JP4481034B2 - Adhesive composition and adhesive kit - Google Patents

Description

  The present invention relates to an adhesive material in the field of dentistry. More specifically, the present invention relates to a dental adhesive composition for bonding a dental restoration made of a metal, an organic polymer, ceramics, or a composite material thereof to a tooth.

  To repair dental caries damaged by caries, especially for caries with relatively small cavities in the first and mid-term, it is usually called a photo-curable composite resin because of its aesthetics, simplicity of operation and quickness. A direct filling method using a filling restoration material is common.

  On the other hand, for relatively large caries, an indirect restoration method in which a dental restoration material such as an inlay or a crown prepared in advance outside the oral cavity using a metal, a ceramic material or the like is adhered to a tooth is common.

  However, since restoration materials such as composite resins, metals, and ceramic materials do not have adhesiveness to the tooth, an adhesive is usually used. In general, such adhesives are treated with a pretreatment material to further increase the adhesive strength with the tooth, and then in the case of the direct restoration method, a photo-curing adhesive material, indirect restoration. In the case of the method, a chemical curing type that cures even in a dark place or a dual cure type adhesive having both a chemical curing function and a light curing function is used.

  When applying to a dark place where light cannot reach, it is very important that sufficient curability and adhesive strength can be obtained without light irradiation. Various chemical polymerization-type polymerization initiators have been proposed so far in order to influence the force, but it is required to obtain higher adhesiveness in response to demands for further certainty and reliability. Yes.

  In order to satisfy the above-mentioned requirements, the present inventors in the chemical polymerization type adhesive material have an acidic group-containing radical polymerizable monomer, an aryl borate compound, a + IV and / or + V vanadium compound, and, if necessary, an organic material. It has been found that a composition containing a peroxide exhibits high adhesiveness. (For example, refer to Patent Documents 1 and 2).

  On the other hand, one of the important requirements for chemical polymerization type adhesives is operability, particularly the pot life. Usually, the chemical polymerization type adhesive is divided and stored in two or more, and mixed and used immediately before use. By mixing, the polymerization initiator that has been divided reacts to initiate polymerization, and cures through gelation. Before this gelation begins, the operator applies the adhesive to the restoration material. However, the repair material must be set in the cavity of the oral cavity. That is, the pot life is from the mixing of the adhesive to the start of gelation. If the pot life is too short, the adhesive will harden before being set in the oral cavity, making it impossible to set or causing poor adhesion. On the other hand, if the time until curing is too long, the burden on the patient increases and the practicality for dental use is significantly reduced. Therefore, the chemical use adhesive for dental use is required to have a pot life of at least 150 seconds or more, preferably about 180 to 300 seconds.

  On the other hand, dental materials are not limited to adhesive compositions, and the necessity of their use depends on the patient's visit and the case, so it is difficult to systematically manufacture, purchase or use. It is also necessary to keep it at hand. For this reason, it is not uncommon for it to take a long time from its production or purchase until the entire amount is used up, and generally storage stability of about 2 to 3 years is required even in storage in a refrigerator.

JP 2003-96122 A International Publication No. 03/27153 Pamphlet

  However, in further studies by the present inventors, the composition containing the acidic group-containing radical polymerizable monomer, the aryl borate compound and the + IV and / or + V vanadium compound has high polymerizability. However, it has been found that due to its polymerizability, gelation is fast and the pot life is not so long. The present inventors have further investigated this point, and by examining the kind and amount of the acidic group-containing radically polymerizable monomer, it becomes a composition having high adhesiveness and good pot life. I found it. However, it has been newly found that the above composition having a good pot life has a problem of poor storage stability and discoloration or curing during storage.

  Accordingly, an object of the present invention is to provide a chemical polymerization type adhesive having high adhesiveness, which has a good pot life and excellent storage stability.

  The present inventors have intensively studied to achieve the above object. As a result, it was found that the use of an acidic phosphate-based compound as an acidic group-containing radical polymerizable monomer improved the storage stability, and various studies were made on the pot life when the compound was used. Proceeded. As a result, the inventors have found that an appropriate pot life can be obtained by further blending a specific amount of an amine compound, thereby completing the present invention.

That is, the present invention comprises (A) a package comprising a composition A in which a radical polymerizable monomer having no acidic group, an aryl borate compound and an organic peroxide are blended, and (B) a phosphate group-containing radical polymerization. The composition A and the composition B are stored separately in a package composed of the composition B containing the functional monomer, the + IV and / or + V vanadium compound, and the aliphatic tertiary amine. The amount of the + IV and / or + V vanadium compound in the composition B is v mol, and the amount of the phosphate group-containing radical polymerizable monomer is p. When the mole and the amount of the aliphatic tertiary amine are n moles, these three components are represented by the following formula:
{(P−n) / v} ≦ 3000 <{p / v}
It is the dental adhesive composition characterized by being mix | blended in the ratio which satisfy | fills.

  Still another invention is a pretreatment material comprising the dental adhesive composition, an acidic group-containing radical polymerizable monomer, water, a + IV and / or + V vanadium compound, and an aliphatic tertiary amine. A dental adhesive kit comprising:

  The dental adhesive composition of the present invention not only gives high adhesive strength as a chemical polymerization type adhesive, but also has excellent operability to give an appropriate pot life, and also has excellent storage stability. Become.

  The dental adhesive composition of the present invention comprises (A) a package comprising a composition A in which a radical polymerizable monomer having no acidic group, an aryl borate compound and an organic peroxide are blended, and (B) It is divided and stored in a package composed of a composition B containing a phosphate group-containing radical polymerizable monomer, a + IV and / or + V vanadium compound, and an aliphatic tertiary amine. The composition A and the composition B are mixed and used.

  Since the aryl borate compound blended in the composition A starts to decompose and polymerize with an acid, the radical polymerizable monomer blended in the composition A must have no acidic group.

  The radically polymerizable monomer having no acidic group (hereinafter sometimes referred to as a non-acidic monomer) does not have an acidic group, and is a (meth) acryloyl group and a (meth) acryloyloxy group, (meta ) A derivative group of a (meth) acryloyl group such as an acryloylamino group or a (meth) acryloylthio group; a vinyl group; an allyl group; a radically polymerizable unsaturated group such as a styryl group, and the like. However, a compound having a (meth) acryloyl group derivative group is preferred from the viewpoint of good polymerizability, and excellent adhesion and handling.

