JP3486626B2 - Adhesive material - Google Patents

Description

Description: BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a novel adhesive. More specifically, the present invention relates to an adhesive composed of a primer solution and a (meth) acrylate-based photocurable adhesive composition that can be suitably used for bonding metal materials, organic polymer materials, ceramic materials, and human hard tissues. 2. Description of the Related Art In recent years, adhesives have been widely used in various fields such as automobiles, electronics industry, construction, and medical treatment, and their respective properties are required. Above all, a dental adhesive used for restoring teeth for medical use is required to have strong adhesiveness and durability that can withstand a special environment in the oral cavity. [0003] Tooth is mainly composed of enamel and dentin. For enamel which is mostly composed of inorganic material, the surface to be adhered is treated in advance with an acid and then an acrylic monomer solution is used. A method of applying such an adhesive is generally adopted, and a sufficient effect has been recognized clinically. However, for dentin, which is rich in organic matter and is constantly exposed to bodily fluids exuding from countless tubules, such acid treatment of the adherent surface is not only ineffective, but also risks pulp damage. is there. As an attempt to obtain excellent adhesion to such dentin without applying acid treatment to the surface to be adhered, carboxylic acid and phosphoric acid are expected in view of strong affinity with dentin. A method of adding a vinyl monomer having an acidic functional group such as sulfonic acid as a component of an adhesive has been performed. Although the adhesive strength has been considerably improved by this method, at present, it is still unsatisfactory in view of long-term durability. SUMMARY OF THE INVENTION The present invention is directed to the development of an adhesive which exhibits excellent adhesive strength to various industrial materials, especially human hard tissues such as dentin containing a large amount of organic matter. It is the purpose. Means for Solving the Problems The inventors of the present invention have conducted studies to solve the above problems, and as a result, after treating with a primer solution having a specific composition, using a specific adhesive composition. When they were bonded, they found that excellent adhesion to dentin was obtained, and completed the present invention. That is, the present invention relates to (a) a carboxyl group or an acid anhydride thereof, which has at least one carbon atom, has two or more carbon atoms, and a part of hydrogen atoms is substituted with a hydroxyl group or a carboxyl group. And an alkylene group represented by the following formula: A primer solution containing a vinyl monomer having any one of hydrophobic groups selected from the group consisting of: (b) a vinyl monomer having an acidic group represented by the following formula: Embedded image Wherein R ₁ is an alkyl group or a hydrogen atom, R ₂ is an organic residue having 2 to 20 carbon atoms, 1 is 1 or 2
M is an integer of 0 or 1; n is an integer of 1 to 3; X is a carboxyl group (when l = 2, X is an acid anhydride group;
—O—CO—), —OPOCl ₂
Group or -OPO (OH) R ₃ group (R ₃ is a hydroxyl group, an aryl group, an alkoxyl group or an aryloxyl group) contained showing a], does not include a chemical polymerization catalyst (meth) acrylate-based light-curable adhesive composition For human hard tissues
Is a medical adhesive material. The primer used in the bonding method of the present invention is:
It comprises a vinyl monomer having at least one carboxyl group or its acid anhydride and a hydrophobic group. Examples of the hydrophobic group include an alkylene group having 2 or more carbon atoms as exemplified below, or a group in which some of the hydrogen atoms of these groups are substituted with a hydroxyl group, a carboxyl group, or the like. Embedded image Or the following formula: Is a group represented by In order to exhibit excellent adhesiveness, a vinyl monomer having a hydrophobic group having 4 to 20 carbon atoms in total is preferable. Specific examples of the vinyl monomer contained in the primer solution in the present invention are as follows: And the like. The primer used in the present invention can be used by dissolving it in a toxicologically acceptable organic solvent or a mixture of the organic solvent and water, if necessary.
It is preferable to set it to 100 wt% from the viewpoint of adhesion.
