JP7282341B2 - adhesive composition - Google Patents

Description

TECHNICAL FIELD The present invention relates to an adhesive composition useful as a primer or adhesive for bonding metals, ceramics, dentin, and the like.

(Meth)acrylate-based polymerizable monomers are used in dental materials such as dental curable compositions or dental adhesive compositions, optical materials, printing plates, photoresist materials, paints, adhesives, inks, stereolithography resins, and the like. It can be used in a wide range of fields. In particular, in the adhesive composition for dental use, the phosphate group-containing polymerizable monomer and the phosphonic acid-containing polymerizable monomer exemplified in Patent Documents 1 and 2 are used to demineralize the smear layer of the tooth and prevent tooth decay. And it is known that it plays an important role in adhesion to metals. For example, Patent Document 1 describes polymerizable specific structures in which a phosphoric residue is bound to a (meth)acryloyloxyalkyl group via an ester bond, such as 5-(meth)acryloyloxypentyl dihydrogenphosphate. A dental adhesive containing the monomer is described to have high adhesion to nickel-chromium alloys.

Further, Patent Document 2 discloses an adhesive composition containing a polymerizable aminophosphonic acid derivative with a specific structure such as N-(meth)acryloyl-1-amino-1-benzylphosphonic acid. According to Patent Document 2, an adhesive containing a (meth)acrylate monomer containing an ester bond as disclosed in Patent Document 1 has (initial) adhesive strength due to hydrolysis of the ester bond. It is explained that there is a problem that the adhesiveness decreases slightly and the adhesiveness decreases due to hydrolysis at the adhesive interface between the adhesive and the tooth substance even after use, and the adhesive composition solves this problem. It is said to be a thing.

Japanese Patent Publication No. 63-13435 JP 2009-46397 A

The adhesive composition disclosed in Patent Document 2 uses a phosphonic acid-containing polymerizable monomer that does not have an ester bond. Due to not containing an ester group (hydrophobicity is higher than the phosphate ester group-containing polymerizable monomer), it is thought that the balance between hydrophilicity and hydrophobicity is lost. When the phosphonic acid group-containing polymerizable monomer was used alone without being used in combination with the acidic group-containing polymerizable monomer, the adhesion to tooth substance was not necessarily sufficient.

Therefore, the present invention provides adhesiveness that exhibits strong adhesion to tooth substances such as enamel and dentin, metals such as base metals and metal oxides, and ceramics, and also has excellent storage stability and long-term durability. The object is to provide a composition.

In order to solve the above problems, the present inventors focused their attention on the molecular structure of the phosphonic acid group-containing polymerizable monomer and conducted extensive studies. As a result, by introducing an ether bond into the main chain of the phosphonic acid group-containing polymerizable monomer, the hydrophilicity and hydrophobicity can be controlled, and good adhesiveness and hydrolysis resistance can be obtained, thereby solving the above problems. and completed the present invention.

That is, the present invention provides an adhesive composition comprising a polymerizable monomer comprising an acidic group-containing polymerizable monomer and a polymerizable monomer other than the acidic group-containing polymerizable monomer, wherein The contained polymerizable monomer has the following general formula (1)

（式中、Ｒは水素原子又はメチル基を表し、ｎは１又は２の整数を表し、ｍは１又は２の整数を表す。）
で示されるホスホン酸基含有重合性単量体を含有する重合性単量体成分を含有し、前記接着性組成物中に含まれる上記ホスホン酸基含有重合性単量体の含有量を１００質量部としたときに、前記ホスホン酸基含有重合性単量体以外の酸性基含有重合性単量体の含有量は５質量部以下であり、前記酸性基含有重合性単量体以外の重合性単量体の含有量は、５０質量部以上１００００質量部以下である、ことを特徴とする接着性組成物である。

(Wherein, R represents a hydrogen atom or a methyl group, n represents an integer of 1 or 2, and m represents an integer of 1 or 2.)
The content of the phosphonic acid group-containing polymerizable monomer contained in the adhesive composition is 100 mass The content of the acidic group-containing polymerizable monomer other than the phosphonic acid group-containing polymerizable monomer is 5 parts by mass or less, and the polymerizable monomer other than the acidic group-containing polymerizable monomer is 5 parts by mass or less. The adhesive composition is characterized in that the content of the monomer is 50 parts by mass or more and 10000 parts by mass or less .