  Specific examples of such non-acidic monomers include methyl (meth) acrylate, ethyl (meth) acrylate, isopropyl (meth) acrylate, butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, and glycidyl (meth) acrylate. , One polymerizable unsaturated group such as benzyl (meth) acrylate, allyl (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, 2- (meth) acryloxyethyl propionate, 2-methacryloxyethyl acetoacetate Water-insoluble (meth) acrylate monomers {hereinafter referred to as water-insoluble monofunctional non-acidic monomers}; 2-hydroxyethyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, glyceryl mono (meth) Acrylate, polyethylene Water-soluble (meth) acrylate monomers such as glycol mono (meth) acrylate {hereinafter referred to as water-soluble monofunctional non-acidic monomers}; ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, triethylene glycol Di (meth) acrylate, butylene glycol di (meth) acrylate, nonaethylene glycol di (meth) acrylate, propylene glycol di (meth) acrylate, dipropylene glycol di (meth) acrylate, neopentyl glycol di (meth) acrylate, 1 , 3-butanediol di (meth) acrylate, 1,4-butanediol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, 1,9-nonanediol di (meth) acrylate, trimethyl Polymerizable propane tri (meth) acrylate, neopentyl glycol di (meth) acrylate, pentaerythritol tri (meth) acrylate, trimethylolmethane tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, urethane (meth) acrylate, etc. Aliphatic (meth) acrylate monomers having a plurality of saturated groups; 2,2-bis ((meth) acryloxyphenyl) propane, 2,2-bis [4- (2-hydroxy-3- (meth) ) Acryloxyphenyl)] propane, 2,2-bis (4- (meth) acryloxyethoxyphenyl) propane, 2,2-bis (4- (meth) acryloxydiethoxyphenyl) propane, 2,2-bis Polymerization of (4- (meth) acryloxypropoxyphenyl) propane and the like As polymerizable unsaturated groups such as aromatic (meth) acrylate monomers having a plurality of polymerizable unsaturated groups {hereinafter referred to as polyfunctional non-acidic monomers together with both aliphatic and aromatic groups} Examples thereof include monomers having a (meth) acrylamide group as polymerizable unsaturated groups such as a monomer having a (meth) acryloxy group, diacetone acrylamide, and N-methylol (meth) acrylamide. These radically polymerizable monomers can be used alone or in admixture of two or more.

  In consideration of initial adhesive strength and adhesion durability, it is preferable to use a combination of a water-soluble monofunctional non-acidic monomer or a polyfunctional non-acidic monomer. In addition, for the purpose of improving adhesion to dental precious metals, a precious metal adhesive monomer described in JP-A-10-1409, JP-A-10-1473, JP-A-8-113763, or the like is blended. Is also preferable.

  The aryl borate compound used in the adhesive of the present invention is not particularly limited as long as it is a tetracoordinate boron compound having at least one boron-aryl bond in the molecule, and a known compound can be used. On the other hand, a borate compound having no boron-aryl bond is extremely poor in stability and is practically impossible to use because it reacts and decomposes easily with oxygen in the air. In order to obtain better storage stability, a compound having 3 to 4 boron-aryl bonds is preferable, and a tetraarylborate compound in which all are boron-aryl bonds is particularly preferable.

  The aryl borate compound used in the present invention is represented by the following general formula (1) from the viewpoint of storage stability and polymerization activity.

(In the above formula, R ₁ and R ₂ are the same or different aryl groups, R ₃ is an alkyl group, an aryl group or an alkenyl group, and all of R _{1 to} R ₃ have a substituent. R ₄ and R ₅ are each independently a hydrogen atom, a halogen atom, a nitro group, an alkyl group or an alkoxy group which may have a substituent, or a phenyl group which may have a substituent. L ⁺ represents a metal cation, a tertiary or quaternary ammonium ion, a quaternary pyridinium ion, a quaternary quinolinium ion or a quaternary phosphonium ion.
The borate compound shown by these is preferable.

In the general formula (1), R ₁ and R ₂ are the same or different aryl groups, and these groups may have a substituent. The aryl group is not particularly limited and may be a known aryl group, but is preferably a substituted or unsubstituted aryl group in which a single ring or two or three rings are condensed. Specifically, a phenyl group, a naphthyl group, an anthranyl group, etc. are illustrated. In addition, examples of the substituent substituted on the aryl group include a halogen atom such as a fluorine atom, a chlorine atom and a bromine atom, an alkyl group having 1 to 5 carbon atoms such as a methyl group, an ethyl group and a butyl group, or a phenyl group, C6-C10 aryl group such as nitrophenyl group and chlorophenyl group, C1-C5 alkoxy group such as methoxy group, ethoxy group and propyl group, C2-C5 acyl group such as acetyl group, hydroxyl group , A nitro group, a cyano group and the like. The number and position of the substituents are not particularly limited.

  Specific examples of the substituted or unsubstituted aryl group include phenyl group, 1- or 2-naphthyl group, 1-, 2- or 9-anthryl group, 1-, 2-, 3-, 4- or 9 -Phenanthryl group, p-fluorophenyl group, p-chlorophenyl group, (3,5-bistrifluoromethyl) phenyl group, 3,5-bis (1,1,1,3,3,3-hexafluoro-2- Methoxy-2-propyl) phenyl group, p-nitrophenyl group, m-nitrophenyl group, p-butylphenyl group, m-butylphenyl group, p-butyloxyphenyl group, m-butyloxyphenyl group, p-octyl Examples thereof include an oxyphenyl group and an m-octyloxyphenyl group.

In the general formula (1), R ₃ represents an alkyl group, an aryl group, or an alkenyl group, and these groups may have a substituent.

The alkyl group is not particularly limited and may be linear or branched, but is preferably an alkyl group having 3 to 30 carbon atoms, more preferably a linear alkyl group having 4 to 20 carbon atoms, Specific examples include an n-butyl group, an n-octyl group, an n-dodecyl group, and an n-hexadecyl group. In addition, the substituent of the alkyl group is the same as those exemplified as the substituent of the aryl group represented by R ₁ and R ₂ (excluding the alkyl group).

  The alkenyl group is not particularly limited, but is preferably an alkenyl group having 4 to 20 carbon atoms, and examples of the substituent include those exemplified as the substituent of the alkyl group.

In the general formula (1), R ₄ and R ₅ may each independently have a hydrogen atom, a halogen atom, a nitro group, an alkyl group or an alkoxy group which may have a substituent, or a substituent. Good phenyl group.