As the organic solvent, those which dissolve the vinyl monomer used in the present primer and which are volatile are preferably used. Specific examples include acetone, methylene chloride, ethanol, and alcohols such as isopropyl alcohol. In particular, it is preferable to dissolve in a mixture of alcohol and water to form a primer for improving the adhesive strength. In the present invention, the term "primer" refers to an undercoating agent for treating the surface to be adhered before bonding with an adhesive. As a primer treatment method, a method is generally employed in which a sponge or a small brush is applied so that the surface to be adhered is completely wetted. After the primer treatment, it is preferable to blow the air to dry and then proceed to the next bonding step for improving the bonding strength. In the bonding method of the present invention, it is essential to use a (meth) acrylate-based photocurable adhesive composition (hereinafter, also referred to as a photocurable adhesive composition) after the above-mentioned primer treatment. The (meth) acrylate-based photocurable adhesive composition is mainly composed of a photopolymerization catalyst and a (meth) acrylate compound polymerized by the photopolymerization catalyst. An agent, a polymerization inhibitor, a filler and the like may be added as necessary. However, when an adhesive composition containing a chemical polymerization catalyst is used instead of the photopolymerization catalyst, a high adhesive strength cannot be obtained. This is because, in the case of chemical polymerization, since the polymerization has started before the adhesive composition is applied to the adherend, the molecular weight of the (meth) acrylate compound increases and the adherend cannot be sufficiently wetted. Also, even if it can be sufficiently wetted, it cannot be polymerized promptly as in the case of photopolymerization on the surface where the exudate from the pulp overflows, such as dentin, and the polymerization at the bonding interface becomes insufficient. Is assumed. The (meth) acrylate compound which is one of the main components of the photocurable adhesive composition used in the present invention includes:
Known materials polymerized by a photopolymerization catalyst can be used without any particular limitation. Specific examples of the (meth) acrylate compounds generally preferably used include methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate, and n- Butyl (meth) acrylate, isobutyl (meth) acrylate, n-hexyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, tridecyl (meth) acrylate, stearyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2 Monofunctional vinyl monomers such as hydroxypropyl (meth) acrylate, glycidyl (meth) acrylate, methoxydiethylene glycol (meth) acrylate, (2-methacryloxyethyl) maleic acid monoester; Koruji (meth) acrylate,
Diethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, tetraethylene glycol di (meth) acrylate, propylene glycol di (meth) acrylate, 1,4-butanediol di (meth) acrylate, 1,6-hexane Diol di (meth) acrylate, neopentyl glycol di (meth) acrylate, 1,10-decanediol di (meth) acrylate, bisphenol A di (meth) acrylate, 2,2′-bis [((meth) acryloyloxypoly Ethoxyphenyl] propane, 2,2'-bis [4- (3-methacryloyloxy-2-hydroxypropoxy) phenyl] propane, trimethylolpropane (meth) acrylate, trimethylolethanetri (meth) acrylate, Polyfunctional vinyl monomers such as lame Chi roll tetra (meth) acrylate is used. [0031] Further, as (meth) acrylate compound,
In order to improve adhesive strength and durability, a vinyl monomer having an acidic group represented by the following formula is blended. Embedded image Wherein R ₁ is an alkyl group or a hydrogen atom, R ₂ is an organic residue having 2 to 20 carbon atoms, 1 is 1 or 2
M is an integer of 0 or 1; n is an integer of 1 to 3; X is a carboxyl group (when l = 2, X is an acid anhydride group;
—O—CO—), —OPOCl ₂