The adhesive composition of the present invention is preferably a dental adhesive composition . In the case of a dental adhesive composition, it preferably further contains at least one selected from the group consisting of a polymerization initiator, water and an organic solvent, and further contains a polyvalent metal compound. "total valence of polyvalent metals" which is a value obtained by multiplying the number of moles of the total polyvalent metal compound contained in the dental adhesive composition by the valence of the polyvalent metal compound ratio of "total number of moles of the acidic group-containing polymerizable monomer" contained in the dental adhesive composition to: "total number of moles of the acidic group-containing polymerizable monomer"/"polyvalent metal is preferably 1.0 to 2.5 .

The adhesive composition of the present invention exhibits strong adhesiveness to all of dental substances such as enamel and dentin, metals such as base metals and metal oxides, and ceramics. In addition, the storage stability and the long-term durability of restoration when the adhesive composition of the present invention is used for restoration are also excellent.

It is presumed that the action mechanism by which such excellent effects are obtained is as follows. That is, instead of ester bonds, ether bonds (low hydrolyzability) are introduced into the main chain to achieve an appropriate balance between hydrophilicity and hydrophobicity, resulting in strong adhesiveness and phosphonic acid groups. It is presumed that good hydrolysis resistance is obtained because partial hydrolysis does not occur.

The adhesive composition of the present invention, like the adhesive compositions disclosed in Patent Documents 1 and 2, contains an acidic group-containing polymerizable monomer (hereinafter also simply referred to as "acidic monomer"). A monomer component is used, and the adhesiveness is improved by the action of the acidic group of the acidic monomer. By using a specific acidic monomer, the above-mentioned excellent effects are exhibited. . That is, the adhesive composition of the present invention has the greatest feature in that a phosphonic acid group-containing polymerizable monomer represented by the following general formula (1) is used as an acidic monomer.

In the general formula (1), R is a hydrogen atom or a methyl group, n is 1 or 2, and m is 1 or 2. Any combination of these R, n and m may be used, and a specific combination may be used alone, or different combinations may be mixed and used.

As the acidic monomer, it is preferable to use only the phosphonic acid group-containing polymerizable monomer represented by the general formula (1). "Other acidic monomers" as used in can also be used together. The amount of the other acidic monomer to be used is generally 5 parts by mass or less, preferably 3 parts by mass or less per 100 parts by mass of the phosphonic acid group-containing polymerizable monomer represented by formula (1).

Specific examples of the phosphonic acid group-containing polymerizable monomer represented by the general formula (1) that can be preferably used in the present invention include polymerizable monomers represented by the following structures A to H, respectively. can be done.

Among these, it is particularly preferable to use the compound represented by A from the viewpoint of good adhesiveness to tooth substance.

The phosphonic acid group-containing polymerizable monomer represented by the general formula (1) is described in U.S. Pat. Although it is also disclosed, it can be produced by the following method. That is, a phosphonic acid group-containing alcohol compound having a phosphonic acid group at one end represented by the following general formula (2) and a hydroxyl group at the other end, and a (meth) at one end represented by the following general formula (3) An alcohol compound having an acrylic group and a hydroxyl group at the other end is reacted with a (meth)acrylic group-containing alcohol compound. can be manufactured.

｛式中、ｍは前記一般式（１）中におけるｍと同義である。｝

{In the formula, m is synonymous with m in the general formula (1). }

｛式中、Ｒ及びｎは前記一般式（１）中におけるｎと同義である。｝
なお、前記一般式（２）で示されるホスホン酸基含有アルコール化合物は、下記一般式（４）で示される化合物を三塩化リンと反応させることにより、容易に得ることができる。

{In the formula, R and n are synonymous with n in the general formula (1). }
The phosphonic acid group-containing alcohol compound represented by the general formula (2) can be easily obtained by reacting the compound represented by the following general formula (4) with phosphorus trichloride.

