichloromethyl) -s-triazine and the like can be mentioned.

Specific examples of the diphenyliodonium salt compound include bromides such as diphenyliodonium and p-octyloxyphenylphenyliodonium.
Tetrafluoroborate, hexafluorophosphate, hexafluoroantimonate, and trifluoromethanesulfonate salts are preferably used.

The above-mentioned other polymerization catalysts can be used not only alone, but also in combination of a plurality of types as required. The use amount of these other polymerization catalysts is not particularly limited as long as the effect of the present invention is not impaired, but 1 to 1000 parts by weight, particularly 10 to 500 parts by weight, per 100 parts by weight of the dental chemical polymerization catalyst of the present invention. Preferably it is a part.

The curable composition of the present invention may contain various fillers for the purpose of imparting physical properties required according to its use.
Organic solvents, water, thickeners, ultraviolet absorbers, polymerization regulators, dyes, antistatic agents, pigments, fragrances and the like can be added. For example, dental adhesives such as dental direct restoration adhesives (bonding materials) and dental indirect restoration adhesives,
When used as a dental restoration material to be a dental prosthesis such as a composite resin or the like, it is preferable to mix a filler such as an inorganic filler, an organic filler, or an organic-inorganic composite filler. When used as a dental pretreatment material such as a primer, it is preferable to add water or an organic solvent. In addition, when used for the purpose of surface lubrication, repair of dentures, temporary crowns, bridges, etc., it is preferable to add various additives commonly used in these materials. .

The curable composition of the present invention is finally used by mixing all components. However, in order to prevent deterioration during storage, the curable composition is divided into two stable packages as necessary. You can also. For example, a combination of a package composed of a part of the polymerizable monomer, an organic peroxide and an acidic compound (A) and a package composed of a part of the polymerizable monomer and an aryl borate compound (B) is common. It is.

Although the dental curable composition of the present invention can be used for various dental materials, it can be used for a dental direct restoration adhesive, a dental indirect restoration adhesive, a dental restoration material, and a dental pretreatment. When used as a material, it shows excellent features not found in conventional products.

For example, 100 parts by weight of a polymerizable monomer containing a polymerizable monomer having an acidic group, 0.01 to 10 parts by weight of an aryl borate compound, an organic peroxide and / or an oxide-based oxidizing agent 0 0.01 to 10 parts by weight, and 1 to 20 parts by weight of a polyvalent metal ion-eluting filler and / or 2 to 30 parts of water.
The direct dental restoration adhesive (bonding material) of the present invention comprising the dental curable composition of the present invention containing parts by weight.
Provides high adhesive strength to both dentin and enamel without performing pretreatment operations on the dentin, and does not require a light irradiation operation during application, and furthermore, a light-curable or chemically-curable dental It shows excellent features not found in conventional bonding materials, which are used for both repair materials. In addition, the dental direct restoration adhesive refers to an adhesive (bonding material) used in a direct restoration method represented by the adhesion between a composite resin and a tooth.

Further, 100 parts by weight of a polymerizable monomer containing a polymerizable monomer having an acidic group, 0.01 to 10 parts by weight of an aryl borate compound, an organic peroxide and / or an oxide-based oxidizing agent .01 to 10 parts by weight, and filler 50 to 9
The adhesive for dental indirect restoration of the present invention comprising the above-mentioned dental curable composition of the present invention containing 00 parts by weight has a feature of high adhesiveness to both enamel and dentin. In addition, the dental indirect restoration adhesive refers to an adhesive such as an adhesive resin cement or a resin-reinforced ionomer cement used in an indirect restoration method represented by adhesion between a crown and a tooth.

Further, the dental composite restorative material of the present invention comprising the dental curable composition of the present invention containing 50 to 900 parts by weight of filler based on 100 parts by weight of the total polymerizable monomer,
High strength cured product without coloring or discoloration can be given,
The use of the composite restoration material for dental makes it possible to perform restoration with high esthetics and reliability.

The dental curable composition of the present invention further comprises an acidic group-containing polymerizable monomer, an aryl borate compound, an organic peroxide and / or an oxidizing agent, and water. The dental pretreatment material has the features of providing high bonding strength to both enamel and dentin in a single operation and high safety even when both light and chemically polymerized adhesives are used. Show.

Hereinafter, each of these materials will be described in detail.

(I) Dental direct restoration adhesive of the present invention and dental indirect restoration adhesive of the present invention (hereinafter, also collectively referred to as the adhesive of the present invention) are used in the adhesive of the present invention. The acidic group-containing polymerizable monomer is
The dental chemical polymerization catalyst of the present invention also functions as an acidic compound. As the acidic group-containing polymerizable monomer, those described above as the acidic compound can be used without any limitation. However, from the viewpoint of adhesion strength to tooth substance or base metal, it is represented by the general formula (2) or (3). Compounds can be suitably used.

Particularly, when a polymerizable monomer containing a phosphoric acid group (phosphinico group or phosphono group) is used, higher adhesive strength can be realized. Furthermore, when the above-mentioned phosphoric acid group polymerizable monomer and carboxyl group-containing polymerizable monomer are used in combination, there is little variation in the adhesive strength to dentin, and moreover, higher adhesive strength can be realized. Can be. The mixing ratio of the phosphoric acid group-containing polymerizable monomer and the carboxylic acid group-containing polymerizable monomer is
What is necessary is just to determine arbitrarily according to the kind, quantity, etc. of another component combined. A preferred combination of a phosphoric acid group-containing polymerizable monomer and a carboxylic acid group-containing polymerizable monomer is, for example, 2- (meth) acryloyloxyethyl dihydrogen phosphate and 11-methacryloyloxy-
A combination of 1,1-undecanedicarboxylic acid, 2-
Combination of (meth) acryloyloxyethyl dihydrogen phosphate and 4- (meth) acryloyloxyethyl trimellitic anhydride, 10- (meth) acryloyloxydecyl acid phosphate and 11-
Preferred examples include a combination with methacryloyloxy-1,1-undecanedicarboxylic acid.

The polymerizable monomer used in the adhesive of the present invention may be composed of only the acidic group-containing polymerizable monomer, but has an acidic group from the viewpoint of the strength of the cured product and the adhesive durability. It is preferable to further include a polymerizable monomer that does not. However, the content ratio of the acidic group-containing polymerizable monomer in the total polymerizable monomer is 5 to 70% by weight, particularly 10% from the viewpoint of adhesive strength.
Preferably it is 〜50% by weight.

The polymerizable monomer having no acidic group is a polymerizable monomer having at least one polymerizable unsaturated group in the molecule and a polymerizable monomer other than the above-mentioned acidic group-containing polymerizable monomer. The polymerizable monomers that can be used in the dental curable composition of the present invention can be used without any limitation. As the polymerizable unsaturated group of such a polymerizable monomer,
Examples include the same as the acidic group-containing polymerizable monomer,
An acryloyl group, a methacryloyl group, an acrylamide group, a methacrylamide group and the like are preferable from the viewpoint of a curing speed.

Further, in the dental adhesive of the present invention, as another polymerizable monomer, a polymerizable monomer having a functional group binding to a noble metal for the purpose of adhering to a noble metal restoration for a crown. Can also be added. Examples of such polymerizable monomers that can be suitably used include thiouracil derivatives, triazinedithione derivatives, and polymerizable polymerizable monomers having a functional group such as a mercaptothiazole derivative. As specific examples of the polymerizable monomer, each polymerizable monomer represented by the following general formula can be used.

That is, a polymerizable monomer capable of forming a mercapto group by tautomerism represented by the following general formulas (4) to (8): having a disulfide group represented by the following general formulas (9) to (12) Polymerizable monomer; the following general formulas (13) to (1)
Polymerizable monomers having a chain or cyclic thioether group shown in 4) are mentioned.