  The alkyl group or alkoxy group which may have the substituent is not particularly limited, and may be linear or branched, but is preferably an alkyl group or alkoxy group having 1 to 10 carbon atoms. Yes, examples of the substituent include those exemplified as the substituent of the aryl group. Specific examples of the alkyl group which may have the substituent include methyl group, ethyl group, n- or i-propyl group, n-, i- or t-butyl group, chloromethyl group, trifluoro group. Examples include a methyl group, a methoxymethyl group, a 1,1,1,3,3,3-hexafluoro-2-methoxy-2-propyl group, and the like, specifically an alkoxy group that may have a substituent. Illustrative examples include methoxy, ethoxy, 1- or 2-propoxy, 1- or 2-butoxy, 1-, 2- or 3-octyloxy, chloromethoxy and the like.

Moreover, the substituent which the phenyl group which may have a substituent is not specifically limited, Specifically, what was illustrated as a substituent of the aryl group shown by said R < ₁ > and R < ₂ > is mentioned.

In the general formula (1), L ⁺ represents a metal cation, a tertiary or quaternary ammonium ion, a quaternary pyridinium ion, a quaternary quinolinium ion, or a quaternary phosphonium ion.

  Examples of the metal cation include alkali metal cations such as sodium ion, lithium ion, and potassium ion, and alkaline earth metal cations such as magnesium ion. Preferred metal cations include tertiary or quaternary ammonium. Examples of ions include tetrabutylammonium ion, tetramethylammonium ion, tetraethylammonium ion, tributylammonium ion, triethanolammonium ion, etc., and quaternary pyridinium ions include methylquinolinium ion, ethylquinolinium ion, and butyl. Examples of quaternary phosphonium ions such as quinolium ions include tetrabutylphosphonium ions and methyltriphenylphosphonium ions.

When the aryl borate compound represented by the above formula (1) is specifically exemplified, as a compound in which R ₃ is an alkyl group, monoalkyltriphenylboron, monoalkyltris (p-chlorophenyl) boron, monoalkyltris (p-fluoro) Phenyl) boron, monoalkyltris (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, mono Alkyltris (m-butyloxyphenyl) boron, monoalkyltris (p-octyloxyphenyl) boron, monoalkyltris (m-octyloxyphenyl) boron (wherein alkyl is n-butyl, n- Octyl or n-dodecyl), sodium salt, lithium salt, potassium salt, magnesium salt, tetrabutylammonium salt, tetramethylammonium salt, tetraethylammonium salt, tributylamine salt, triethanolamine salt, methylpyridinium Examples thereof include salts, ethylpyridinium salts, butylpyridinium salts, methylquinolinium salts, ethylquinolinium salts, and butylquinolinium salts.

Further, as borate compounds in which R ₃ is an aryl group, 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 (wherein alkyl represents any of n-butyl, n-octyl and n-dodecyl in any compound), sodium salt, lithium salt, potassium salt, magnesium salt, tetrabutylammonium salt, tetramethylammonium salt Salt, tetraethylammonium salt, tributylamine salt, triethanolamine salt, methylpyridinium salt, ethylpyridinium salt, butylpyridinium salt, methylquinolinium salt, ethylquinolinium salt or butylquinolinium salt .

Among these, R ₁ , R ₂ , R ₃ and particularly preferably from the viewpoint of storage stability, handling, synthesis, and availability.

Are aryl borate compounds in which all the groups represented by are the same, that is, the boron atom is substituted with four identical aryl groups.

Further, as L ⁺ , a tertiary or quaternary ammonium ion is preferable, and a tertiary ammonium ion is more preferable.

  These aryl borate compounds can be used alone or in combination.

  The organic peroxide blended in the composition A is not particularly limited, and any known one can be used without any limitation. As typical organic peroxides, organic peroxides classified into known ketone peroxides, peroxyketals, hydroperoxides, diaryl peroxides, peroxyesters, diacyl peroxides, and peroxydicarbonates are preferable. .

  More specifically, examples of ketone peroxides include methyl ethyl ketone peroxide, cyclohexanoperoxide, methylcyclohexanone peroxide, methyl acetoacetate peroxide, and acetylacetone peroxide. Peroxyketals include 1,1-bis (t-hexylperoxy) 3,3,5-trimethylcyclohexane, 1,1-bis (t-hexylperoxy) cyclohexane, 1,1-bis (t- Butylperoxy) 3,3,5-trimethylcyclohexanone, 1,1-bis (t-butylperoxy) cyclohexane, 1,1-bis (t-butylperoxy) cyclodecane, 2,2-bis (t-butyl Peroxy) butane, n-butyl 4,4-bis (t-butylperoxy) valerate, 2,2-bis (4,4-di-t-butylperoxycyclohexyl) propane and the like. Hydroperoxides include P-methane hydroperoxide, diisopropylbenzene peroxide, 1,1,3,3-tetramethylbutyl hydroperoxide, cumene hydroperoxide, t-hexyl hydroperoxide, and t-butyl hydro A peroxide etc. are mentioned. Dialkyl peroxides include α, α-bis (t-butylperoxy) diisopropylbenzene, dicumyl peroxide, 2,5-dimethyl-2,5-bis (t-butylperoxy) hexane, and t-butylcumi. Examples include ruperoxide, di-t-butyl peroxide, 2,5-dimethyl-2,5-bis (t-butylperoxy) hexane-3, and the like. Diacyl peroxides include isobutyryl peroxide, 2,4-dichlorobenzoyl peroxide, 3,5,5-trimethylhexanoyl peroxide, octanoyl peroxide, lauroyl peroxide, stearyl peroxide, succinic acid peroxide. Examples thereof include oxides, m-toluoyl benzoyl peroxide, and benzoyl peroxides. Peroxycarbonates include di-n-propyl peroxydicarbonate, diisopropyl peroxydicarbonate, bis (4-t-butylcyclohexyl) peroxydicarbonate, di-2-ethoxyethyl peroxydicarbonate, di- Examples include 2-ethylhexyl peroxydicarbonate, di-2-methoxybutyl peroxydicarbonate, di (3-methyl-3-methoxybutyl) peroxydicarbonate, and the like.

  Peroxyesters include α, α-bis (neodecanoylperoxy) diisopropylbenzene, cumylperoxyneodecanoate, 1,1,3,3-tetramethylbutylperoxyneodecanoate, 1- Cyclohexyl-1-methylethylperoxyneodecanoate, t-hexylperoxyneodecanoate, t-butylperoxyneodecanoate, t-hexylperoxypivalate, t-butylperoxypivalate, , 1,3,3-Tetramethylbutylperoxy-2-ethylhexanoate, 2,5-dimethyl-2,5-bis (2-ethylhexanoylperoxy) hexane, 1-cyclohexyl-1-methylethyl Peroxy-2-ethylhexanoate, t-hexylperoxy-2-ethylhexanoate , T-butylperoxy-2-ethylhexanoate, t-butylperoxyisobutyrate, t-hexylperoxyisopropyl monocarbonate, t-butylperoxymaleic acid, t-butylperoxy-3.5 , 5-trimethylhexanoate, t-butylperoxylaurate, 2,5-dimethyl-2,5-bis (m-toluoylperoxy) hexane, t-butylperoxyisopropyl monocarbonate, t-butylper Oxy-2-ethylhexyl monocarbonate, t-hexylperoxybenzoate, 2,5-dimethyl-2,5bis (benzoylperoxy) hexane, t-butylperoxyacetate, t-butylperoxy-m-toluoylbenzoate , T-butylperoxybenzoate, bis ( - butylperoxy) isophthalate.