｛式中、ｍは前記一般式（１）中におけるｍと同義である。｝
このようにして得られたホスホン酸基含有重合性単量体の構造は、核磁気共鳴スペクトル（^１Ｈ－ＮＭＲ）測定等の一般的な分析法や構造解析法により、容易に確認することができる。なお、製造過程において、ホスホン酸基含有重合性単量体のホスホン酸塩およびホスホン酸エステル化合物が一部含まれる場合がある。

{In the formula, m is synonymous with m in the general formula (1). }
The structure of the phosphonic acid group-containing polymerizable monomer thus obtained can be easily confirmed by general analytical methods such as nuclear magnetic resonance spectroscopy ( ¹ H-NMR) and structural analysis methods. can. In the production process, the phosphonate of the phosphonic acid group-containing polymerizable monomer and the phosphonate ester compound may be partly contained.

The polymerizable monomer component of the adhesive composition of the present invention contains polymerizable monomers other than acidic monomers, similarly to conventional adhesive compositions using acidic monomers. As the polymerizable monomer other than such an acidic monomer, conventionally known ones can be used without any limitation. It is preferred to use a monovalent monomer. Specific examples of these other polymerizable monomers are shown below.

Monofunctional polymerizable monomers [polymerizable monomers having one olefinic double bond (functional group)] include methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, isopropyl ( meth)acrylate, butyl (meth)acrylate, isobutyl (meth)acrylate, benzyl (meth)acrylate, lauryl (meth)acrylate, 2-(N,N-dimethylamino)ethyl (meth)acrylate, 2,3-dibromopropyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, 6-hydroxyhexyl (meth) acrylate, 10-hydroxydecyl (meth) acrylate, propylene glycol mono (meth) acrylate, Glycerin mono (meth) acrylate, erythritol mono (meth) acrylate, N-methylol (meth) acrylamide, N-hydroxyethyl (meth) acrylamide, N,N-(dihydroxyethyl) (meth) acrylamide, etc. be.

Examples of bifunctional polymerizable monomers (polymerizable monomers having one functional group) include ethylene glycol di(meth)acrylate, triethylene glycol di(meth)acrylate, polyethylene glycol di(meth)acrylate, and propylene glycol. Di(meth)acrylate, neopentyl glycol di(meth)acrylate, 1,6-hexanediol di(meth)acrylate, 1,10-decanediol di(meth)acrylate, bisphenol A diglycidyl (meth)acrylate, 2,2 -bis[4-(meth)acryloyloxyethoxyphenyl]propane, 2,2-bis[4-(meth)acryloyloxypolyethoxyphenyl]propane, 2,2-bis[4-[3-(meth)acryloyloxy -2-hydroxypropoxy]phenyl]propane, 1,2-bis[3-(meth)acryloyloxy-2-hydroxypropoxy]ethane, pentaerythritol di(meth)acrylate, 1,2-bis(3-methacryloyloxy- 2-hydroxypropoxy)ethane, [2,2,4-trimethylhexamethylenebis(2-carbamoyloxyethyl)]dimethacrylate and the like.

Polyfunctional polymerizable monomers (polymerizable monomers having 3 or more functional groups) include trimethylolpropane tri(meth)acrylate, trimethylolethane tri(meth)acrylate, and tetramethylolmethane tri(meth)acrylate. , pentaerythritol tetra(meth)acrylate, N,N'-(2,2,4-trimethylhexamethylene) bis[2-(aminocarboxy)propane-1,3-diol]tetramethacrylate, 1,7-diacryloyl Oxy-2,2,6,6-tetraacryloyloxymethyl-4-oxyheptane and the like can be mentioned.