A group or —OPO (OH) R ₃ group (R ₃ is a hydroxyl group, an aryl group, an alkoxyl group or an aryloxyl group)] In the above general formula, the group represented by R ₁ is a hydrogen atom or an alkyl group, and an alkyl group Specific examples include a methyl group and an ethyl group. R ₂ is an organic acid group having 2 to 20 carbon atoms. When the number of carbon atoms is 1 or less, the adhesion durability under wet conditions is low. When the number of carbon atoms is 21 or more, it is difficult to obtain a material, and the adhesive strength is low because the strength of the cured body cannot be obtained. The organic residue may be an aliphatic or aromatic organic residue as long as the number of carbon atoms is satisfied, and may be partially substituted with a substituent such as a halogen, an amino group, or a hydroxyl group. In the general formula, X is a carboxyl group, -OPO
Cl ₂ or —OPO (OH) R ₃ group, which is bonded to one or two organic residues. Here, the group represented by R ₃ is a hydroxyl group; an aryl group such as a phenyl group; a methoxy group;
An alkoxyl group such as an ethoxy group or a butoxy group; or an aryloxyl group such as a phenoxy group or a benzyloxy group. Specific examples of vinyl monomers having an acidic group which are generally preferably used include p-methacryloxybenzoic acid, p-vinylbenzoic acid, 2-methacryloxyethyl phthalic acid and 2-methacryloxyethyl succinic acid. Vinyl monomer having one carboxyl group in the molecule; 7-methacryloxy-1,1-heptanedicarboxylic acid, 11-methacryloxy-1,1-undecanedicarboxylic acid, 13-methacryloxy-1,1-tridecanedicarboxylic acid, 4 Vinyl monomers having two carboxyl groups in the molecule, such as-(β-methacryloxyethyl) trimellitate and anhydride; 6-methacryloxyhexyl dihydrogen phosphate, 10-methacryloxydecyl dihydrogen phosphate, 6 −
Methacryloxyhexyl butyl phosphate, 6-methacryloxyhexyl phenyl phosphate, 2-methacryloxyethyl hydrogen phenyl phosphate,
And vinyl monomers having two phosphate groups in a molecule such as a reaction product of bisphenol A diglycidyl methacrylate and phosphorus oxychloride. In order to exhibit excellent adhesiveness, the vinyl monomer having an acidic group represented by the above-mentioned general formula is required to have R
₂ is preferably an alkylene group having 4 to 20 carbon atoms, and furthermore, when X is a carboxyl group, the alkylene group has 4 to 20 carbon atoms;
Is -OPO (OH) R ₃ , and when R ₃ is a hydroxyl group, it may have 6 to 20 carbon atoms, and when R ₃ is an aryl group, an alkoxyl group or an aryloxyl group, it may have 2 to 12 carbon atoms. Particularly preferred. Specific examples of these preferred vinyl monomers include 7-methacryloxy-1,1
-Heptanedicarboxylic acid, 11-methacryloxy-1,
1-undecanedicarboxylic acid, 13-methacryloxy-
Dicarboxylic acids having two carboxyl groups in the molecule, such as 1,1-tridecanedicarboxylic acid, or 6-methacryloxyhexyl dihydrogen phosphate;
Monophosphates such as 0-methacryloxydecyl dihydrogen phosphate are exemplified. The vinyl monomer having such an acidic group is
Normally all polymerizable monomers 100 in the photocurable adhesive composition
It is contained in an amount of 1 to 50 parts by weight per part by weight. Another one of the main components of the photocurable adhesive composition used in the present invention is a photopolymerization catalyst. Known photopolymerization catalysts are used without any limitation. In particular,
Diacetyl, acetylbenzoyl, benzyl, 2,3-
Pentadione, 2,3-octadione, 4,4′-dimethoxybenzyl, α-naphthyl, β-naphthyl, 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; thioxanthone derivatives such as 2,4-diethoxythioxanthone, 2-chlorothioxanthone and methylthioxanthone Benzophenone, p, p '
Benzophenone derivatives such as -dimethylaminobenzophenone and p, p'-methoxybenzophenone are preferably used. These photopolymerization catalysts are used in an amount of 0.0
It is desirable to add 5 to 10 parts by weight, preferably 0.1 to 5 parts by weight. Further, other additives may be added, if necessary, simultaneously with the above-mentioned photopolymerization catalyst. For example, a curing accelerator can be added. Examples of the curing accelerator include N, N-dimethyl-p-toluidine, N, N'-dimethylbenzylamine, N-methyldibutylamine, dimethylaminoethyl methacrylate, N, N-dimethyl-m-anisidine, amine compounds such as ethyl p-dimethylaminobenzoate; thiourea compounds such as allyl thiourea and o-tolyl thiourea; phosphite compounds such as dimethyl phosphite and dioctyl phosphite; The curing accelerator is added in an amount of 0.0 to 100 parts by weight of the total polymerizable monomers in the photocurable adhesive composition.