  Further, t-butyltrimethylsilyl peroxide, 3,3 ', 4,4'-tetra (t-butylperoxycarbonyl) benzophenone, and the like can be used as suitable organic peroxides.

  The organic peroxide to be used may be appropriately selected and used depending on the structure and amount of the radically polymerizable monomer and aryl borate compound used in combination, and may be used alone or in combination of two or more. Of these, hydroperoxides, ketone peroxides, peroxyesters and diacyl peroxides are particularly preferred from the viewpoint of polymerization activity. Furthermore, among these, it is preferable to use an organic peroxide having a 10-hour half-life temperature of 60 ° C. or higher from the viewpoint of storage stability when a curable composition is used.

  Composition A in which the non-acidic monomer, aryl borate compound and organic peroxide are blended is a phosphate group-containing radical polymerizable monomer, a + IV and / or + V vanadium compound, and an aliphatic tertiary. It is used by mixing with Composition B containing amine.

  In the composition B, a phosphate group-containing radical polymerizable monomer (hereinafter sometimes referred to as a phosphate monomer) is essential. The reason is not clear, but if the phosphate monomer is not blended in a specific range, good storage stability cannot be obtained even if other acidic group-containing polymerizable monomers are blended, When stored for a long period of time, the color changes or the composition A hardens during storage.

  As the phosphoric acid monomer, any compound known as a dental compound can be employed as long as it is an acidic ester of phosphoric acid (including polyphosphoric acids) and has a polymerizable unsaturated group. However, a compound having a (meth) acrylic radically polymerizable unsaturated group is preferred in that it has good polymerizability and can easily obtain high tooth adhesion.

  Specific examples of such phosphoric acid monomers include 2-methacryloyloxyethyl dihydrogen phosphate, 6-methacryloyloxyhexyl dihydrogen phosphate, 10-methacryloyloxydecyl dihydrogen phosphate, 1- Monoester compounds of phosphoric acid such as methacryloxymethyl-2-methacryloxyethyl dihydrogen phosphate, esters of bisphenol A diglycidyl methacrylate and phosphoric acid, 2-methacryloylaminoethyl dihydrogen phosphate; bis (2 -(Meth) acryloyloxyethyl) hydrogen phosphate, bis (6- (meth) acryloyloxyhexyl) hydrogen phosphate, bis (10- (meth) a Liloyloxydecyl) Hydrogen phosphate, 2- (meth) acryloyloxyethyl phenyl hydrogen phosphate, 2- (meth) acryloyloxyethyl naphthyl hydrogen phosphate, 2- (meth) acryloyloxyethyl 2-bromoethyl hydro Examples of the phosphoric acid diester compounds such as jenphosphate and bis (2-methacryloylaminoethyl) hydrogenphosphate, and acrylic compounds corresponding to these methacrylic compounds. In the present invention, these phosphate group-containing radical polymerizable monomers may be used in combination.

  The vanadium compound used in the adhesive composition of the present invention is a + IV and / or + V vanadium compound. By adding + IV and / or + V vanadium compounds, quaternary radical polymerization initiators are formed with acidic compounds such as phosphate group-containing radical polymerizable monomers, aryl borate compounds and organic peroxides. In addition, the adhesiveness can be made extremely good. The vanadium compound has an oxidation number ranging from −I to + V, but the vanadium compound used in the present invention has a + IV or + V valence. From -I value to + I value, the stability of the compound is poor, and when + II value and + III value, the activity is low, and sufficient adhesive strength and cured product strength cannot be obtained. As the + IV or + V vanadium compound, a known compound can be used without limitation. Specific examples include divanadium tetroxide (IV), vanadium acetylacetonate (IV), vanadyl oxalate (IV), vanadyl sulfate (IV), oxobis (1-phenyl-1,3-butanedionate) Examples thereof include vanadium compounds such as vanadium (IV), bis (maltolate) oxovanadium (IV), vanadium pentoxide (V), sodium metavanadate (V), and ammonium metavanadate (V). These + IV or + V valent vanadium compounds may be used in combination of a plurality of types.

  In the following, for the sake of simplicity, unless otherwise specified, when simply referred to as a vanadium compound, it indicates a + IV or + V valent vanadium compound.

  The aliphatic tertiary amine is a tertiary amine in which an aromatic group is not directly bonded to a nitrogen atom. In other words, it is a compound in which all three organic groups bonded to the nitrogen atom are substituted or unsubstituted aliphatic groups. Examples of the aliphatic group include a methyl group, an ethyl group, and a propyl group. Examples of the group substituted on the aliphatic group include a halogen atom such as a fluorine atom and a chlorine atom; a hydroxyl group; (meth) acryloyl An acyloxy group such as an oxy group; and an aromatic group such as a phenyl group.

  Specific examples of such aliphatic tertiary amines include trimethylamine, triethylamine, tri-n-propylamine, triisopropylamine, tributylamine, N-methyl-diethylamine, N-ethyl-dimethylamine, triethanolamine. N, N-dimethylaminoethyl methacrylate and the like.

  Among these, N, N are incorporated in the cured product by having a polymerizable group, so that the possibility of elution after curing is low, and the reason is not clear, but problems such as discoloration and curing are less likely to occur during long-term storage. -It is particularly preferable to use a tertiary amine having a polymerizable group represented by dimethylaminoethyl methacrylate.

  On the other hand, when the compound is an aromatic tertiary amine, that is, a compound in which at least one of organic groups directly bonded to the nitrogen atom is an aromatic group, the effect of the present invention cannot be obtained.

In the present invention, the three components of the phosphoric acid monomer, vanadium compound, and aliphatic tertiary amine, which are blended in the composition B, are added in pmoles of the phosphate group-containing radical polymerizable monomer. When the amount of the vanadium compound is v mol and the amount of the aliphatic tertiary amine is n mol,
{(P−n) / v} ≦ 3000 <{p / v}
It is essential that it is blended in a ratio that satisfies the above.
When (p−n) / v exceeds 3000, sufficient pot life cannot be obtained, and the resin is cured before the bonding operation is completed. On the other hand, when p / v is smaller than 3000, the storage stability is lowered, for example, the composition B is cured during storage.