These other polymerizable monomers (other than acidic monomers) may be used singly or in combination of two or more. Further, the mixing ratio of the phosphonic acid group-containing polymerizable monomer represented by the general formula (1) and the other polymerizable monomer in the polymerizable monomer component of the adhesive composition of the present invention is usually , With respect to 100 parts by mass of the phosphonic acid group-containing polymerizable monomer, the other polymerizable monomer is in the range of 50 parts by mass to 10000 parts by mass, preferably 100 parts by mass to 2000 parts by mass Range.

It is preferable to add water to the adhesive composition from the viewpoint of exhibiting a high degree of demineralizing effect on tooth substance and obtaining high adhesiveness. Moreover, in this case, even if the adhesive composition is stored for a long period of time, the effect of the present invention that the initial adhesive strength can be maintained at a high level is exhibited remarkably, which is preferable. It is preferable to use water that does not contain as much as possible impurities that adversely affect the development of adhesive strength between the tooth substance and the restorative material, and is generally distilled water or ion-exchanged water. is used.

From the viewpoint of improving the demineralization effect on tooth substance and improving the mechanical strength of the cured product, the amount of water blended in the adhesive composition is 100 mass of all polymerizable monomers contained in the adhesive composition. It is preferably in the range of 5 to 50 parts by mass, more preferably 6 to 30 parts by mass. If the amount is less than 5 parts by mass, the deashing action may be insufficient and the adhesive strength may decrease. If the amount is more than 50 parts by mass, water may not be completely removed by air blowing and will remain, hindering adhesion. In some cases, the hydrolysis of the polymerizable monomer tends to be accelerated and the storage stability tends to decrease.

From the viewpoint of obtaining adhesion to various adherends, it is preferable to add a polyvalent metal compound to the adhesive composition. It is believed that the reason for this is that ionic cross-linking formed by ionic bonding between the acidic group of the acidic monomer and the polyvalent metal ion provides high adhesive strength. A polyvalent metal compound is a compound selected from at least one of polyvalent metal alkoxides, polyvalent metal fluorides, polyvalent metal carbonates, polyvalent metal hydroxides, polyvalent metal hydrides, and alkyl polyvalent metals. is.

The organic group in the polyvalent metal alkoxide is not particularly limited, and examples thereof include methyl, ethyl, propyl, isopropyl, butyl, isobutyl, pentyl, hexyl, cyclohexyl, heptyl, 2-ethylhexyl, octyl and the like. An alkyl group having 4 or less carbon atoms is preferred.

The alkyl group in the alkyl polyvalent metal is not particularly limited, and examples thereof include alkyl groups having 1 to 20 carbon atoms.

Among these, the above polyvalent metal alkoxides are preferable because of their high storage stability and excellent adhesive strength. In addition, these may be used individually by 1 type, and may use 2 or more types together.

In addition, the metal element constituting the polyvalent metal compound is not particularly limited, and includes metal elements of Groups 2 to 13 of the periodic table. Metal elements are preferred, and titanium is particularly preferred. The valence of the polyvalent metal compound is not particularly limited as long as it is divalent or higher.

Specific compounds of the polyvalent metal alkoxide include, for example, magnesium diethoxide, calcium diisopropoxide, barium diisopropoxide, aluminum triethoxide, aluminum triisopropoxide, gallium triethoxide, scandium triethoxide, isopropoxide, lanthanum triisopropoxide, ytterbium triisopropoxide, yttrium tetraisopropoxide, cerium tetraisopropoxide, samarium tetraisopropoxide, titanium tetramethoxide, titanium tetraethoxide, titanium tetraisopropoxide, titanium tetrabutoxide, zirconium tetraisopropoxide, hafnium tetraisopropoxide, tantalum (V) ethoxide, chromium (III) isopropoxide, molybdenum (V) ethoxide, tungsten (VI) isopropoxide, iron (III) ethoxide, copper (II) ethoxide, zinc (II) ethoxide, etc. Specific compounds of the polyvalent metal fluorides include, for example, magnesium fluoride, calcium fluoride, barium fluoride, strontium fluoride, fluoride aluminum, titanium fluoride, lanthanum fluoride, zirconium fluoride, zinc fluoride, etc., and specific compounds of the polyvalent metal carbonates include, for example, calcium carbonate, barium carbonate, aluminum carbonate, lanthanum carbonate, yttrium carbonate, zirconium carbonate, zinc carbonate and the like. Specific examples of the polyvalent metal hydride compounds include calcium hydride, aluminum hydride, zirconium hydride and the like. Specific compounds of include, for example, diethylmagnesium and trimethylaluminum.