[0091]

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Wherein R ₈ is a hydrogen atom or a methyl group, R ₉ is a divalent saturated hydrocarbon group having 1 to 12 carbon atoms,
—CH ₂ —C ₆ H ₄ —CH ₂ — group, — (CH ₂ ) _{2 O—} Si (C
_{H 3) 2 OSi (CH 3} ) 2 - (CH 2) p - group (o and p
Is an integer of 1 to 5 each independently. ) Or-
A CH ₂ CH ₂ OCH ₂ CH ₂ — group, and Z represents —OC (=
O) —, —OCH ₂ — or —OCH ₂ —C ₆ H ₄ — (in each case, the rightmost carbon atom is bonded to the unsaturated carbon, and the leftmost oxygen atom is bonded to the group R ₉₎ ), Z ′ is a —OC (＝ O) — group, a —C ₆ H ₄ — group, or a bond, and in the case of a ｛—OC (ＯO) — group, the rightmost carbon atom is an unsaturated carbon. And the leftmost oxygen atom is bonded to the group R ₉ . {, Y is -S-, -O-, or -N (R ')-(R' is a hydrogen atom or an alkyl group having 1 to 5 carbon atoms). The case of means the state where the group R ₉ and the unsaturated carbon are directly bonded.

Specific examples of these compounds include the following as polymerizable monomers capable of forming a mercapto group by tautomerism represented by the general formulas (4) to (8).

[0094]

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[0095]

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[0096]

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The polymerizable monomers having a disulfide group represented by the general formulas (9) to (12) include the following compounds.

[0098]

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Further, examples of the polymerizable monomer having a chain or cyclic thioether group represented by the general formulas (13) to (14) include the following compounds.

[0100]

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These polymerizable monomers having a functional group capable of binding to a noble metal can be used alone or in combination of two or more. The compounding amount may be appropriately determined in consideration of the viscosity of the composition and the mechanical strength of the cured body, but is generally 100 parts by weight based on the total polymerizable monomer in the dental adhesive. 0.1 to 50 parts by weight, more preferably 0.2 to 50 parts by weight
It is in the range of 20 parts by weight.

The aryl borate compound used in the adhesive of the present invention is a component of the dental chemical polymerization catalyst of the present invention, and those described above in the description thereof can be used without limitation. The amount of the aryl borate compound used must be 0.01 to 10% by weight based on all polymerizable monomers in order to obtain an excellent adhesive effect. Although the optimum amount varies depending on the type and amount of the polymerizable monomer used and the mixing ratio of other components, it is usually 0.05 to 8% by weight, particularly 0.5 to 6% by weight.
Preferably, it is in weight%.

The organic peroxide used in the adhesive of the present invention is one component of the dental chemical polymerization catalyst of the present invention, and those described above in the description thereof can be used without limitation. The amount of the organic peroxide to be used must be 0.01 to 10% by weight based on all polymerizable monomers in order to obtain an excellent adhesive effect. Although the optimum amount varies depending on the type and amount of the polymerizable monomer used and the mixing ratio of other components, it is usually 0.0
It is preferably from 5 to 8% by weight, especially from 0.5 to 5% by weight.

In order to further enhance the adhesiveness of the adhesive of the present invention, it is more preferable to add the above-mentioned decomposition accelerator.

When the adhesive of the present invention is an adhesive for direct dental restoration (bonding material), a polyvalent metal ion eluting filler is added as a filler. By adding such a filler, the chelation reaction between the acidic group-containing polymerizable monomer and the polyvalent metal ion proceeds together with the polymerization reaction, and the strength of the cured product can be improved. The polyvalent metal ion eluting filler is not particularly limited as long as it has the above properties. Specific examples of the polyvalent metal ion eluting filler that can be used in the present invention,
Examples include hydroxides such as calcium hydroxide and strontium hydroxide, zinc oxide, silicate glass, fluoroaluminosilicate glass, barium glass, and strontium. Among these, fluoroaluminosilicate glass is the most excellent in terms of color resistance of the cured product, and it is preferable to use this. As the fluoroaluminosilicate glass, known ones used as dental cements can be used. Commonly known compositions of fluoroaluminosilicate glass are, by weight percent ion, silicon, 10-33; aluminum, 4-30; alkaline earth metal, 5-36; alkali metal, 0-10;
0.2-16; fluorine, 2-40 and residual oxygen. In addition to those having such a composition, those obtained by substituting part or all of the alkaline earth metal with magnesium, strontium or barium can also be used. In particular, those substituted with strontium are often suitably used because they give radiopaque and high strength to the cured product. These polyvalent metal ion eluting fillers may be treated with a surface treatment agent represented by a silane coupling agent without any problem. The surface treatment may be performed by a known method. As the silane coupling agent, γ-methacryloxypropyltrimethoxysilane, ε-methacryloxyoctyltrimethoxysilane, vinyltrimethoxysilane and the like are suitably used.

The amount of the polyvalent metal ion-eluting filler added is 1 to 20 parts by weight based on 100 parts by weight of the total polymerizable monomer.
It is sufficient if it is part by weight, but from the viewpoint of the effect, it is more preferably from 2 to 15 parts by weight.

Further, in the dental direct restorative adhesive of the present invention, water may be added for the purpose of improving the adhesive strength, particularly the adhesive strength to enamel, without the need for pretreatment and light irradiation. It is valid. Addition of water promotes the demineralization of the dentin, and the use of the filler together with the polyvalent ion-eluting filler is particularly preferable because it promotes the chelation reaction. The water preferably does not substantially contain impurities harmful to storage stability, biocompatibility and adhesiveness, and examples include deionized water and distilled water. The amount of addition may be 2 to 30 parts by weight with respect to 100 parts by weight of the total amount of all polymerizable monomers, but it is more preferable to add 3 to 20 parts by weight. If the amount of water exceeds 30 parts by weight, the strength of the cured product is significantly reduced, which is not preferable.

The filler used in the adhesive for dental indirect restoration according to the present invention is an inorganic filler, an organic filler, or a composite of an inorganic oxide and a polymer used in a general dental adhesive. Inorganic-organic composite fillers are used without any restrictions.

Specific examples of the inorganic filler that can be used in the adhesive for dental indirect restoration of the present invention include quartz, silica,
Silica-alumina, silica-titania, silica-zirconia, silica-magnesia, silica-calcia, silica-barium oxide, silica-strontium oxide, silica-titania-sodium oxide, silica-titania-potassium oxide, titania, zirconia, alumina, etc. Is mentioned. Further, as the inorganic filler, the above-mentioned polyvalent ion-eluting filler is also suitably used. These inorganic fillers may be treated with a surface treatment agent represented by a silane coupling agent, as described above, without any problem.

Specific examples of the organic filler which can be used in the adhesive for indirect dental restoration of the present invention include polymethyl methacrylate, polyethyl methacrylate, methyl methacrylate-ethyl methacrylate copolymer, ethyl methacrylate-butyl methacrylate. Copolymers, methyl methacrylate-trimethylolpropane methacrylate copolymer, polyvinyl chloride, polystyrene, chlorinated polyethylene, nylon, polysulfone. Polyether sulfone, polycarbonate and the like can be mentioned.

The shape of the filler is not particularly limited, and may be pulverized particles or spherical particles obtained by ordinary pulverization. Also, the particle size of these fillers is not particularly limited, but those having a thickness of 100 μm or less are preferable, and those having a particle size of 30 μm or less are preferably used in terms of coating thickness for obtaining good compatibility. You.

The filler may be added in an amount of 50 to 900 parts by weight based on 100 parts by weight of the total polymerizable monomer. If the amount is less than 50 parts by weight, the physical strength of the material decreases, and
If the amount is more than 00 parts by weight, the fluidity of the material decreases, and the operability decreases. A more preferable addition amount is 100 to 800.
Parts by weight.

It is preferable to add a photopolymerization catalyst to the dental adhesive of the present invention as long as the physical properties are not reduced. When a photopolymerization catalyst is used in combination, it can be used as a chemical and light dual-cure adhesive, and is particularly suitable because it has a wide range of clinical applications.

The dental adhesive of the present invention may contain, in addition to the above-mentioned components, an organic solvent and an organic solvent as long as the effects of the present invention are not impaired.
Thickeners, inorganic acids, organic acids, ultraviolet absorbers, polymerization regulators,
Dyes, antistatic agents, pigments, fragrances and the like can be added.

