JP5155294B2 - Adhesive between dental alginate impression material and impression tray and kit including the same - Google Patents

Description

  The present invention relates to an adhesive for bonding a dental alginate impression material and an impression tray, and a kit including the same.

  When a cast crown restoration process or a defect prosthesis process is required to restore a tooth or the like, first, a mold such as an abutment tooth is taken. Next, a model made of gypsum or the like is produced using the obtained mold. And a prosthesis is produced based on the model, and the produced prosthesis is attached to an abutment tooth or the like. A mold such as an abutment tooth is referred to as an impression, and a cured body for obtaining an impression is referred to as an impression material.

  Generally, an alginate impression material, an agar impression material, a silicone rubber impression material, a polysulfide rubber impression material, a polyether rubber impression material, or the like is used as an impression material. Among them, the alginate impression material is most widely used because it is inexpensive and easy to handle. The alginate impression material is composed of a base material mainly composed of alginate and a hardened material mainly composed of calcium sulfate. When the base material and the hardened material are kneaded in the presence of water, a gel-like hardening is achieved. It is an impression material that makes use of the body.

  The following procedure is used to obtain an impression using an alginate impression material. First, an impression tray simulating a dentition is provided with a mixture of a base material before curing and a curing material. Next, a tray with impression material is pressed against the teeth so as to wrap the teeth in the oral cavity. Then, after the impression material is cured, the impression material and the tray are integrally removed from the teeth and removed from the oral cavity.

  The trays used when taking an impression are roughly classified into two types: ready-made trays and personal trays. A ready-made tray is a tray having a ready-made size and shape. Specific examples of the ready-made tray include stainless steel, brass, or a metal tray in which brass is plated with chromium. The personal tray is a tray whose shape is individually made for each individual. Specific examples of the personal tray include a resin tray made of polymethacrylic acid ester and a modeling compound tray made of a thermoplastic resin.

  Since the alginate impression material has low adhesion to the aforementioned trays, the impression material may peel from the tray when the impression material is removed from the teeth. When the impression material is peeled off from the tray, the shape of the impression is likely to change greatly, which causes a problem that a highly accurate impression cannot be obtained.

  In order to solve the above-described problem, a method using a tray having a net shape, an undercut shape, or a punched hole is also conceivable. By using a tray having such a shape, the area of the impression material that comes into contact with the tray increases, so that the holding force between the impression material and the tray is improved. Therefore, the impression material can be made difficult to peel from the tray.

On the other hand, when using a pre-made tray such as a plate or a personal tray instead of the tray having the above-described shape, it is necessary to increase the holding force between the impression material and the tray by another method. As one of the methods, a method of adhering between an tray and an impression material using an adhesive containing an alkaline earth metal compound has been proposed. (For example, see Patent Document 1.)
Japanese Patent Laid-Open No. 10-175812

  However, the above prior art has the following problems. If a specific shape such as a net is provided, the cost of the tray increases. In addition, it is desired to further increase the adhesive force rather than using an adhesive containing an alkaline earth metal compound.

  In addition, in resin trays, after the tray is made, operations such as sandblasting or grinding bars are used to remove the surface organic matter and improve adhesion, but such operations are not often performed. On the other side, there is a problem that the adhesive force varies depending on the smoothness of the tray surface. Therefore, it is desired to stabilize the adhesive force of the adhesive between the impression material and the tray regardless of the surface roughness of the tray surface.

  Therefore, an object of the present invention is to further improve the adhesive force of the adhesive between the impression material and the tray and to stabilize the adhesive force.

  In order to achieve such an object, the present inventor has intensively studied, and as a result, a composition comprising a polyamine compound containing two or more amino groups in one molecule in water or an organic solvent, a tray and an alginate impression material. As a result, it was found that a stable and high adhesive force was developed between the tray and the alginate impression material, and the present invention was completed.

  That is, the present invention provides (A) a polyamine compound containing two or more amino groups in one molecule, and (B) an adhesive between a dental alginate impression material containing a solvent and an impression tray. Yes.

  Another invention of the present invention is an adhesive between a dental alginate impression material and an impression tray, which further contains at least one of (C) an arylborate compound and (D) an organic peroxide.

  When the adhesive having such a composition is employed, for example, the adhesive containing (C) an aryl borate compound can stably impart an adhesive force between the alginate impression material and the impression tray. Moreover, (D) the adhesive containing an organic peroxide can strengthen the adhesive force between the alginate impression material and the impression tray. Furthermore, by using an adhesive containing both (C) arylborate and (D) organic peroxide, the alginate impression material can be peeled off from the impression tray without being affected by the roughness of the tray surface. Can be effectively prevented.