  In the composition B, the non-acidic monomer described as a component of the composition A may be blended. However, arylborate compounds are decomposed by acidic group-containing polymerizable monomers such as phosphate monomers and vanadium compounds, and organic peroxides are decomposed by aliphatic tertiary amine compounds and vanadium compounds. These components need to be distributed to the composition A or the composition B as described above.

  The adhesive composition of the present invention is used by mixing the above-described composition A and composition B immediately before use. That is, it is used as a composition containing a non-acidic monomer, an aryl borate compound, an organic peroxide, a phosphoric acid monomer, a vanadium compound, and an aliphatic tertiary amine immediately before use. The ratio of each compound in the composition after mixing is non-acidic in a total of 100 parts by mass of all radical polymerizable monomers (non-acidic monomer, phosphoric acid monomer and other polymerizable monomer described later). The monomer is 50 to 97 parts by mass, the phosphoric acid monomer is 3 to 50 parts by mass (more preferably 5 to 40 parts by mass), and aryl borate with respect to a total of 100 parts by mass of all radical polymerizable monomers. The compound is 0.01 to 10 parts by mass (more preferably 0.1 to 8 parts by mass), the organic peroxide is 0.01 to 10 parts by mass (more preferably 0.1 to 8 parts by mass), and the vanadium compound is 0.0001 to 10 parts by mass (more preferably 0.001 to 8 parts by mass) and an amount in a range satisfying the above formula with respect to the phosphoric acid monomer in which the aliphatic tertiary amine is blended. preferable.

  In addition to the non-acidic monomer, aryl borate compound, organic peroxide, phosphate monomer, vanadium compound, and aliphatic tertiary amine, the adhesive composition of the present invention has the effects of the present invention. Other components may be blended as necessary as long as they are not impaired.

  Examples of the optional component include acidic group-containing polymerizable monomers other than phosphoric monomers such as carboxylic acid group-containing polymerizable monomers and sulfonic acid group-containing polymerizable monomers, and organic fillers and inorganic fillers. Examples include fillers (fillers), polymerization initiators such as photopolymerization initiators, antibacterial agents, colorants such as dyes and pigments, ultraviolet absorbers, polymer thickeners, polymerization inhibitors, and polymerization inhibitors. . These may be added to either one or both of the composition A and the composition B in the present invention in consideration of the storage stability of the composition.

  Phosphoric acids such as the above carboxylic acid group-containing polymerizable monomers (hereinafter sometimes referred to as carboxylic acid monomers) and sulfonic acid group-containing polymerizable monomers (hereinafter sometimes referred to as sulfonic acid monomers) Acidic group-containing polymerizable monomers other than the system monomers (hereinafter sometimes collectively referred to as acidic monomers) can be blended in the composition B. By blending these acidic group-containing polymerizable monomers, it is possible to improve adhesiveness and curability.

  Specific examples of such carboxylic acid monomers include (meth) acrylic acid, N- (meth) acryloylglycine, N- (meth) acryloylaspartic acid, N- (meth) acryloyl-5-aminosalicylic acid, 2 -(Meth) acryloyloxyethyl hydrogen succinate, 2- (meth) acryloyloxyethyl hydrogen phthalate, 2- (meth) acryloyloxyethyl hydrogen maleate, 6- (meth) acryloyloxyethyl naphthalene-1,2, 6-tricarboxylic acid, O- (meth) acryloyl tyrosine, N- (meth) acryloyl tyrosine, N- (meth) acryloylphenylalanine, N- (meth) acryloyl-p-aminobenzoic acid, N- (meth) acryloyl-o -Aminobenzoic acid, p-bi Benzoic acid, 2- (meth) acryloyloxybenzoic acid, 3- (meth) acryloyloxybenzoic acid, 4- (meth) acryloyloxybenzoic acid, N- (meth) acryloyl-5-aminosalicylic acid, N- (meta) ) Radical polymerizable monomers having one carboxyl group in the molecule such as acryloyl-4-aminosalicylic acid, and acid anhydrides and acid halides thereof; 11- (meth) acryloyloxyundecane-1,1- Dicarboxylic acid, 10- (meth) acryloyloxydecane-1,1-dicarboxylic acid, 12- (meth) acryloyloxidedecane-1,1-dicarboxylic acid, 6- (meth) acryloyloxyhexane-1,1-dicarboxylic acid 2- (meth) acryloyloxyethyl-3′-methacryloyloxy-2 ′-(3,4-dica Ruboxybenzoyloxy) propyl succinate, 1,4-bis (2- (meth) acryloyloxyethyl) pyromellitate, N, O-di (meth) acryloyltyrosine, 4- (2- (meth) acryloyloxyethyl) trimellitic anne Hydride, 4- (2- (meth) acryloyloxyethyl) trimellitate, 4- (meth) acryloyloxyethyl trimellitate, 4- (meth) acryloyloxybutyl trimellitate, 4- (meth) acryloyloxyhexyl trimellitate Tate, 4- (meth) acryloyloxydecyl trimellitate, 4-acryloyloxybutyl trimellitate, 6- (meth) acryloyloxyethylnaphthalene-1,2,6-tricarboxylic anhydride, 6- (meth) acryloyl Oxyethyl Naphthalene-2,3,6-tricarboxylic acid anhydride, 4- (meth) acryloyloxyethylcarbonylpropionoyl-1,8-naphthalic anhydride, 4- (meth) acryloyloxyethylnaphthalene-1,8-tricarboxylic acid Examples thereof include radical polymerizable monomers having a plurality of carboxyl groups or acid anhydride groups in the molecule such as acid anhydrides, and acid anhydrides and acid halides thereof.

  Specific examples of the sulfonic acid monomer include 2- (meth) acrylamide-2-methylpropanesulfonic acid, p-vinylbenzenesulfonic acid, vinylsulfonic acid and the like.

  Moreover, by mix | blending a filler, the viscosity and consistency of an adhesive composition can be adjusted, or the mechanical strength after hardening can be adjusted.

  Such fillers may be organic fillers or inorganic fillers. Examples of organic fillers include polymethyl (meth) acrylate and polyethyl (meth) acrylate, and examples of inorganic fillers include quartz, barium glass, and silica. , Silica-titania, silica-zirconia and the like. Further, as the inorganic filler, a polyvalent ion-eluting filler such as aluminosilicate glass can also be suitably used. These fillers, particularly inorganic fillers, are preferably used after surface treatment with a surface treatment agent such as a silane coupling agent.