As the organic solvent, water-soluble organic solvents such as methanol, ethanol, propanol, butanol, ethylene glycol, propanediol, butanediol, pentanediol, butenediol, glycerin, trimethylolpropane, hexanetriol, allyl alcohol and diethylene glycol , Diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, triethylene glycol, triethylene glycol monomethyl ether, tetraethylene glycol, propylene glycol, dipropylene glycol, tripropylene glycol, 2-methoxyethanol, 2-ethoxyethanol, 2- (methoxyethoxy ) Ethanol, 2-isopropoxyethanol, 2-
Alcohols or ethers such as butoxyethanol, 1-methoxy-2-propanol, 1-ethoxy-2-propanol, dipropylene glycol monomethyl ether, tripropylene glycol monomethyl ether, and glycerin ether; ketones such as acetone and methyl ethyl ketone; acetic acid And carboxylic acids such as acetic anhydride and propionic acid. Further, as a water-insoluble organic solvent, hexane, heptane, octane, toluene, dichloromethane, chloroform, carbon tetrachloride, dichloroethane, trichloroethane, methyl ethyl ketone,
Pentanone, ethyl formate, propyl formate, butyl formate,
Ethyl acetate, propyl acetate, butyl acetate and the like can be used. Among these, those having little harmful effect on the living body are desirable, and ethanol, propanol, ethylene glycol, propanediol, butanediol, pentanediol, glycerin, trimethylolpropane, hexanetriol, diethylene glycol, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, Triethylene glycol, triethylene glycol monomethyl ether, tetraethylene glycol, propylene glycol, dipropylene glycol, tripropylene glycol, dipropylene glycol monomethyl ether, tripropylene glycol monomethyl ether, glycerin ether, acetone,
2-hydroxyethyl methacrylate and the like are preferred,
Especially ethanol, propanol, ethylene glycol,
Propanediol, acetone and the like are most preferably used. These organic solvents can be used as a mixture of two or more as necessary.

As the thickener, polymer compounds such as carboxymethyl cellulose and polyvinyl alcohol and highly dispersible silica can be used.

As inorganic acids, hydrochloric acid, sulfuric acid, nitric acid, phosphoric acid and the like can be used. Examples of the organic acid include carboxylic acids such as acetic acid, propionic acid, maleic acid, fumaric acid, phthalic acid, benzoic acid, trichloroacetic acid, trifluoroacetic acid, citric acid and trimellitic acid, p-toluenesulfone, benzenesulfonic acid And sulfonic acids such as methanesulfonic acid and trifluoromethanesulfonic acid, and phosphoric acids such as methylphosphonic acid, phenylphosphonic acid, dimethylphosphinic acid and diphenylphosphinic acid.

The packaging form of the adhesive of the present invention is preferably such that the aryl borate compound is packaged separately from the acidic group-containing polymerizable monomer. Since the aryl borate compound decomposes under acidic conditions, for example, in a bonding material, a polymer containing an acidic group-containing polymerizable monomer or another polymerizable monomer as a main component and a polymer containing no acidic group are polymerized. In the case of dental cement, a liquid containing an acidic monomer, an organic peroxide and an aryl borate compound as main components is separately packaged. Packaging of a liquid containing a peroxide as a main component and a powder containing a filler and an aryl borate compound as a main component, or containing an acidic group-containing polymerizable monomer, a filler and an organic peroxide as a main component It is preferable to use a mixture of a paste and a paste composed of another polymerizable monomer, a filler and an aryl borate compound which are separately packaged when used.

The method of using the adhesive of the present invention is not particularly limited, but it can be suitably used, for example, as follows.

That is, in the case of an adhesive for direct restoration for dental use (bonding material), the curable dental composition to be used as the adhesive is applied to the tooth surface using a sponge or a small brush, and is immediately or several seconds to After standing for several minutes, a restoration material such as a composite resin is filled and polymerized and cured, so that the restoration material and the dentin can be firmly bonded.

On the other hand, in the case of an adhesive for dental indirect restoration (dental cement), a dental curable composition serving as the adhesive is directly applied to the tooth surface and / or various restorations by using a spatula or a small brush. After application using the method, the two may be brought into contact with each other and then polymerized and cured, or, for the purpose of obtaining stronger adhesive strength, the tooth surface may be preliminarily prepared with an aqueous acid solution or an acidic group-containing polymerizable monomer and water. After the treatment with a pretreatment material containing the above, the method of bonding as described above can also be adopted.

(II) Dental composite restoration material of the present invention The dental composite restoration material of the present invention contains 50 to 900 parts by weight of a filler based on 100 parts by weight of the total polymerizable monomer. It consists of a dental curable composition. Here, the composite restoration material for dental means a dental restoration material in which different materials such as a filler and a monomer or a cured product thereof are combined, and specifically, a direct restoration material such as a composite resin. Restorative materials, such as indirect restoration materials, such as those used in the production of inlays, inlays, crowns, bridges, etc., replace prostheses, i.e., those that replace tooth defects.

As the polymerizable monomer used in the dental composite restorative material of the present invention, the polymerizable monomer in the dental curable composition of the present invention can be used without any limitation.

As the filler used in the dental composite restorative material of the present invention, an inorganic filler and an organic filler are used without any limitation depending on the application. However, when used in combination with the inorganic filler, chemical filling polymer is used. When a composition such as a mold composite resin or a composite resin for constructing an abutment is combined with an organic filler, the composition is suitable as a material for a dental room temperature curing resin or the like for producing a temporary crown or bridge.

As the inorganic filler, those exemplified in the dental adhesive for indirect restoration of the present invention are preferably used. These inorganic fillers may be treated with a surface treatment agent represented by a silane coupling agent without any problem.

As the organic filler, those exemplified for the adhesive for dental indirect restoration of the present invention are preferably used.

The shape of the filler is not particularly limited, and may be pulverized particles or spherical particles obtained by ordinary pulverization. In addition, the particle size of these fillers is not particularly limited, but is 100 μm from the viewpoint of operability.
It is common to use:

The addition amount of these fillers is not unequivocally determined depending on the intended use, but is preferably 50 to 900 parts by weight, more preferably 100 to 100 parts by weight, based on 100 parts by weight of the total polymerizable monomer.
It may be selected from a range of up to 800 parts by weight.

A photopolymerization catalyst may be added to the composite restorative material of the present invention as long as the physical properties are not reduced. When a photopolymerization catalyst is used in combination, it can be used as a chemical and light dual-cure adhesive, and is particularly suitable because it has a wide range of clinical applications.

[0130] In addition to the above-mentioned components, the dental composite restorative material of the present invention may contain a thickener, an inorganic acid, an organic acid, an ultraviolet absorber, a polymerization modifier, a dye, It is possible to add antistatic agents, pigments, fragrances and the like. As these components, those exemplified in the dental adhesive of the present invention can be suitably used.

As described above, since the aryl borate compound is easily decomposed under acidic conditions, the packaging form of the dental composite restoration material of the present invention includes the aryl borate compound,
It is preferable that the acidic group-containing polymerizable monomer and the organic peroxide are separately packaged so that they come into contact for the first time in use. For example, a liquid containing a polymerizable monomer, an acidic compound and an organic peroxide as a main component and a liquid containing a polymerizable monomer and an aryl borate compound as a main component are separately prepared, and these solutions are separately prepared. It is preferable to package and mix immediately before use.

(III) Dental pre-treatment material of the present invention The dental pre-treatment material of the present invention comprises an acidic group-containing polymerizable monomer,
The dental curable composition of the present invention contains an aryl borate compound, an organic peroxide, and water.

The acidic group-containing polymerizable monomer used in the dental pretreatment material of the present invention also functions as an acidic compound of the dental chemical polymerization catalyst of the present invention. As the acidic group-containing polymerizable monomer, those described above as the acidic compound can be used without limitation, but from the viewpoint of adhesion strength to tooth or base metal, those that can be suitably used in the adhesive of the present invention are described. It is preferred to use the same acidic group-containing polymerizable monomers as indicated. In addition, when a combination of a phosphoric acid group-containing polymerizable monomer and a polyvalent carboxylic acid group-containing polymerizable monomer having a plurality of carboxylic acid groups in one molecule is used, the adhesive strength of dentin is reduced. There is little variation,
Moreover, higher adhesive strength can be realized as in the case of the adhesive of the present invention.