5 to 5 parts by weight, preferably 0.1 to 3 parts by weight is desirable. When the photocurable adhesive composition of the present invention is used, the polymerization is carried out by using a high-pressure, Nakasho, low-pressure mercury lamp for ultraviolet rays;
The irradiation can be performed by irradiating visible light with a halogen lamp, a xenon lamp, or the like. The photocurable adhesive composition used in the present invention comprises:
If necessary, it is preferable to add a small amount of a polymerization inhibitor such as hydroquinone, hydroquinone monomethyl ether, and butylhydroxytoluene. In the present invention, it is preferable to add a filler depending on an object to be bonded. By adding a filler, mechanical strength and water resistance are improved, and further, fluidity and coatability can be controlled. Examples of the filler include quartz, amorphous silica, silica zirconia, clay, aluminum oxide, talc, mica,
Kaolin, glass, barium sulfate, zirconium oxide,
Titanium oxide, silicon nitride, aluminum nitride, titanium nitride, silicon carbide, boron carbide, calcium carbonate,
Inorganic substances such as hydroxyapatite and calcium phosphate;
Organic substances such as polymers or oligomers such as polymethyl methacrylate, polyethyl methacrylate, polyvinyl chloride, polystyrene, polyester, and nylon; and organic-inorganic composite fillers. Usually, it is preferable to use the inorganic filler that has been treated with a silane coupling agent such as γ-methacryloyloxypropylmerimethoxysilane or vinyltriethoxysilane. The amount of the filler to be added can be appropriately selected as needed. For example, the filler may be selected from a range of 1 to 300 parts by weight based on 100 parts by weight of the total polymerizable monomer in the photocurable adhesive composition. Good. It is desirable that the photocurable adhesive composition used in the present invention does not contain an organic solvent. In particular, when alcohols such as ethanol are contained, the adhesive strength tends to decrease. This is presumably because the adhesive layer is too thin to cause a defect on the adhesive surface, and alcohol plays a role as a polymerization inhibitor. Next, the bonding method will be described in detail, but the present invention is not limited to these specific examples. When one of the adherends is a solid and the other is a paste-like material such as a photocurable composite resin, a primer is provided on the solid side,
Then, after applying the photocurable adhesive composition, visible light is preferably applied to the adhesive composition for increasing the adhesive strength.
Irradiate for ~ 60 seconds. Next, the paste-like material is put on the plate, and further press-contacted, and then polymerized and cured by irradiating light to bond both adherends. When both adherends are solid, apply a primer to one, apply a photocurable adhesive composition to the other, and then press the two bodies together, then irradiate light from the adhesion boundary or from above the solid surface And make it adhere by curing. The adhesive of the present invention is pretreated with a primer composed of a specific component, and then adhered by using a (meth) acrylate-based photocurable adhesive composition, whereby the adhesiveness is improved. Significant improvements can be made. In particular, an excellent effect is exhibited in bonding human hard tissues such as teeth and bones, particularly dentin, which has been conventionally difficult to bond by containing a large amount of organic components. The adhesive of the present invention is also effective for bonding metals, ceramics, organic polymers and the like in addition to the above-mentioned bonding. Hereinafter, the present invention will be described in more detail with reference to the following Examples.