（上式中、Ｒ_１、Ｒ_２及びＲ_３は、それぞれ独立に、アルキル基、アリール基、又はアルケニル基であり、Ｒ_４及びＲ_５は、それぞれ独立に、水素原子、ハロゲン原子、ニトロ基、アルキル基、アルコキシ基、又はフェニル基であり、Ｌ^＋は、金属陽イオン、第３級又は第４級アンモニウムイオン、第４級ピリジニウムイオン、第４級キノリニウムイオン、または第４級ホスホニウムイオンを示す。）で示される化合物としている。In another aspect of the present invention, when the (C) aryl borate compound is included, the (C) aryl borate compound is represented by the general formula (1):

(In the above formula, R ₁ , R ₂ and R ₃ are each independently an alkyl group, an aryl group or an alkenyl group, and R ₄ and R ₅ are each independently a hydrogen atom, a halogen atom or a nitro group. , An alkyl group, an alkoxy group, or a phenyl group, and L ⁺ is a metal cation, a tertiary or quaternary ammonium ion, a quaternary pyridinium ion, a quaternary quinolinium ion, or a quaternary phosphonium. It represents a compound.

  When the adhesive having such a composition is employed, the adhesive force between the alginate impression material and the impression tray can be more stably imparted. Therefore, it is possible to effectively prevent the alginate impression material from being peeled off from the impression tray without being affected by the roughness of the surface of the tray.

Another aspect of the present invention relates to (A) a dental alginate impression material and impression tray containing a polyamine compound containing two or more amino groups in one molecule, (B) a solvent and (D) an organic peroxide. In the adhesive, a compound represented by (E) the following general formula (2) (wherein R ₆ and R ₇ are each independently a hydrogen atom or an alkyl group having 1 to 3 carbon atoms) ( D) It shall contain with an organic peroxide.

  When the adhesive having such a composition is employed, the storage stability of the adhesive between the dental alginate impression material containing the organic peroxide and the impression tray is improved.

  Another invention of the present invention is (B) an adhesive between a dental alginate impression material and an impression tray, wherein the solvent is at least one selected from alcohols, acetone, and acetates.

  When an adhesive having such a composition is employed, a dental alginate impression material and an impression tray, which are easy to dry as described later, have high penetrating power to resin trays and modeling compound trays, and have low toxicity. It becomes an adhesive.

  Another invention of the present invention is an adhesive between a dental alginate impression material and an impression tray using a polyamine compound having 5 or more amino groups in one molecule as the polyamine compound.

  Adopting such an adhesive between dental alginate impression material and impression tray can further enhance the adhesion between not only metal trays but also resin trays or modeling compound trays and alginate impression materials. .

  Another embodiment of the present invention is a kit including an adhesive between the dental alginate impression material and the impression tray described above, and a paste type alginate impression material.

  Adopting such a kit is convenient because it is not necessary to prepare the adhesive and the alginate impression material separately. Even if the kit uses a paste type alginate impression material that is easy to operate, the impression material does not easily peel from the tray when the impression material is removed from the tooth.

  According to the present invention, the adhesive force of the adhesive between the impression material and the tray can be further improved and the adhesive force can be stabilized.

It is a schematic diagram for demonstrating bridge | crosslinking with the alginate impression material and the polyamine compound in an adhesive agent.

  Hereinafter, a preferred embodiment of an adhesive between a dental alginate impression material and an impression tray according to the present invention will be described. However, the present invention is not limited to the embodiments described below.

  FIG. 1 is a schematic diagram for explaining cross-linking between an alginate impression material and a polyamine compound in an adhesive.

By using an adhesive containing a polyamine compound having two or more amino groups (—NH ₂ ) in one molecule, the amino group in the polyamine compound and the carboxyl in the alginate impression material as shown in FIG. It is thought that a bridge is formed between the groups. Furthermore, since the polyamine compound has a high affinity for the tray material, the polyamine compound adheres firmly when it comes into contact with the tray material. Therefore, the tray and the alginate impression material can be stably and firmly bonded via the polyamine compound.