The compounding amount of the acidic group-containing polymerizable monomer in the pretreatment material of the present invention is preferably 3 to 50% by weight when all components constituting the pretreatment material composition are 100% by weight. Preferably it is 7 to 40% by weight. If it is less than 3% by weight, the adhesive strength to enamel tends to be insufficient. If it exceeds 50% by weight, the adhesive strength of both dentin and enamel tends to decrease.

The aryl borate compound used in the pretreatment material of the present invention is one component of the dental chemical polymerization catalyst of the present invention, and those described above in the description can be used without limitation. The addition amount of the aryl borate compound varies depending on the type and the mixing ratio of the other components, but is preferably 0.01 to 10% by weight, more preferably 0.01 to 10% by weight, when all the components constituting the pretreatment material composition are 100% by weight. Is 0.05-8% by weight,
Most preferably, it is 0.5 to 6% by weight.

The organic peroxide used in the pretreatment material of the present invention is a component of the dental chemical polymerization catalyst of the present invention, and those described above in the description can be used without any limitation. The amount of the organic peroxide used is 0.01% by weight based on 100% by weight of all components constituting the pretreatment material in order to obtain an excellent adhesive effect.
Preferably from 10 to 10% by weight, more preferably from 0.05 to 10% by weight.
8% by weight, most preferably 0.5-5% by weight. If the addition amount is less than 0.01% by weight, the effect as a polymerization catalyst is reduced, so that the adhesive strength of both enamel and dentin tends to be reduced. 10% by weight
When the ratio exceeds the above, a problem may occur in the storage stability of the composition. In order to further enhance the adhesiveness of the dental pretreatment material of the present invention, it is more preferable to add the above-mentioned decomposition accelerator.

The water used in the pretreatment material of the present invention is necessary for demineralizing the dentin. This water preferably does not substantially contain impurities harmful to storage stability, biocompatibility and adhesion, and examples include deionized water and distilled water. The preferable addition amount of the water is 5 to 90% by weight, and more preferably 20 to 80% by weight, when all components constituting the pretreatment material composition are 100% by weight. If it is less than 5% by weight, the demineralization of the dentin tends to be insufficient, so that the adhesive strength of both enamel and dentin may be insufficient. If it exceeds 90% by weight, the adhesive strength of both dentin and enamel tends to decrease.

In addition to the above components, the dental pretreatment material of the present invention may contain a water-soluble organic solvent, as long as the effects are not impaired.
It is possible to add a water-insoluble organic solvent, a polymerizable monomer other than the acidic group-containing polymerizable monomer, another polymerization catalyst, a strong inorganic acid, a metal salt, and the like. In addition, as each of the additives that can be used, the same additives as those described as the additives in the adhesive of the present invention can be used.

In particular, when the acidic group-containing polymerizable monomer to be used is difficult to dissolve in water, each component is dissolved by using a water-soluble organic solvent, and the solution is formed into a uniform solution or a solution which is long enough to use. It is preferred that the emulsion be stable over time. Examples of the water-soluble organic solvent that can be used at this time include the same ones as exemplified for the adhesive of the present invention. Among them, it is preferable to use those exemplified as having little harmful effect, especially alcohols such as ethanol. A plurality of water-soluble organic solvents can be used as a mixture if necessary. The amount of the water-soluble organic solvent is preferably 80% by weight or less based on all the components of the pretreatment material.

The method for using the dental pretreatment material of the present invention is not particularly limited, and is compounded with an acidic group-containing polymerizable monomer, an organic peroxide, an aryl borate compound, water, and if necessary. The desired components are weighed in a desired ratio into a container, stirred and mixed to form a uniform solution or an emulsion, which is applied to the tooth surface using a sponge or a small brush, and left for a few seconds to a few minutes. A method of spraying and drying, applying an adhesive on the pretreated tooth surface, bringing various restoration materials into contact, and polymerizing and curing the adhesive is preferably employed. The dental pretreatment material of the present invention may be used by dividing its constituent components. For example, after pretreatment with a solution containing an organic peroxide, treatment with a solution containing an acidic group-containing polymerizable monomer, water and an aryl borate compound is also possible. In this case, the curable composition of the present invention is formed on the tooth surface. In the dental pretreatment material of the present invention, a uniform film is formed on the tooth surface after the treatment, and the adhesive component applied later diffuses into the film, so that good adhesion to the tooth material is achieved. It seems to be chosen.

As described above, since the aryl borate compound is easily decomposed under acidic conditions, the packaging form of the dental pretreatment material of the present invention includes an aryl borate compound, an acidic group-containing polymerizable monomer, It is preferable to package these separately so that the organic peroxides come into contact for the first time in use. For example, an acid group-containing polymerizable monomer, an oxidizing agent such as an organic peroxide, and a solution mainly containing other components, and a solution mainly containing water and an aryl borate compound, prepared separately. It is preferable to pack the solutions separately and mix them immediately before use.

[0142]

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

The compounds used in the examples and comparative examples and their abbreviations are shown in (1), the method for measuring the curing time in (2),
The methods for measuring various physical properties of the cured body are described in (3) to (6), and the method for measuring the adhesive strength of the adhesive for dental direct restoration of the present invention is described in (7).
Next, (8) shows a method for measuring the adhesive strength of the adhesive for indirect restoration of dental material of the present invention, and (9) shows a method for measuring the adhesive strength using the dental pretreatment material of the present invention.

(1) Abbreviations and structure [Polymerizable monomer containing acidic group] PM; a mixture of 2-methacryloyloxyethyl dihydrogen phosphate and bis (2-methacryloyloxyethyl) hydrogen phosphate MAC-10; 11- Methacryloyloxy-1,1
-Undecanedicambonic acid 4-META; 4-methacryloyloxyethyl trimellitic anhydride MTS; 2-methacryloyloxyethyl-3'-methacryloyloxy-2 '-(3,4-dicarboxybenzoyloxy) propyl succinate.

[Polymerizable monomer other than acidic group-containing polymerizable monomer] MMA; methyl methacrylate TMPT; trimethylolpropane trimethacrylate bis-GMA; 2,2-bis (4- (2-hydroxy-3- Methacryloyloxypropoxy) phenyl)
Propane 3G; Triethylene glycol dimethacrylate D2.6E; 2,2-bis [(4-methacryloyloxy polyethoxyphenyl) propane] HEMA; 2-hydroxyethyl methacrylate MTU-6; 6-methacryloyloxyhexyl-2
-Thiouracil-5-carboxylate NPG; neopentyl glycol dimethacrylate.

[Organic peroxide] Permec N; methyl ethyl ketone peroxide perhexa H; cyclohexanone peroxide perhexyl H; t-hexyl hydroperoxide parkmill P; diisopropylbenzene hydroperoxide perbutyl H; t-butyl hydroperoxide BPO; benzoyl Peroxide Perhexyl I; t-hexyl peroxyisopropyl monocarbonate Perbutyl I; t-butyl peroxyisopropyl monocarbonate Parkmill H; cumene hydroperoxide (10) perbutyl D; di-t-butyl peroxide.

[Borate compound] PhBNa; sodium tetraphenylboron PhBTEOA; tetraphenylboron triethanolamine salt PhBDMPT; tetraphenylboron dimethyl-p
-Toluidine salt PhBDMBE; ethyl tetraphenylboron dimethylaminobenzoate FPhBNa; tetrakis (p-fluorophenyl)
Sodium boron PhBTEA; tetraphenylboron triethylamine salt PhBDMEM; tetraphenylboron dimethylaminoethyl methacrylate salt BFPhBNa; sodium butyltri (p-fluorophenyl) boron.

[Decomposition accelerator] VOAA; vanadium (V) acetylacetonate FeAA; iron (III) acetylacetonate CuAA; copper (II) acetylacetonate V2O5; vanadium (V) FeCl3; iron (III) chloride .