  What is necessary is just to select the compounding quantity of this filler suitably according to the objective, Generally, preferably 50-1900 mass parts with respect to 100 mass parts of all the radically polymerizable monomers which comprise an adhesive composition, More preferably, it is 100-1200 mass parts.

  Moreover, a photocuring initiator can be mix | blended with the adhesive composition of this invention, and it can be set as a dual cure type adhesive composition. The photopolymerization initiator is not particularly limited, and known photopolymerization initiators of radical polymerizable monomers can be used.

  Examples of the photopolymerization initiator include diacetyl, acetylbenzoyl, benzyl, 2,3-pentadione, 2,3-octadione, 4,4′-dimethoxybenzyl, 4,4′-oxybenzyl, camphorquinone, 9,10- Α-diketones such as phenanthrenequinone and acenaphthenequinone, benzoin alkyl ethers such as benzoin methyl ether, benzoin ethyl ether, and benzoin propyl ether, 2,4-diethoxythioxanthone, 2-chlorothioxanthone, Thioxanthone derivatives such as methylthioxanthone, benzophenone derivatives such as benzophenone, p, p′-dimethylaminobenzophenone, p, p′-methoxybenzophenone, 2,4,6-trimethylbenzoyldiphenylphosphine oxide, bis (2,6- Methoxy) -2,4,4-trimethylpentyl phosphine oxide, bis (2,4,6-trimethylbenzoyl) such acylphosphine oxide derivatives such as phenylphosphine oxide are exemplified.

  Furthermore, a system comprising an aryl borate compound / dye / photoacid generator can also be suitably used. In this case, the aryl borate compound functions as both a component of the chemical polymerization initiator that works together with the acidic monomer, the vanadium compound, and the organic peroxide, and a component of the photopolymerization initiator.

  Among these photopolymerization initiators, an α-diketone photopolymerization catalyst, an acylphosphine oxide photopolymerization catalyst, and a photopolymerization catalyst comprising a combination of an aryl borate compound / dye / photoacid generator are particularly preferable. It is.

  The α-diketone is preferably camphorquinone or benzyl, and the acyl phosphine oxide is 2,4,6-trimethylbenzoyldiphenylphosphine oxide or bis (2,6-dimethoxybenzoyl) -2,4,4- Trimethylpentylphosphine oxide and bis (2,4,6-trimethylbenzoyl) phenylphosphine oxide are preferred. These α-diketone and acyl phosphine oxide alone exhibit photopolymerization activity, but it is preferable to use an amine compound in combination because higher activity can be obtained. Particularly in the case of α-diketone, it is better to use an amine compound in combination. The amine compound may be the aliphatic tertiary amine, but more preferably an aromatic tertiary amine. Specific examples of the aromatic tertiary amine include 4-dimethylaminobenzoic acid, ethyl 4-dimethylaminobenzoate, lauryl 4-dimethylaminobenzoate, and dimethylaminoacetophenone.

  As the aryl borate compound / dye / photoacid generator photopolymerization catalyst, those described in JP-A-9-3109 and the like are preferably used. More specifically, those using a coumarin dye as a dye and a halomethyl group-substituted s-triazine derivative or a diphenyliodonium salt compound as a photoacid generator can be used particularly preferably.

  The photopolymerization initiators as described above can be blended not only individually but also in combination of a plurality of types as necessary.

  The blending amount of the photopolymerization initiator is not particularly limited and may be appropriately determined according to the blending ratio of other components to be blended. In the case of α-diketone or acylphosphine oxide, these are adhesive properties. Preferably it is 0.01-20 mass parts with respect to 100 mass parts of all the radically polymerizable monomers which comprise a composition, More preferably, it is 0.1-10 mass parts, Furthermore, an amine compound is added as needed. What is necessary is just to add 0.01-20 mass parts. In the case of an aryl borate compound / dye / photoacid generator system, the dye may be 0.001 to 5 parts by mass and the photoacid generator may be 0.01 to 10 parts by mass. In this case, the compounding amount of the aryl borate compound may be in the above range.

  Moreover, the storage stability of an adhesive composition can be improved more by mix | blending a polymerization inhibitor. Specific examples of the polymerization inhibitor include hydroquinone, hydroquinone monomethyl ether, and 2,6-di-tert-isobutylphenol. The compounding quantity is generally about 0.00001 to 5 parts by mass, more preferably about 0.0001 to 1 part by mass in the adhesive composition.

  The method for producing an adhesive composition in the present invention is not particularly limited, and may be carried out according to a known method for producing an adhesive composition containing a radical polymerizable monomer and a polymerization initiator.

  The adhesive composition in the present invention is particularly combined with a pretreatment material containing an acidic group-containing radically polymerizable monomer, water, a + IV and / or + V vanadium compound, and an aliphatic tertiary amine. Good adhesion can be obtained.

  As the acidic group-containing radical polymerizable monomer used in the pretreatment material of the present invention, those described in the above-described phosphoric acid monomer and other acidic monomers can be used without limitation.

  The compounding amount of the acidic monomer in the pretreatment material of the present invention is not particularly limited, but is preferably 3 to 50% by mass in the total components of the pretreatment material in order to obtain high adhesiveness. 7 to 40% by mass is more preferable.

  Water that is a component used in the pretreatment material of the present invention preferably contains substantially no impurities harmful to storage stability, biocompatibility, and adhesiveness. Examples include deionized water and distilled water. Can be mentioned.

  The blending amount of the water is not particularly limited, but is preferably 5 to 90% by mass and more preferably 20 to 80% by mass in all components constituting the pretreatment material.

  The + IV and / or + V vanadium compounds used in the pretreatment material of the present invention are the same as those described as the components of the adhesive composition in the present invention.

  Although the compounding quantity of the vanadium compound in the pretreatment material of the present invention is not particularly limited, it is preferably 0.001 to 10% by mass, and 0.005 to 8% by mass in all components of the pretreatment material. % Is more preferred.

  As the aliphatic tertiary amine used in the pretreatment material of the present invention, those described above as constituent components of the adhesive composition of the present invention can be used without limitation. By blending the aliphatic tertiary amine in the pretreatment material, the storage stability when the primer is stored in one liquid can be significantly improved. If the aliphatic tertiary amine is added in a large amount, all of the acidic monomer is neutralized and the deashing action of the acidic monomer is lost. Therefore, the pH of the pretreatment material is at least 4 or less. The amount is preferably about 3 or less. On the other hand, in order to obtain high storage stability, the pH is preferably high, and it is preferable to add in a range where the pH is 1.5 or more, more preferably 1.6 or more.