The content of the polyvalent metal compound in the adhesive composition is not particularly limited and can be appropriately selected depending on the intended purpose. It is preferable that the sum of the number of moles of the acidic monomers is in a range larger than the total valence of the polyvalent metals in the polyvalent metal compound.

Here, the "total valence of the polyvalent metal compound in the polyvalent metal compound" means the number of moles of the total amount of the polyvalent metal compound contained in the adhesive composition and the valence of the polyvalent metal compound. It is a combination.

Within the above range, the ratio of the number of moles of the acidic monomer to the total valence of the polyvalent metal (acidic monomer/total valence of polyvalent metal) is 1.0 to 2.5. is preferred, and 1.0 to 2.0 is more preferred.
The adhesive composition of the invention preferably contains a polymerization initiator. Both a photopolymerization initiator and a chemical polymerization initiator can be used as the polymerization initiator. It is also possible to use a photopolymerization initiator and a chemical polymerization initiator together to form a dual-cure type in which polymerization can be initiated by either photopolymerization or chemical polymerization.

Typical photoinitiators include diacetyl, acetylbenzoyl, benzyl, 2,3-pentadione, 2,3-octadione, 4,4'-dimethoxybenzyl, 4,4'-oxybenzyl, camphorquinone, 9, α-diketones such as 10-phenanthrenequinone and acenaphthenequinone, benzoin alkyl ethers such as benzoin methyl ether, benzoin ethyl ether, and benzoin propyl ether, 2,4-diethoxythioxanthone, 2-chlorothioxane thioxanthone derivatives such as methylthioxanthone, benzophenone, p,p'-dimethylaminobenzophenone, p,p'-methoxybenzophenone and other benzophenone derivatives, 2,4,6-trimethylbenzoyldiphenylphosphine oxide, bis(2,6 -dimethoxybenzoyl)-2,4,4-trimethylpentylphosphine oxide, bis(2,4,6-trimethylbenzoyl)phenylphosphine oxide and other acylphosphine oxide derivatives, furthermore, arylborate compounds/dyes/photoacid generators A system consisting of From the viewpoint of curability, particularly preferred among these are α-diketone-based photopolymerization initiators, acylphosphine oxide-based photopolymerization initiators, and a system consisting of a combination of an aryl borate compound/dye/photoacid generator. It is a photoinitiator.

In the case of using α-diketones and acylphosphone oxide derivatives, these alone show photopolymerization activity, but ethyl 4-dimethylaminobenzoate, lauryl 4-dimethylaminobenzoate, dimethylaminoethyl (meth) ) Combined use with an amine compound such as acrylate is preferable because higher polymerization activity can be obtained.

Typical chemical polymerization initiators include combinations of organic peroxides and amines, combinations of organic peroxides, amines and sulfinates, combinations of acidic compounds and aryl borates, barbituric acid, alkylboranes. and other chemical polymerization initiators such as

The amount of the polymerization initiator compounded in the adhesive composition may be an effective amount, and is generally 0.01 to 30 parts by mass with respect to 100 parts by mass of all polymerizable monomers contained in the adhesive composition. and more preferably 0.1 to 20 parts by mass. Most preferably, it is in the range of 1 to 10 parts by mass.

Furthermore, organic solvents and fillers may be added to the adhesive composition. It is effective to add an organic solvent when the adhesive composition is used as a primer. As such an organic solvent, conventionally known organic solvents can be used without any limitation, but ethanol, isopropanol, or acetone is preferably used in consideration of adverse effects on living organisms. The blending amount thereof is preferably in the range of 10 to 300 parts by mass, more preferably 30 to 200 parts by mass, based on 100 parts by mass of the total polymerizable monomers contained in the adhesive composition.