[Filler] PMMA; polymethyl methacrylate PEMA; polyethyl methacrylate P (MMA-EMA); methyl methacrylate-ethyl methacrylate copolymer 0.5Si-Zr; spherical silica-zirconia (or an aggregate thereof), γ -Surface treatment of methacryloyloxypropyltrimethoxysilane: average particle size of primary particles 0.5
μm 0.06 Si-Zr; spherical silica-zirconia (or an aggregate thereof), γ-methacryloyloxypropyltrimethoxysilane surface treatment: average particle diameter of primary particles
06 μm FASG; fluoroaluminosilicate glass powder:
The average particle size of 0.5 for dental direct restoration adhesives
μm, and those having an average particle diameter of 3 μm were used for the adhesive for dental indirect restoration. 3Si-Zr; amorphous silica-zirconia, γ-methacryloyloxypropyltrimethoxysilane surface treatment: average particle size 3 μm 0.3Si-Ti; spherical silica-titania (or aggregate thereof), γ-methacryloyloxypropyltrimethoxy Silane surface treatment: average particle size of primary particles 0.3μ
m.

[Other components] DEPT; p-tolyldiethanolamine TCT; 2,4,6-tris (trichloromethyl)-
s-triazine DMPT; dimethylamino-p-toluidine CDAC; 3,3′-carbonylbis (7-diethylamino) coumarin BAPO; bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide BDTPO; bis (2,6 -Dimethoxybensoyl)
-2,4,4-trimethylpentylphosphine oxide IPA; isopropyl alcohol.

(2) Measurement of Curing Time The curing time was measured by a heat generation method using a thermistor thermometer. That is, 5 g (a) of the polymerizable monomer solution containing the organic peroxide and the acidic compound of the present invention and 5 g (b) of the polymerizable monomer solution containing the aryl borate compound are stirred and mixed for 20 seconds to form a uniform solution. did. Then 2cm ×
After pouring into a Teflon (registered trademark) mold having a hole of 6 mmφ at the center of 2 cm × 1 cm, a thermistor thermometer was inserted, and the time from the start of mixing to the recording of the maximum temperature was defined as the curing time. The measurement was performed in a constant temperature room at 23 ° C.

(3) Evaluation of Curability and Surface Stickiness A curable composition was prepared in the same manner as described above, poured into a mold of the same mold, and cured in air at 23 ° C. for 15 minutes. The hardness of the cured product and the stickiness of the surface were evaluated on a 5-point scale. That is, those having sufficient hardness, those having no stickiness on the surface are ◎, those having sufficient hardness and sticky only on the surface become ○, jelly-like, and the unpolymerized monomer is on the surface.も の for the remaining ones, × for the partially jelly-like ones,
Those that did not cure at all were marked as XX.

(4) Initial Coloring and Discoloration Resistance Test of the Cured Product The discoloration resistance test of the cured product was performed by the following method. First,
Each component was mixed at a predetermined ratio and kneaded for 20 seconds. Then pour it into a 10 mm x 10 mm x 2 mm mold,
Cured at 37 ° C. for 24 hours. The initial coloring of the obtained cured product was visually evaluated in the following three stages.

Score 1 Colorless and transparent Score 2 Yellow Score 3 Brown.

Further, the obtained cured product was placed in water at 80 ° C. for 60 hours.
The cured product was stored for days, and the degree of discoloration of the cured product after storage was evaluated according to the following evaluation criteria.

Score 1 No change Score 2 Only cloudiness Score 3 Slightly yellow discoloration Score 4 Yellow discoloration Score 5 Discoloration to brown.

(5) Measurement of Flexural Strength and Hardness The flexural strength of the cured product was measured by the following method. First, each component was uniformly mixed at a predetermined ratio, and 25 mm × 4
It was poured into a mold of 2 mm × 2 mm and cured at 37 ° C. for 24 hours. The obtained cured product was subjected to a bending fracture test at a distance between supporting points of 20 mm. Crosshead speed is 1mm /
min. The hardness was measured by buffing the surface of the cured product, and measured with a micro hardness tester manufactured by Matsuzawa Seiki.
Knoop hardness was measured under a load of 0 g for 20 seconds. The measurement was performed in a constant temperature room at 23 ° C.

(6) Measurement of residual monomer amount The residual monomer amount in the cured product was measured by the following method. First, each component was mixed at a predetermined ratio, and 20 mm × 2
It was poured into a 0 mm × 1 mm mold and cured at 37 ° C. for 24 hours. The obtained cured product was immersed in 20 ml of acetonitrile at 23 ° C. for 24 hours, and the amount of monomer in the solution was quantified by high performance liquid chromatography.

(7) Method for Measuring Adhesive Strength of Dental Adhesive for Direct Restoration (Bonding Material) of the Present Invention Within 24 hours after slaughter, the lower front teeth of the bovine mandible were removed, and water was injected.
The enamel or dentin plane was cut out with 800 emery paper so as to be parallel to the lips. Next, compressed air was blown onto these surfaces for about 10 seconds to dry them. After that, a double-sided tape having a hole having a diameter of 3 mm was fixed to the flat surfaces, and the adhesion area was defined. Next, wax having a thickness of 1 mm and having a hole of 8 mmφ was adhered so as to be concentric with the double-sided tape to prepare a simulated cavity. The bonding material prepared immediately before use was applied to the simulated cavity, and left for 20 seconds.

When a light-curable composite resin is used, a light-curable composite resin,
Palfique Esterite [manufactured by Tokuyama Co., Ltd.] is charged, covered with a polypropylene sheet, and irradiated with light for 30 seconds using Power Light [manufactured by Tokuyama Co., Ltd.] to polymerize and cure the composite resin. Then, a test piece was prepared.

When a chemically curable composite resin was used, a chemically polymerizable composite resin, Parfike (manufactured by Tokuyama Corporation) was similarly charged and cured to prepare a test piece.

The test piece prepared by the above method was
After immersion in 7 ° C. water, a crosshead speed of 1 was measured using a tensile tester (Autograph AG5000 manufactured by Shimadzu Corporation).
A tensile test was performed under the condition of mm / min. Eight adhesive test pieces were measured per test, and the average value was defined as the adhesive strength.

(8) Method for Measuring Adhesive Strength of Dental Adhesive for Indirect Restoration (Dental Cement) of the Present Invention The tooth surface pretreatment material used in the adhesion test was prepared by stirring, mixing and preparing the following composition, and immediately before use. Used as a mixture. However,
() Indicates parts by weight.

Tooth surface pretreatment material A; Solution A: PM (15) MAC-10 (5) bis-GMA (5) Isopropyl alcohol (16) Solution B: Water (38) Isopropyl alcohol (19) PhBTEOA (2).

Tooth surface pretreatment material b; Solution A: PM (15) MAC-10 (5) bis-GMA (5) Acetone (10) Isopropyl alcohol (6) Solution B: Water (38) Acetone (19) p- Sodium toluene sulfinate (2).

[0166] Adhesion test method: Within 24 hours after slaughter, the lower teeth of the lower jaw of the cow were extracted, and under water injection, an enamel or dentin plane was cut out with an # 800 emery paper so as to be parallel to the lips. Next, after compressed air was blown onto these surfaces for about 10 seconds to dry them, a double-sided tape having a hole having a diameter of 3 mm was fixed to the flat surfaces, and the adhesion area was defined. Next, for the tooth surface treatment, a tooth surface treatment material was thinly applied, left for 20 seconds, and then dried by blowing compressed air for about 5 seconds.

[0167] The dental cement of the present invention prepared immediately before use was applied to the treated or untreated tooth surface, and a stainless steel attachment having a diameter of 8 mmφ was pressed against the tooth surface to prepare a test piece. This test piece was placed at 37 ° C and humidity
After maintaining for 1 hour in an atmosphere of 00%, the sample was further immersed in water at 37 ° C. for 24 hours, and a crosshead speed of 1 mm / cm.sup.
A tensile test was performed at min. Eight adhesive test pieces were measured per test, and the average value was defined as the adhesive strength.