(A) Polyamine compound containing two or more amino groups in one molecule Specific examples of the polyamine compound used in the adhesive according to the present embodiment include ethylenediamine, 1,4-butanediamine, and 1,7-heptane. Aliphatic polyamine compounds having two or more amino groups in one molecule, such as diamine, 4- (aminomethyl) -1,8-octanediamine or tris (2-aminoethyl) amine, 1,2-diaminocyclohexane , Alicyclic polyamine compounds having two or more amino groups in one molecule such as 1,4-diaminocyclohexane or 1,3-cyclohexanebis (methylamine), 1,3-phenylenediamine, 3,3 ′ -Methylenedianiline, 1,2,4-triaminobenzene, diaminoalkanes, 1,3,5-triazine-2, Aromatic polyamine compounds having two or more amino groups in one molecule, such as 1,6-triamine or 3,3′-diaminobenzidine, or polyallylamine, polyethyleneamine, polyvinylamine, polyethyleneimine, polyornithine, polylysine or A polymer or copolymer composed of a monomer having one or more amino groups such as chitosan can be suitably used. These can be used alone or in admixture of two or more.

  The molecular weight of the polyamine compound used for the adhesive according to the present embodiment is not particularly limited, but is preferably 500,000 or less in consideration of solubility in a solvent. Furthermore, the molecular weight is more preferably 1,000 to 20,000. Further, when a polyamine compound having a molecular weight of 2,000 or more is used, in order to obtain a sufficiently high adhesive force, it is preferable to contain one or more amino groups per 300 molecular weight, and one or more amino groups per 200 molecular weight. It is more preferable to use a polyamine compound containing. Moreover, in the adhesive which concerns on this Embodiment, it is preferable that the polyamine compound of the range of 1 mass part or more and 50 mass parts or less is contained in 100 mass parts of adhesive agents. In particular, the preferable amount of the polyamine compound is 3 parts by mass or more and 40 parts by mass or less, and most preferably 10 parts by mass or more and 35 parts by mass or less in 100 parts by mass of the adhesive.

  Further, the adhesive according to this embodiment can be suitably used for bonding at least between a metal tray and an alginate impression material. When using an adhesive containing a polyamine compound having 5 or more, more preferably 15 or more amino groups in one molecule such as polyallylamine, polyethyleneamine, polyvinylamine, polyethyleneimine, polyornithine, polylysine, or chitosan, Resin tray or modeling compound tray and alginate impression material can be stably bonded. Examples of metal trays that can use the adhesive according to the present embodiment include known trays made of brass, brass plated with chromium, stainless steel, and the like. Resin trays are made by mixing and polymerizing methacrylate polymer powder and methyl methacrylate, thermoplastic trays with natural resin as the main component, and ready-made polystyrene products that are cut when used. Etc. Further, as the modeling compound tray, a tray mainly composed of a natural thermoplastic resin such as corpal or a synthetic thermoplastic resin such as phthalic acid resin can be cited.

(B) Solvent The solvent used in the adhesive according to the present embodiment is used to improve the operability of the adhesive. Therefore, any known solvent can be used without any limitation as long as it is excellent in fluidity and affinity with the tray. Specifically, water, alcohols such as methanol, ethanol, isopropyl alcohol or butanol, ketones such as acetone and methyl ethyl ketone, aromatic hydrocarbons such as toluene, xylene or benzene, chlorine such as methylene chloride and chloroform And aliphatic hydrocarbons such as hexane, pentane, or butane. In particular, a solvent having high volatility and low toxicity such as ethanol or isopropyl alcohol is preferably used because it can be easily dried later. Furthermore, alcohols such as ethanol and isopropyl alcohol; acetone; acetates such as ethyl acetate and butyl acetate are particularly preferred because of their high penetrating power and low toxicity to resin trays and modeling compound trays. Used.

(C) Aryl borate compound The aryl borate compound used in the adhesive according to the present embodiment is not particularly limited as long as it is a compound having at least one boron-aryl bond in the molecule, and a known compound can be used. When such an aryl borate compound is used together with a polyamine compound, a stable adhesive force can be obtained particularly for a resin tray and a modeling compound tray. In particular, the adhesive force of the adhesive between the impression material and the tray can be further stabilized even on the surface of the tray where the operation of roughening the surface of the tray by sand blasting, a grinding bar, or the like is not performed. Further, unlike organic peroxides, it is not necessary to pay attention to the handling during production. 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.

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

(In the above formula, R ₁ , R ₂ and R ₃ are each independently an alkyl group, an aryl group or an alkenyl group, and R ₄ and R ₅ are each independently a hydrogen atom, a halogen atom or a nitro group. , An alkyl group, an alkoxy group, or a phenyl group, and L ⁺ is a metal cation, a tertiary or quaternary ammonium ion, a quaternary pyridinium ion, a quaternary quinolinium ion, or a quaternary phosphonium. Indicates ions.)
The compound shown by these is preferable.