Further, as the filler, conventionally known fillers can be used without any limitation. Specifically, organic fillers, inorganic fillers, and organic-inorganic composite fillers can be exemplified, and these fillers can be used alone or in combination of two or more. There are no particular restrictions on the amount to be blended, and it may be determined appropriately in consideration of the viscosity (operability) and mechanical properties of the cured product according to the application of the composition. When used, it is preferably 0.5 to 100 parts by mass, more preferably 5 to 50 parts by mass, based on 100 parts by mass of the total polymerizable monomer component. When used as a dental composite resin or dental cement, it is preferably 30 to 1,500 parts by mass, more preferably 50 to 1,000 parts by mass based on 100 parts by mass of the total polymerizable monomer.

In addition, if necessary, the adhesive composition may contain organic thickening agents, polymerization inhibitors, polymerization modifiers, ultraviolet absorbers, dyes, antistatic agents, pigments, fragrances, etc., as long as the performance is not reduced. It is possible to add various additives.

EXAMPLES Hereinafter, in order to describe the present invention in detail, examples and comparative examples will be given, but the present invention is not limited to these.

The abbreviations of the substances used in the adhesive compositions of Examples and Comparative Examples are described below <Phosphonic acid group-containing polymerizable monomer represented by the general formula (1)>

<Other acid monomers>
• PM1: 2-methacryloyloxyethyl dihydrogen phosphate.

<Polyvalent metal compound>
• Al(O-iPr) ₃ : aluminum triisopropoxide.
• Ca(O-iPr) ₂ : calcium diisopropoxide.
• Ti(O-iPr) ₄ : titanium tetraisopropoxide.
<Other polymerizable monomers>
- BisGMA: 2.2'-bis[4-(2-hydroxy-3-methacryloxypropoxy)phenyl]propane.
- 3G: triethylene glycol dimethacrylate.
• HEMA: 2-hydroxyethyl methacrylate.
<Polymerization initiator>
- CQ: camphorquinone.
• DMBE: ethyl 4-dimethylaminobenzoate.
<Polymerization inhibitor>
BHT: 2,6-di-tert-butyl-p-cresol.

Examples 1-4 and Comparative Examples 1-2
An adhesive composition was prepared by mixing each component as shown in Table 1.

Next, the obtained adhesive composition was evaluated for adhesive strength between various adherends and the composite resin as follows.

That is, first, four types of adherends shown in (1) to (4) below were prepared.
(1) A bovine anterior tooth extracted within 24 hours after slaughter was polished with water-resistant abrasive paper P600 under water, and the enamel plane was shaved so as to be parallel and flat to the lip surface.
(2) A bovine anterior tooth extracted within 24 hours after slaughter was polished with water-resistant abrasive paper P600 under pouring water, and the dentin plane was shaved so as to be parallel and flat to the lip surface.
(3) An adherend made of a base metal alloy obtained by sandblasting a cobalt-chromium alloy "Workrom" (10 mm long, 10 mm wide, 3 mm thick, manufactured by Towa Giken Co., Ltd.) with #1500 water-resistant abrasive paper.
(4) Zirconia ceramic "TZ-3Y-E sintered body" (manufactured by Tosoh Corporation, length 10 mm × width 10 mm × thickness 3 mm) is sandblasted after polishing with # 120 waterproof abrasive paper From metal oxide (zirconia ceramics) adherend.

After that, a double-faced tape having a hole of 3 mm in diameter was attached to the polished surface of each of these four adherends. Subsequently, the adhesive composition of each example and each comparative example shown in Table 1 was applied to the adhesive surface exposed from the holes of the double-sided tape among the polished surfaces, and dried by blowing air for 5 seconds. After that, using a visible light irradiator (Tokuso Power Light, manufactured by Tokuyama Corporation), photocuring was performed by light irradiation for 10 seconds.