(9) Method of Measuring Adhesive Strength Using Dental Pretreatment Material of the Present Invention Adhesive materials A to F used in the adhesive test were prepared by stirring and mixing with the following compositions. However, () indicates parts by weight.
The commercially available products were used as they were according to the method specified by the manufacturer.

Chemically curable adhesive Adhesive A; powder component: PMMA (5) P (MMA-EMA) (95) BPO (1) Liquid component: MMA (65) HEMA (20) bis-GMA (6) 3G (4) MAC-10 (5) DMPT (3).

Adhesive B; powder component: PMMA (5) P (MMA-EMA) (95) PhBTEOA (3) Liquid component: MMA (65) HEMA (20) MAC-10 (5) PM (5) bis- GMA (3) 3G (2) Park Mill H (2).

Adhesive C; powder component: PMMA (5) P (MMA-EMA) (95) PhBTEOA (3) VOAA (0.005) Liquid component: MMA (65) HEMA (20) MAC-10 (5) PM (5) bis-GMA (3) 3G (2) Park Mill H (2).

Adhesive D: Cement paste A and B attached to Bistite II [manufactured by Tokuyama Corporation] Adhesive E: Panavia fluorocement [manufactured by Kuraray Co., Ltd.]
Attached adhesive cement A paste and B paste.

Light-curing adhesive Adhesive F: Bonding agent attached to Tokso Mac Bond II [manufactured by Tokuyama Corporation] Adhesive G: Bonding agent attached to Clearfill Mega Bond (manufactured by Kuraray Co., Ltd.)

Pretreatment method: Within 24 hours after slaughter, the lower teeth of the lower jaw of the cow were removed, and under water injection, enamel or dentin plane was cut in parallel with the lips with # 800 emery paper. Next, after compressed air was blown onto these surfaces for about 10 seconds to dry them, a double-sided tape having a hole having a diameter of 3 mm was fixed to the flat surfaces, and the adhesion area was defined. The dental composition of the present invention was thinly applied to this range, allowed to stand for 20 seconds, and then dried by blowing compressed air for about 5 seconds.

Adhesion with Chemically Curable Adhesive: A chemically curable adhesive is applied to the pretreated tooth surface as in the case of the photocurable adhesive, and a stainless steel attachment having a diameter of 8 mmφ is pressed from above. Then, a test piece was prepared. This test piece was kept for 1 hour in an atmosphere of 37 ° C. and 100% humidity, then immersed in water at 37 ° C. for 24 hours, and at a crosshead speed of 1 mm / min using a tensile tester (Autograph AG5000 manufactured by Shimadzu Corporation). A tensile test was performed. Eight adhesive test pieces were measured per test, and the average value was defined as the adhesive strength.

Adhesion by photo-curable adhesive: A photo-curable adhesive is applied to the adhesive surface prepared by the above method, and cured by irradiating with light using a power light [manufactured by Tokuyama Corporation] for 10 seconds. Was. Next, a 1 mm thick hole with an 8 mmφ hole
The wax was adhered so as to be concentric with the double-sided tape to prepare a simulated cavity, and a light-curable composite resin, Parfique Esterite (manufactured by Tokuyama Corporation) was filled in the simulated cavity. After covering with a polypropylene sheet, the composite resin was polymerized and cured by light irradiation for 30 seconds to prepare a test piece. This test specimen was applied for 24 hours 3
After immersion in 7 ° C. water, a crosshead speed of 1 was measured using a tensile tester (Autograph AG5000 manufactured by Shimadzu).
A tensile test was performed under the condition of mm / min. Eight adhesive test pieces were measured per test, and the average value was defined as the adhesive strength.

[Examples and Comparative Examples on Chemical Polymerization Catalyst of the Present Invention and Dental Curable Composition of the Present Invention] Example 1 MMA / TMPT (90 wt% / 10 wt%) solution 10
4 parts by weight of Permec N as an organic peroxide and 5 parts by weight of PM as an acidic compound were added to 0 parts by weight to obtain a uniform solution (a). Separately, MMA / TMPT (90w
(t% / 10 wt%) solution, 3 parts by weight of PhBNa as an aryl borate compound was added to obtain a uniform solution (b).
After mixing the two solutions at a 1: 1 weight ratio until uniform, the curing time, curability and surface tackiness were evaluated. In addition, the obtained cured product was evaluated for initial coloring and discoloration resistance. The results are shown in Table 1.

[0178]

[Table 1]

Examples 2 to 24 MMA / TMPT (90
(wt% / 10 wt%) solution was prepared, cured by the same method as in Example 1, and each physical property was measured. The results are shown in Table 1.

In all of the examples, the curability and the surface tackiness were good, and further, the cured product did not have initial coloring and there was no or slight discoloration after storage.

Examples 25 to 29 MMA / TMPT (90
(wt% / 10 wt%) solution was prepared, cured by the same method as in Example 1, and each physical property was measured. The results are shown in Table 1.

In these examples, a decomposition accelerator for organic peroxide was added, but the curing activity was further increased. The curability and surface tackiness were also good, and the cured product had no initial coloring and no or little discoloration after storage.

Comparative Examples 1 to 4 MMA / TMPT (90
(wt% / 10 wt%) solution was prepared, cured by the same method as in Example 1, and each physical property was measured. The results are shown in Table 1.

Comparative Examples 1 to 3 are cases in which one of the essential components of the chemical polymerization catalyst of the present invention was not added, and Comparative Examples 1 and 2 did not cure at all. Further, in Comparative Example 3, although it was cured, it took not only a long time to cure, but also only partially gelled.

Comparative Example 4 shows the case where a conventional BPO / DMPT-based chemical polymerization catalyst was used. However, the cured product was more sticky than in the examples, and the cured product was also initially colored, and was further preserved. Later it changed color significantly.

Examples 30 to 35 Powder components and liquid components having the compositions shown in Table 2 were prepared. These are compositions of the dental restorative material of the present invention.
After kneading at 1, the curing time, the bending strength of the cured product, the Knoop hardness, the measurement of the residual monomer amount, and the discoloration resistance test of the cured product were performed. Table 3 shows the results.

[0187]

[Table 2]

[0188]

[Table 3]

Comparative Example 5 The physical properties were measured in the same manner as in Examples 31 to 36 except that the powder component and the liquid component were prepared according to the compositions shown in Table 2. Table 3 shows the results.

Comparative Example 5 used BPO / D as a chemical polymerization catalyst.
Although an example using EPT was shown, the amount of residual monomer was larger than that of the example, and the discoloration of the cured product was also large.

[Examples and Comparative Examples Regarding Amount of Dental Composite Restorative Material of the Present Invention] Examples 36 to 41 Two kinds of paste components having the compositions shown in Table 4 were prepared. These are compositions of the dental composite restorative material of the present invention. After kneading at a weight ratio of 1/1, measurement of curing time, bending strength of the cured product, Knoop hardness, and discoloration resistance test of the cured product were performed. Was. Table 5 shows the results.

[0192]

[Table 4]

[0193]

[Table 5]

Comparative Example 6 Physical properties were measured in the same manner as in Examples 29 to 32 except that two kinds of paste components were prepared with the compositions shown in Table 4. Table 5 shows the results.

Comparative Example 6 uses BPO / D as a chemical polymerization catalyst.
Although the example using EPT was shown, the discoloration of the cured product was large.

[Examples and Comparative Examples Regarding the Dental Adhesive (Bonding Material) for Direct Restoration of the Present Invention] Example 42 First Example consisting of 3 g of PM, 1.5 g of D2.6E, and 0.5 g of TMPT. Liquid composition A, 3.2 g HEM
A, 1.4 g MMA, 0.1 g perhexa H, 0.1 g
A second liquid composition a consisting of 3 g of PhBTEOA was separately prepared, and the first liquid and the second liquid were mixed at a ratio of 1: 1 just before use to prepare a bonding material. Using this bonding material, the adhesive strength was measured by a method using a photocurable composite resin. As a result, 13.1 (1.
8) MPa, adhesive strength of 12.0 (2.1) MPa [where () is standard deviation] to dentin was obtained.