  Although the suitable compounding quantity of this amine compound is based also on the kind and quantity of another component, generally it is 0.1-10 mass% in a pre-processing material, Preferably it is about 1-5 mass%.

  In the pretreatment material of the present invention, for various purposes, it is possible to blend other than the above-described components within a range that does not impair the performance as the pretreatment material.

  Examples of such components include water-soluble organic solvents, non-acidic monomers, polymerization inhibitors, and the like.

  When acidic monomers and non-acidic monomers blended in the pretreatment material have low solubility in water, blend the water-soluble organic solvent to make the pretreatment material a uniform solution or a long-term stable emulsion. It becomes easy, and it becomes very easy to treat the adherend surface evenly.

  Specific examples of such a water-soluble organic solvent include methanol, ethanol, 1-propanol, 2-propanol, 1-butanol, 2-butanol, 2-methyl-1-propanol, and 2-methyl-2. -Propanol, 1-pentanol, 2-pentanol, 3-pentanol, 2-methyl-1-butanol, isopentyl alcohol, 2-methyl-2-butanol, 3-methyl-2-butanol, 2,2 -Dimethyl-1-propanol, 1-hexanol, 2-methyl-1-pentanol, 4-methyl-2-pentanol, 2-ethyl-1-butanol, 1-heptanol, 2-heptanol, 3-he Ptanol, 1-octanol, 2-octanol, 2-ethyl-1-hexanol, 3,5,5-trimethyl-1-hexanol, Alcohol, propargyl alcohol, cyclohexanol, 1-methylcyclohexanol, 2-methylcyclohexanol, 3-methylcyclohexanol, 4-methylcyclohexanol, abiethinol, 1,2-ethanediol, 1,2-propanediol, 1 , 2-butanediol, 23-butanediol, 2-methyl-2,4-pentanediol, alcohols such as 1,2,6-hexanetriol, triethylene glycol monomethyl ether, triethylene glycol monoethyl ether, dipropylene Glycol monomethyl ether, tripropylene glycol monomethyl ether, 1,3-dioxolane, tetrahydrofuran, dimethoxyethane, 1,2-dimethoxyethane, 1,2-diethoxyethane, bis ( -Methoxyethyl) ether, ether compounds such as bis (2-ethoxyethyl) ether, ketone compounds such as acetone and methylethylketone, phosphate esters such as hexamethylphosphoric triamide, acid amides such as dimethylformamide and dimethylacetamide Examples thereof include water-soluble organic solvents such as compounds, carboxylic acid compounds such as acetic acid and propionic acid, and sulfur oxide compounds such as dimethyl sulfoxide and sulfolane.

  Among these water-soluble organic solvents, it is most preferable to use a water-soluble organic solvent having high safety for a living body such as ethanol, isopropanol, or acetone in view of harmful effects on the living body.

  These water-soluble organic solvents may be used alone or in combination with different types. Although the compounding quantity of the said water-soluble organic solvent is not restrict | limited in particular, It is preferable that it is 1-80 mass% in a pretreatment material, and it is more preferable that it is 3-50 mass%.

  The polymerization inhibitor is preferably added in an amount that does not significantly affect the adhesive strength in order to prevent gelation when the pretreatment material of the present invention is stored and to improve storage stability. Specific examples of such polymerization inhibitors include those described above. The general blending amount of the polymerization inhibitor is about 0.00001 to 5% by mass, more preferably about 0.0001 to 2% by mass in the pretreatment material.

  In addition to the above-mentioned components, the pretreatment material in the present invention includes a thickener, a polymerization regulator, an ultraviolet absorber, various metal salts other than vanadium, inorganic acid or organic acid, water-insoluble organic solvent, Examples include dyes, pigments, acid breeding materials, redox type polymerization initiators, thermal polymerization initiators, photopolymerization initiators, and antibacterial agents.

  The preparation method of the pre-treatment material is not particularly limited, and each component obtained by measuring a predetermined amount may be mixed to obtain a uniform solution or emulsion. As described above, in the case of a pretreatment material in which an aliphatic tertiary amine is blended and the pH is adjusted, it can be stored as a one-pack package in which all are mixed.

  The method of using the adhesive composition and adhesive kit of the present invention is not particularly limited, and can be used in the same manner as a kit comprising a known dental pretreatment material and an adhesive composition. That is, the pretreatment material is applied to the tooth surface to be bonded with a small brush, sponge, etc. After about 5 to 120 seconds, it is dried by air blow or the like, and then the adhesive composition is applied to the metal or ceramic By adhering a restoration such as, a clinically good adhesive force can be obtained.

  EXAMPLES Hereinafter, although an Example is given and this invention is shown concretely, this invention is not restrict | limited at all by these Examples.

The compounds used in Examples and Comparative Examples and their abbreviations are shown below.
Abbreviations and structures
[Phosphoric acid monomer]
PM: Mixture of 2-methacryloyloxyethyl dihydrogen phosphate and bis (2-methacryloyloxyethyl) hydrogen phosphate Phenyl-P; 2-methacryloyloxyethyl phenyl hydrogen phosphate [acidic monomer (other than phosphate monomer)]
MAC-10; 11-methacryloyloxy-1,1-undecanedicanbonic acid [non-acidic monomer]
bis-GMA; 2,2-bis (4- (2-hydroxy-3-methacryloyloxypropoxy) phenyl) propane UDMA; 1,6-bis (methacrylethyloxycarbonylamino) 2,2,4-trimethylhexane and 1 , 6-Bis (methacrylethyloxycarbonylamino) 2,4,4-trimethylhexane mixture 3G; triethylene glycol dimethacrylate D2.6E; 2,2-bis [(4-methacryloyloxypolyethoxyphenyl) propane]
HEMA; 2-hydroxyethyl methacrylate [aryl borate compound]
PhBNa; tetraphenyl boron sodium PhBTEOA; tetraphenyl boron triethanolamine salt [vanadium compound]
VOAA; vanadium oxide (IV) acetylacetonate BMOV; bis (maltolate) oxovanadium (IV)
[Organic peroxide]
Parkmill H; cumene hydroperoxide perocta H; 1,1,3,3-tetramethylbutyl hydroperoxide [aliphatic tertiary amine compound]
DMEM; N, N-dimethylaminoethyl methacrylate TEOA; triethanolamine [aromatic tertiary amine compound]
DMBE; 4-dimethylaminobenzoic acid ethyl ether DMPT; N, N-dimethyl-p-toluidine DEPT; N, N-diethanol-p-toluidine [photoinitiator component]
CQ; camphorquinone [filler]
Filler A; spherical silica-zirconia, γ-methacryloyloxypropyltrimethoxysilane surface-treated product (average particle size: 0.15 μm)
Filler B: Amorphous silica-zirconia, γ-methacryloyloxypropyltrimethoxysilane surface-treated product (average particle size: 3.0 μm)
[Polymerization inhibitor]
BHT; dibutylhydroxytoluene HQME; hydroquinone monomethyl ether [others]
IPA; isopropyl alcohol Each evaluation method is shown below.