In the general formula (1), R ₁ , R ₂ and R ₃ each independently represents an alkyl group, an aryl group, or an alkenyl group. Moreover, 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, as the substituent of the alkyl group, a halogen atom such as a fluorine atom, a chlorine atom or a bromine atom, a hydroxyl group, a nitro group, a cyano group, or a phenyl group, a nitrophenyl group, a chlorophenyl group or the like having 6 to 10 carbon atoms. Examples include C1-C5 alkoxy groups such as aryl groups, methoxy groups, ethoxy groups, and propyl groups, and C2-C5 acyl groups such as acetyl groups. The number and position of the substituents are not particularly limited.
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. Examples thereof include groups exemplified as substituents for alkyl groups, and alkyl groups having 1 to 5 carbon atoms such as methyl, ethyl and butyl groups.

  Specifically, the substituted or unsubstituted aryl group is a 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-octyloxy Examples thereof include a phenyl group and an m-octyloxyphenyl 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 are each independently a hydrogen atom, a halogen atom, a nitro group, an alkyl group, an alkoxy group, or a phenyl group. Among these, an alkyl group, an alkoxy group, and a phenyl group are an alkyl group or an alkoxy group that may have a substituent, or an optionally substituted group.

The alkyl group or alkoxy group 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. As the substituent of the alkyl group or alkoxy group include those exemplified as the substituent of the alkyl group represented by R ₁ to R _3. 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. A methyl group, a methoxymethyl group, a 1,1,1,3,3,3-hexafluoro-2-methoxy-2-propyl group, etc. are exemplified, and an alkoxy group which may have a substituent is specifically exemplified. Illustrative examples include methoxy, ethoxy, 1- or 2-propoxy, 1- or 2-butoxy, 1-, 2- or 3-octyloxy, chloromethoxy and the like.

Also, a substituent having a phenyl group is not particularly limited, and specific examples thereof include those exemplified as the substituent of the aryl group represented by R ₁ to R _3.

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.

  Specific examples of the aryl borate compound represented by the above formula (1) include trialkylphenyl boron, trialkyl (p-chlorophenyl) boron, triborate having a boron-aryl bond in one molecule. Alkyl (p-fluorophenyl) boron, trialkyl (3,5-bistrifluoromethyl) phenylboron, trialkyl [3,5-bis (1,1,1,3,3,3-hexafluoro-2-methoxy -2-propyl) phenyl] boron, trialkyl (p-nitrophenyl) boron, trialkyl (m-nitrophenyl) boron, trialkyl (p-butylphenyl) boron, trialkyl (m-butylphenyl) boron, tri Alkyl (p-butyloxyphenyl) boron, trialkyl (m-butyloxy) Phenyl) boron, trialkyl (p-octyloxyphenyl) boron, trialkyl (m-octyloxyphenyl) boron [wherein alkyl is any of n-butyl, n-octyl or n-dodecyl in any compound. Of], sodium salt, lithium salt, potassium salt, magnesium salt, tetrabutylammonium salt, tetramethylammonium salt, tetraethylammonium salt, tributylamine salt, triethanolamine salt, methylpyridinium salt, ethylpyridinium salt, butylpyridinium salt And methylquinolinium salt, ethylquinolinium salt, butylquinolinium salt, and the like.

  Further, as borate compounds having two boron-aryl bonds in one molecule, dialkyldiphenyl boron, dialkyldi (p-chlorophenyl) boron, dialkyldi (p-fluorophenyl) boron, dialkyldi (3,5-bistrifluoromethyl) Phenylboron, dialkyldi [3,5-bis (1,1,1,3,3,3-hexafluoro-2-methoxy-2-propyl) phenyl] boron, dialkyl (p-nitrophenyl) boron, dialkyldi (m -Nitrophenyl) boron, dialkyldi (p-butylphenyl) boron, dialkyldi (m-butylphenyl) boron, dialkyldi (p-butyloxyphenyl) boron, dialkyldi (m-butyloxyphenyl) boron, dialkyldi (p-octyloxy) Phenyl) Sodium salt, lithium salt, potassium salt of boron, dialkyldi (m-octyloxyphenyl) boron (wherein alkyl represents any of n-butyl, n-octyl or n-dodecyl in any compound), Magnesium salt, tetrabutylammonium salt, tetramethylammonium salt, tetraethylammonium salt, tributylamine salt, triethanolamine salt, methylpyridinium salt, ethylpyridinium salt, butylpyridinium salt, methylquinolinium salt, ethylquinolinium salt or A butyl quinolinium salt etc. can be mentioned.