Examples 43 to 64 Except that the bonding material was prepared so that the first liquid of each liquid composition shown in Table 6 and the second liquid of each liquid composition shown in Table 7 had the bonding material composition shown in Table 8. An adhesion test was performed in the same manner as in Example 42. Table 8 shows the results. The numbers in parentheses in the “first liquid composition” and “second liquid composition” columns in Table 8 represent parts by weight of each liquid.

[0198]

[Table 6]

[0199]

[Table 7]

[Table 8]

Examples 42 to 68 show examples in which a light-curable composite resin was used, but all showed high adhesive strength to enamel and dentin.
From this, it is clear that when the bonding material of the present invention is used as the adhesive between the composite resin and the tooth, no pretreatment and no light irradiation are required.

In Example 42, only the phosphoric acid group (phosphinico group or phosphono group) -containing polymerizable monomer was used as the acidic group-containing polymerizable monomer. When the monomer is used in combination with a carboxyl group-containing polymerizable monomer (Example 46 and the like), and when a polyvalent metal ion-eluting filler and / or water is further added (Example 43).
-45 etc.), and when both (Examples 47-49 etc.) were performed, the adhesive strength was higher than in Example 42.

Further, Examples 62 to 64 are examples in which an organic peroxide decomposition accelerator was added, but all of them exhibited further improved adhesive strength.

In Examples 65 to 68, the composition was a dual cure type by adding a dye and a photoacid generator, but the adhesive strength was further improved by light irradiation during curing of the composite resin. .

Comparative Examples 7 to 13 A bonding material was prepared in such a manner that the first liquid of each liquid composition shown in Table 6 and the second liquid of each liquid composition shown in Table 7 had the bonding material composition shown in Table 8. Was subjected to an adhesion test in the same manner as in Example 42. Table 8 shows the results.

In contrast to the above Examples, Comparative Examples 7 to 12 lacked at least one of the essential components of the present invention, and in each case, the adhesive strength of both enamel and dentin was significantly reduced. Further, Comparative Example 13 showed the result using an organic peroxide / tertiary amine polymerization catalyst, but did not adhere to both enamel and dentin.

Example 69 First liquid composition A consisting of 3 g of PM, 1.5 g of D2.6E, and 0.5 g of TMPT, and 3.2 g of HEM
A, 1.4 g MMA, 0.1 g perhexa H, 0.1 g
A second liquid composition a consisting of 3 g of PhBTEOA was separately prepared, and the first liquid and the second liquid were mixed at a ratio of 1: 1 just before use to prepare a bonding material. Using this bonding material, the adhesive strength was measured by the method using a chemically curable composite resin. As a result, 11.4 (1.
5) MPa, adhesive strength of 11.0 (1.7) MPa [where () is standard deviation] to dentin was obtained.

Examples 70 to 91 A bonding material was prepared by using a first liquid having each liquid composition shown in Table 6 and a second liquid having each liquid composition shown in Table 7 so as to have a bonding material composition shown in Table 9. Example 6 except that
An adhesion test was performed in the same manner as in No. 9. Table 9 shows the results.

[0208]

[Table 9]

Examples 69 to 91 are examples using the same adhesive composition as in Examples 42 to 64 and using a chemically curable composite resin, and all showed high adhesive strength to enamel and dentin. From this, it is clear that even when the bonding material of the present invention is used as an adhesive for a chemically curable composite resin, no pretreatment is required and light irradiation can be omitted.

Comparative Examples 14 to 17 In the same manner as in Example 69, except that the bonding material was prepared so as to have the bonding material composition shown in Table 9 using the first liquid shown in Table 6 and the second liquid shown in Table 7. An adhesion test was performed. Table 9 shows the results.

In contrast to the above Examples, Comparative Examples 14 to 16 lacked at least one of the essential components of the present invention, and in each case, the adhesive strength of both enamel and dentin was significantly reduced. Further, Comparative Example 17 shows that the organic peroxide /
The results showed that a tertiary amine-based polymerization catalyst was used, but no adhesion was observed to both enamel and dentin.

[Examples and Comparative Examples Related to the Indirect Restorative Dental Adhesive (Dental Cement) of the Present Invention] Example 92 9.5 g of P (MMA-EMA), 0.5 g of PEMA
And a powder composition A comprising 0.3 g of PhBTEOA;
5g PM, 0.5g MAC-10, 6.5g MM
A, a polymerizable monomer liquid composition a consisting of 2 g of HEMA, 0.5 g of bis-GMA, and 0.1 g of Parkmill H was separately prepared, and the polymerizable monomer composition liquid and the powder composition were prepared immediately before use. And the mixture at a ratio of 1: 1.4 to obtain a dental cement. The adhesive strength was measured with respect to the tooth surface which had been subjected to the surface treatment using the pretreatment material A in advance. As a result, 19.6 (3.3) MPa for enamel and 17.5 (4.
1) An adhesive strength of MPa (where () is a standard deviation) was obtained.

Examples 93 to 116 A dental cement was prepared by using a powder composition of each powder composition shown in Table 10 and a polymerizable monomer liquid of each liquid composition shown in Table 11 so as to have a cement composition shown in Table 12. Was prepared in the same manner as in Example 92, except that the tooth surface was previously treated with the tooth surface pretreatment material a. Table 12 shows the results.

[0214]

[Table 10]

[0215]

[Table 11]

[0216]

[Table 12]

All of Examples 92 to 116 showed high adhesive strength to enamel and dentin.

Comparative Example 18 A dental cement was prepared in such a manner that the powder composition of each powder composition shown in Table 10 and the polymerizable monomer liquid of each liquid composition shown in Table 11 had the cement composition shown in Table 12. In the same manner as in Example 92, an adhesion test was performed on the tooth surface previously treated with the tooth surface pretreatment material A. Table 12 shows the results.

Comparative Example 18 showed the results using an organic peroxide / tertiary amine polymerization catalyst. However, the adhesive strength of both enamel and dentin was significantly reduced as compared with the examples.

Examples 117 to 123 Dental cements were prepared from the powder compositions having the respective powder compositions shown in Table 10 and the polymerizable monomer solutions having the respective liquid compositions shown in Table 11 so as to have the cement compositions shown in Table 12. Then, the adhesion test was performed without performing the pretreatment of the tooth surface. Table 12 shows the results.
Examples 117 to 123 are compositions of resin-reinforced glass ionomers, and comparatively high adhesive strength was obtained for both enamel and dentin without any pretreatment of the tooth surface.

Comparative Example 19 A dental cement was prepared in such a manner that the powder composition of each powder composition shown in Table 10 and the polymerizable monomer liquid of each liquid composition shown in Table 11 had the cement composition shown in Table 12. Measured the adhesive strength in the same manner as in Examples 117 to 123. Table 12 shows the results.

In Comparative Example 19, the adhesive strength of both enamel and dentin was lower than that of Example.

Example 124 5 g of 3Si—Zr, 5 g of 0.3Si—Ti, 1.2
g of bis-GMA, 1.8 g of 3G and 0.1 g of PhBNa were kneaded in an agate mortar to obtain a uniform paste composition A. Similarly, 5 g of 3Si-Zr and 5 g of 0.3
Si-Ti, 1 g PM, 0.2 g MAC-10,
0.6 g NPG, 1.2 g D2.6E and 0.0
3 g of Park Mill H was kneaded to obtain a uniform paste composition a. Immediately before use, paste compositions A and a were
The mixture was kneaded at a weight ratio of 1 to obtain a dental adhesive composition. The adhesive strength was measured with respect to the tooth surface which had been subjected to the surface treatment using the pre-treated material B in advance. As a result, 21.4 was added to the enamel.
(3.2) MPa, 19.2 (2.5) MPa for dentin
[However, () is the standard deviation], and the adhesive strength was obtained.

Examples 125 to 137 The same procedures as in Example 124 were carried out except that a dental cement was prepared so that the paste having the paste composition shown in Table 13 and the paste having the paste composition shown in Table 14 had the cement composition shown in Table 15. Then, an adhesion test was performed on the tooth surface previously treated with the tooth surface pretreatment material B. Table 15 shows the results.

[0225]

[Table 13]

[0226]

[Table 14]

[0227]

[Table 15]

Each of Examples 124 to 137 showed high adhesive strength to enamel and dentin.