Paraffin wax having a thickness of 0.5 mm provided with a hole having a diameter of 8 mm is attached to the adhesive surface coated with the adhesive composition so that the hole of the paraffin wax and the hole of the double-sided tape are concentric, to form a simulated cavity. was made. This simulated cavity was filled with a dental composite resin (Esterite Σ Quick, manufactured by Tokuyama Dental Co., Ltd.) and lightly pressed with a polyester film. After that, a pre-polished SUS304 round bar (diameter 8 mm, height 18 mm) was adhered with resin cement (Bistite II, manufactured by Tokuyama Dental). Finally, a sample for adhesive strength measurement was obtained by immersing it in water at 37°C for 24 hours. The composite resin (Esterite Σquick) used is a photopolymerizable composition containing camphorquinone and an amine compound.

When preparing the sample, in order to evaluate storage stability and durability, the adhesive composition to be applied to the adherend was immediately after the adhesive composition was prepared, and after the adhesive composition was prepared. After being sealed in a container and further stored in a constant temperature bath at 50° C. for 8 weeks, two samples were used to prepare the following three samples.
(a) Sample for initial adhesive strength evaluation: sample obtained by applying the adhesive composition immediately after preparation to the adhesive surface (b) Sample for adhesive strength evaluation after long-term storage: after preparation to the adhesive surface Furthermore, a sample obtained by applying the adhesive composition after storage for 8 weeks in a constant temperature bath at 50 ° C. (c) Sample for adhesive strength evaluation after durability test: Adhesive composition immediately after preparation to the adhesive surface The sample obtained by applying the substance was further immersed alternately in a water tank of 5°C and a water temperature of 55°C for 30 seconds each, and this was repeated 3000 times. The tensile adhesive strength of these samples was measured using an autograph manufactured by Shimadzu Corporation (crosshead speed: 2 mm/min). For each example and comparative example, the measured values of four samples were averaged to obtain the measurement results. Table 2 shows the measurement results.

Examples 1, 2, 3 and 4 use adhesive compositions formulated to satisfy the constitution of the present invention. In any case, the adhesion test results showed good adhesion strength at the initial stage, after long-term storage, and after the endurance test.
On the other hand, since Comparative Example 1 did not contain an acidic group-containing polymerizable monomer, each adhesive strength was a low value. Since Comparative Example 2 uses a phosphate ester group-containing polymerizable monomer as the acidic group-containing polymerizable monomer, hydrolysis of the phosphate ester group reduces the adhesive strength after long-term storage and durability testing. bottom.

Claims (4)

In an adhesive composition comprising a polymerizable monomer consisting of an acidic group-containing polymerizable monomer and a polymerizable monomer other than the acidic group-containing polymerizable monomer,
The acidic group-containing polymerizable monomer has the following general formula (1)

(Wherein, R represents a hydrogen atom or a methyl group, n represents an integer of 1 or 2, and m represents an integer of 1 or 2.)
Containing a phosphonic acid group-containing polymerizable monomer represented by
When the content of the phosphonic acid group-containing polymerizable monomer contained in the adhesive composition is 100 parts by mass,
The content of the acidic group-containing polymerizable monomer other than the phosphonic acid group-containing polymerizable monomer is 5 parts by mass or less,
The content of the polymerizable monomer other than the acidic group-containing polymerizable monomer is 50 parts by mass or more and 10000 parts by mass or less.
An adhesive composition characterized by: A dental adhesive composition comprising the adhesive composition according to claim 1 . 3. The dental adhesive composition according to claim 2 , further comprising at least one selected from the group consisting of a polymerization initiator, water and an organic solvent. further containing a polyvalent metal compound,
The dental adhesive composition for the "total valence of the polyvalent metal", which is a value obtained by multiplying the total number of moles of the polyvalent metal compound contained in the dental adhesive composition by the valence of the polyvalent metal compound. Ratio of "total number of moles of the acidic group-containing polymerizable monomer" contained in the adhesive composition: "total number of moles of the acidic group-containing polymerizable monomer"/"total valence of polyvalent metal " is 1.0 to 2.5,
A dental adhesive composition according to claim 2 or 3 .