(1) Measurement method of adhesive strength The anterior teeth of the bovine mandible were extracted within 24 hours after slaughter, and the enamel or dentin plane was cut out with water using # 600 emery paper so as to be parallel to the lip surface. Next, compressed air was blown onto these surfaces for about 10 seconds to dry them, and then a double-sided tape having a hole with a diameter of 3 mm was fixed to this plane to define the bonding area. Next, a pretreatment material was applied to the simulated cavity and left for 20 seconds, followed by drying with compressed air. An adhesive composition was applied to the pretreated tooth surface, and then a stainless steel jig was pressed to prepare a test piece.

After the test piece produced by the above method was immersed in water at 37 ° C. for 24 hours, a tensile test was performed using a tensile tester (Autograph AG5000, manufactured by Shimadzu Corporation) at a crosshead speed of 2 mm / min. Eight adhesion test pieces were measured per test, and the average value was taken as the adhesive strength.
(2) Method for measuring pot life At a constant temperature of 23 ° C., 0.05 g of each of the adhesive compositions A and B was weighed, mixed or kneaded for 20 seconds, and then left on the PP film. At predetermined time intervals, a PP film was pressed from above to confirm the presence or absence of curing, and the time from the start of mixing to the start of curing was defined as the pot life.

A practically sufficient pot life is preferably 180 seconds or more.
(3) Storage stability Adhesive composition B was stored in a 37 ° C. constant temperature room for 10 weeks. The case where this composition B did not change in particular was rated as ◯, and the case where it was cured was marked as x. In addition, 37 degreeC 10 weeks is a period which can withstand the specification as a product, corresponds to the time limit of 2-3 years in terms of 4 to 25 degreeC actually stored or used as a dental adhesive composition. .

Example 1
Non-acidic monomer liquid consisting of 10.0 g of 3G, 7.0 g of D2.6E, 2.0 g of HEMA, 0.1 g of PhBNa as an aryl borate compound, 0.3 g of Parkmill H as an organic peroxide, polymerization As an inhibitor, 0.005 g of BHT and 0.01 g of HQME were added to obtain a composition A as a homogeneous solution.

  On the other hand, 1.0 g of PM as a phosphoric acid monomer, 0.0003 g of VOAA as a vanadium compound, 0.3 g of DMEM as an aliphatic tertiary amine, and 0.015 g of BHT and 0.02 g of HQME as a polymerization inhibitor. In addition, a uniform solution was obtained to obtain a composition B.

  A mixture obtained by mixing the composition A and the composition B so as to have a composition ratio shown in Table 1 was used as an adhesive composition, and the pot life, storage stability, and adhesive strength were measured. As a pretreatment material for the adhesion test, a primer attached to Tokuyama Multibond (manufactured by Tokuyama Dental Co.) was used. The primer does not contain a vanadium compound.

  As a result, the pot life was 210 seconds, 14.5 (2.3) MPa for enamel and 15.4 (4.3) MPa for dentin [where () is the standard deviation; the same shall apply hereinafter) Adhesive strength was obtained. Also, the storage stability was good.

Examples 2-4
In a solution consisting of 2.0 g PM, 3.0 g water, 4.1 g acetone, 0.7 g UDMA, 0.02 g vanadium compound (BMOV), 0.03 g polymerization inhibitor (BHT) and 0 A uniform solution in which 2 g of aliphatic tertiary amine (DMEM) was mixed was obtained and used as pretreatment material P-1.

  The adhesive composition was prepared by dividing into the composition A and the composition B shown in Table 1, and various physical properties were evaluated in the same manner as in Example 1 using this. Table 2 shows the amounts and ratios of the phosphoric acid monomer, the vanadium compound and the aliphatic tertiary amine in the composition B, and the evaluation results. The pretreatment material for the adhesion test includes Tokuyama Multibond attached primer, or a solution consisting of 2.0 g PM, 3.0 g water, 4.1 g acetone, 0.7 g UDMA, and 0.02 g vanadium. A homogeneous solution (hereinafter P-1) obtained by mixing the compound (BMOV), 0.03 g of a polymerization inhibitor (BHT) and 0.2 g of an aliphatic tertiary amine (DMEM) was used. (In Table 1, the numerical value described after the blending component represents the blending ratio of the component in parts by mass. The same applies hereinafter.)

Examples 5-11, Comparative Examples 1-5
As the composition A, the same composition as the composition A used in Example 4 was used, and various physical properties were evaluated in combination with the composition B shown in Table 3. The results are shown in Table 4. The P-1 was used as the pretreatment material.

Comparative Examples 6-8
The same composition as the composition used in Example 3 was used as the composition A, and various physical properties were evaluated in combination with the composition B shown in Table 3. The results are shown in Table 4. The P-1 was used as the pretreatment material.

Examples 12-14
As composition B, the same composition as the composition used in Example 11 was used, and various physical properties were evaluated in combination with composition A shown in Table 5. The results are shown in Table 6. The P-1 was used as a pretreatment material.

Claims (2)

(A) a radical polymerizable monomer having no acidic group, a package comprising the composition A in which an aryl borate compound and an organic peroxide are blended; and (B) a phosphate group-containing radical polymerizable monomer, + IV and / or + V valent vanadium compound and a package composed of a composition B containing an aliphatic tertiary amine is stored separately. In use, the composition A and the composition B are mixed. Adhesive composition to be used, wherein the amount of + IV and / or + V vanadium compound in composition B is v mole, the amount of phosphate group-containing radical polymerizable monomer is p mole, and aliphatic When the amount of tertiary amine is nmol, these three components are represented by the following formula:
{(P−n) / v} ≦ 3000 <{p / v}
A dental adhesive composition characterized in that it is blended at a ratio satisfying the above. A dental composition comprising a pretreatment material containing an acidic group-containing radically polymerizable monomer, water, a + IV and / or + V vanadium compound, and an aliphatic tertiary amine, and an adhesive composition according to claim 1. Adhesive kit.