Comparative Example 20 A dental cement was prepared in the same manner as in Example 124 except that the paste having the paste composition shown in Table 13 and the paste having the paste composition shown in Table 14 were prepared to have the cement composition shown in Table 15. An adhesion test was performed on the tooth surface treated with the tooth surface pretreatment material (b). Table 15 shows the results.

Comparative Example 20 showed the results using an organic peroxide / tertiary amine-based polymerization catalyst, but the adhesive strength of both enamel and dentin was significantly reduced as compared with the examples.

Examples 138 to 142 A dental cement was prepared from the paste having the paste composition shown in Table 13 and the paste having the paste composition shown in Table 14 so as to have the cement composition shown in Table 15, and the tooth surface was pretreated. Without an adhesive test. Table 15 shows the results.
Examples 138 to 142 are compositions of a resin-reinforced glass ionomer composed of a paste / paste, and in each case, a relatively high adhesive strength was obtained for both enamel and dentin without pretreatment of the tooth surface.

Comparative Example 21 A dental cement was prepared in the same manner as in Examples 138 to 142 except that the paste having the paste composition shown in Table 13 and the paste having the paste composition shown in Table 14 were prepared to have the cement composition shown in Table 15. The adhesive strength was measured. Table 15 shows the results.

In Comparative Example 21, the adhesive strength of both enamel and dentin was lower than that of Example.

[Examples and Comparative Examples Related to the Dental Pretreatment Material of the Present Invention] Example 143 A composed of 2 g of PM and 0.1 g of Park Mill H
B consisting of a liquid, 0.3 g of PhBNa and 7.6 g of water
The liquids were mixed immediately before use to make a homogeneous solution. After the tooth surface treatment using this solution as a primer, the chemically polymerized adhesive A
Was used to perform the bonding operation, and the bonding strength was measured. As a result, 18.6 (3.2) MPa for enamel and 17.3 (2.5) MPa for dentin (where () indicates standard deviation).
Was obtained.

Examples 144 to 164 A chemical polymerization type adhesive was used in the same manner as in Example 143 except that primers were prepared with the compositions shown in Tables 16 and 17.
The adhesive strength to dentin and enamel was measured.
The results are shown in Tables 16 and 17.

[0236]

[Table 16]

[0237]

[Table 17]

EXAMPLES In all compositions, good adhesion to both enamel and dentin was obtained by using a pretreatment material containing a polymerizable monomer having an acidic group, an organic peroxide, water and an aryl borate compound. It is clear that the object of the present invention can be achieved.

Comparative Examples 22 to 27 Adhesion strength to dentin and enamel was measured using a chemically polymerizable adhesive in the same manner as in Example 143 except that primers having the compositions shown in Table 17 were prepared. The results are shown in Table 17.

In contrast to the above Examples, Comparative Examples 22 to 25 lack one component which is an essential component of the present invention, and it can be seen that the adhesive strength to dentin or enamel is reduced in any case. . Furthermore, in Comparative Examples 26 and 27, the composition ratio of each essential component was out of the range of the invention, and in each case, the adhesive strength to dentin or enamel was reduced.

Example 165 A solution consisting of 2.0 g of PM and 0.1 g of Parkmill H and B solution consisting of 0.3 g of PhBNa and 7.6 g of water were mixed immediately before use to obtain a uniform solution. And After performing tooth surface treatment using this solution as a primer, an adhesive operation was performed using an adhesive E, which is a photopolymerizable adhesive, and a composite resin was further charged to measure adhesive strength. As a result, 19.3 (2.9) MPa for dentin and 19.6 (2.2) MPa for enamel (where () is the standard deviation).
Was obtained.

Examples 166 to 181 The adhesive strength to dentin and enamel was measured using a photopolymerizable adhesive in the same manner as in Example 166 except that the primers were prepared according to the compositions shown in Tables 18 and 19. The results are shown in Tables 18 and 19.

[0243]

[Table 18]

[0244]

[Table 19]

In all the compositions, good adhesion to both enamel and dentin was obtained by the pretreatment material containing the acidic group-containing polymerizable monomer, the organic peroxide, water and the aryl borate compound. It is clear that the object of the present invention can be achieved.

Comparative Examples 28 to 33 Using a photopolymerizable adhesive in the same manner as in Example 166 except that primers having the compositions shown in Table 19 were used, the adhesive strength to dentin and enamel was measured. The results are shown in Table 19.

In contrast to the above Examples, Comparative Examples 28 to 31 lack one component which is an essential component of the present invention, and it can be seen that the adhesive strength to dentin or enamel is reduced in any case. . Furthermore, in Comparative Examples 32 and 33, the composition ratio of each essential component was out of the range of the invention, and in each case, the adhesive strength to dentin or enamel was reduced.

[0248]

The dental chemical polymerization catalyst of the present invention does not cause coloring or discoloration of the cured product, has high polymerization activity even in the presence of oxygen and acidic compounds, is easy to handle, and has an appropriate operation allowance time. Can be secured.

Further, the adhesive material for direct dental restoration (bonding material) of the present invention does not require the pretreatment which has been conventionally performed when bonding dental material with a dental restoration material represented by a composite resin. , High adhesive strength to both dentin and enamel. In addition, the application does not particularly require a light irradiation operation, and exhibits high adhesiveness to not only a photopolymerization type but also a chemical polymerization type dental restorative material.

Further, the dental adhesive for indirect restoration (dental cement) of the present invention can obtain higher adhesive strength to both dentin and enamel as compared with conventional adhesive dental cement.

Further, the composite restoration material for dental use of the present invention has high strength without coloring or discoloration, and can perform restoration with high aesthetics and reliability.

In addition, the dental pretreatment material of the present invention can be used in a single pretreatment for both light and chemically polymerizable adhesives, compared to a conventional dental pretreatment material, in enamel and ivory. High adhesive strength can be given to the quality.

Continued on the front page F-term (reference) 4C089 AA10 AA12 BA19 BC06 4J011 PA05 PA13 PA15 PA16 PA64 PA65 PA66 PA70 PA89 PA96 PA98 PB06 PB14 PB16 PB22 PC02 QA03 QA06 QA09 QA11 QA15 SA00 UA01 UA06 VA01 WA05 CA08 CA07

Claims (9)

[Claims] An aryl borate compound, an acidic compound,
And a chemical polymerization catalyst for dental use, comprising an organic peroxide and substantially free of an amine compound as a catalyst component. 2. The dental chemical polymerization catalyst according to claim 1, further comprising a metal compound that promotes decomposition of an organic peroxide. 3. The dental chemical polymerization catalyst according to claim 1, which contains an acidic group-containing polymerizable monomer as the acidic compound. 4. A dental curable composition comprising a polymerizable monomer and the dental chemical polymerization catalyst according to any one of claims 1 to 3. 5. The dental curable composition according to claim 4, further comprising a photopolymerization initiator. 6. 100 parts by weight of a polymerizable monomer containing a polymerizable monomer having an acidic group, and an aryl borate compound of 0.1 part by weight.
The composition according to claim 4, comprising 0.01 to 10 parts by weight, 0.01 to 10 parts by weight of an organic peroxide, 1 to 20 parts by weight of a polyvalent metal ion-eluting filler and / or 2 to 30 parts by weight of water. An adhesive for direct dental restoration, comprising a dental curable composition. 7. 100 parts by weight of a polymerizable monomer containing a polymerizable monomer having an acidic group, and an aryl borate compound of 0.1 part by weight.
The dental curable composition according to claim 4 or 5, comprising 0.01 to 10 parts by weight, 0.01 to 10 parts by weight of an organic peroxide, and 50 to 900 parts by weight of a filler. Adhesive for indirect dental restoration. 8. The dental curable composition according to claim 4, further comprising 50 to 900 parts by weight of a filler based on 100 parts by weight of the total polymerizable monomer. Dental composite restoration. 9. A pre-dental composition comprising the dental curable composition according to claim 4, which contains an acidic group-containing polymerizable monomer, an aryl borate compound, an organic peroxide, and water. Processing materials.