Examples are shown, but the present invention is not limited to these examples. (Meth) acrylate compounds used in the following Examples, Reference Examples and Comparative Examples are abbreviated as follows. Embedded image Reference Examples 1 to 9 and Comparative Example 1 Adhesion strength to dentin was measured using the primer of the present invention and a (meth) acrylate-based photocurable adhesive composition containing no vinyl monomer having an acidic group. Was done. The measuring method is as follows. The anterior bovine teeth were removed within 24 hours after slaughter, and dentin was cut out under water by using # 800 emery paper so as to be horizontal to the lips. Next, after blowing compressed air on the surface for about 10 seconds and drying, a paraffin wax with a hole of 4 mm in diameter is fixed to this dentin surface with a double-sided tape to form a simulated cavity having the surface as the bottom surface. did. A primer having a composition shown in Table 1 was applied to the surface, left for 60 seconds, dried by blowing compressed air, and subsequently a (meth) acrylate-based photocurable adhesive composition having the following composition: The product was applied, and then irradiated with light for 10 seconds using a commercially available visible light irradiator “White Light” (manufactured by Takara Labelmont). Further, a commercially available light-curable composite resin “PARF EQUILITE” (manufactured by Tokuyama Soda Co., Ltd.) was loaded thereon, pressed, and then irradiated with light again for 30 seconds to cure. After the composite resin was cured, the paraffin wax was removed, and the composite resin was left in water at 37 ° C. for 24 hours. A metal attachment was attached to each of the cow front teeth and the composite resin cured body, and the adhesion strength between the dentin and the photocurable adhesive composition was measured using a tensile tester (crosshead speed: 10 mm / min). . The composition of the photocurable adhesive composition is as follows. 2-hydroxyethyl methacrylate 28.3 parts by weight Bisphenol A diglycidyl methacrylate 26.6 {triethylene glycol dimethacrylate 45.1} camphorquinone 0.4 {ethyl p-dimethylaminobenzoate 0.6} hydroquinone monomethyl Ether 0.05% Table 1 shows the adhesive strength obtained by the above method and the adhesive strength when no primer was applied as a comparative example. [Table 1] Examples 1 to 16 and Comparative Examples 2 to 4 The primers of Reference Examples 3, 6 and 8 were used as reference materials except that the compositions shown below and in Table 2 were used as the photocurable adhesive composition. The adhesive force was measured in the same manner as in Examples 1 to 9. Vinyl monomer having acidic group X parts by weight Bisphenol A diglycidyl methacrylate 40 {triethylene glycol dimethacrylate 60-X} camphorquinone 0.4 {ethyl p-dimethylaminobenzoate 0.6} hydroquinone monomethyl ether 05〃 The adhesive strength obtained by the above method, and as a comparative example, the case where the primer does not contain the “vinyl monomer having at least one carboxyl group or its acid anhydride and a specific hydrophobic group” of the present invention; Table 2 also shows the adhesive strength when using a vinyl monomer that is not a monomer.
Shown in [Table 2] [Table 3] Examples 17 to 20 Using the primer of Example 1, the photocurable adhesive composition was changed to camphorquinone and ethyl p-dimethylaminobenzoate in the composition by photopolymerization shown in Table 3. The adhesive strength was measured in the same manner as in Example 1 except that a catalyst and a curing accelerator were used. Table 3 also shows the results. [Table 4] Examples 21 to 23 Using the primer of Example 1 and the vinyl monomer having an acidic group, the results are shown in Table 4 in place of bisphenol A diglycidyl methacrylate and triethylene glycol dimethacrylate in the photocurable adhesive composition. The adhesive strength was measured in the same manner as in Example 1 except that the (meth) acrylate compound was used. The results are shown in Table 4. [Table 5] Comparative Examples 5 to 7 Adhesion strength was measured in the same manner except that the primer of Reference Example 3 was used and the chemically curable adhesive composition shown in Table 5 was used instead of the photocurable adhesive composition. . Table 5 with the results
Shown in [Table 6]

────────────────────────────────────────────────── ─── Continuation of the front page (56) References JP-A-4-323283 (JP, A) JP-A 1-113057 (JP, A) JP-A-62-223289 (JP, A) (58) Survey Field (Int.Cl. ⁷ , DB name) A61K 6/00 C09D 4/00 C09D 5/00 C09J 4/02

Claims (1)

(57) [Claim 1] (a) At least one carboxyl group or an acid anhydride thereof, has two or more carbon atoms, and a part of hydrogen atoms is a hydroxyl group or a carboxyl group. And an alkylene group optionally substituted with the following formula: A primer solution comprising a vinyl monomer having any hydrophobic group selected from the group consisting of: and (b) a vinyl monomer having an acidic group represented by the following formula: [Wherein, R ₁ is an alkyl group or a hydrogen atom, R ₂ is an organic residue having 2 to 20 carbon atoms, ₁ is an integer of 1 or 2, m is 0
Or the integer 1, n represents an integer of 1-3, X is (when l = 2, X is an acid anhydride group, may also be present in -CO-O-CO- form of) a carboxyl group, - OPOCl ₂ Group or -OP
O (OH) R ₃ group (R ₃ represents a hydroxyl group, an aryl group, an alkoxyl group or an aryloxyl group)];
A medical adhesive material for human hard tissues, comprising a (meth) acrylate-based photocurable adhesive composition containing no chemical polymerization catalyst.