  Furthermore, as borate compounds having three boron-aryl bonds in one molecule, monoalkyltriphenylboron, monoalkyltris (p-chlorophenyl) boron, monoalkyltris (p-fluorophenyl) boron, monoalkyltris ( 3,5-bistrifluoromethyl) phenylboron, monoalkyltris [3,5-bis (1,1,1,3,3,3-hexafluoro-2-methoxy-2-propyl) phenyl] boron, monoalkyl Tris (p-nitrophenyl) boron, monoalkyltris (m-nitrophenyl) boron, monoalkyltris (p-butylphenyl) boron, monoalkyltris (m-butylphenyl) boron, monoalkyltris (p-butyloxy) Phenyl) boron, monoalkyltris (m-buty) Oxyphenyl) boron, monoalkyltris (p-octyloxyphenyl) boron, monoalkyltris (m-octyloxyphenyl) boron (wherein alkyl is n-butyl, n-octyl or n-dodecyl in any compound) Sodium salt, lithium salt, potassium salt, magnesium salt, tetrabutylammonium salt, tetramethylammonium salt, tetraethylammonium salt, tributylamine salt, triethanolamine salt, methylpyridinium salt, ethylpyridinium salt, Examples thereof include butylpyridinium salt, methylquinolinium salt, ethylquinolinium salt, and butylquinolinium salt.

  Moreover, as a borate compound having four boron-aryl bonds in one molecule, tetraphenyl boron, 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-octyloxy) Phenyl) boron, tetrakis (m-o Tiloxyphenyl) boron (wherein alkyl represents any of n-butyl, n-octyl or n-dodecyl in any compound), sodium salt, lithium salt, potassium salt, magnesium salt, tetrabutylammonium salt Tetramethylammonium salt, tetraethylammonium salt, tributylamine salt, triethanolamine salt, methylpyridinium salt, ethylpyridinium salt, butylpyridinium salt, methylquinolinium salt, ethylquinolinium salt, butylquinolinium salt, etc. Can be mentioned.

Among these, in consideration of adhesiveness, it is preferable to use an aryl borate compound having 3 or 4 boron-aryl bonds in one molecule, and further 4 boron from the viewpoint of easy handling, synthesis, and availability. -An aryl borate compound having an aryl bond is more preferred. Particularly preferably, R ₁ , R ₂ , R ₃ and

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. In addition, in the adhesive according to the present embodiment, in order to obtain a sufficiently stable adhesive force, an aryl borate compound in a range of 0.1 parts by mass or more and 30 parts by mass or less is included in 100 parts by mass of the adhesive. It is particularly preferable to include 1 to 20 parts by mass of an aryl borate compound in 100 parts by mass of the adhesive.

(D) Organic peroxide In the adhesive according to the present embodiment, the organic peroxide can be used to further improve the adhesive performance of the adhesive. As the organic peroxide, diacyl peroxides, peroxyesters, dialkyl peroxides, peroxydicarbonates, peroxyketals, ketone peroxides, hydroperoxides, and the like can be used. Of these, the use of diacyl peroxides allows for stronger adhesion. Specific examples of diacyl peroxides include benzoyl peroxide, stearoyl peroxide, 2,4-dichlorobenzoyl peroxide, and m-toluoyl peroxide. In order to obtain a sufficiently strong adhesive force, it is preferable to include 0.1 to 30 parts by mass of organic peroxide in 100 parts by mass of the adhesive, and 1 in 100 parts by mass of the adhesive. It is particularly preferable to include an organic peroxide of not less than 12 parts by mass.

(E) Compound represented by general formula (2) In the adhesive according to the present embodiment, the following general formula (2) (wherein R ₆ and R ₇ are each independently a hydrogen atom or a carbon number of 1 to 3 (hereinafter referred to as α-alkylstyrene dimer) can be used to improve the storage stability of an adhesive containing an organic peroxide.

Specifically, by adding α-alkylstyrene dimer to the adhesive, it is possible to effectively prevent the adhesive strength after long-term storage of the adhesive from being reduced compared to the initial adhesive strength. . The α-alkylstyrene dimer is not particularly limited as long as it is represented by the general formula (2). For example, 2,4-diphenyl-4-methyl- in which R ₆ and R ₇ are both methyl groups. 1-pentene, 2,4-diphenyl-4-ethyl-1-hexene, or the like in which R ₆ and R ₇ are both ethyl groups can be used. Further, α-alkylstyrene dimers in which R ₆ and R ₇ are different from each other, for example, 2,4-diphenyl-4-methyl-1-hexene in which R ₆ is a methyl group and R ₇ is an ethyl group are used. May be. In order to sufficiently improve the storage stability of the adhesive, 0.05 to 5 parts by mass, more preferably 0.1 to 3 parts by mass α- in 100 parts by mass of the adhesive. It is preferred to include alkyl styrene dimers.

  The method for using the adhesive according to the present embodiment is not particularly limited. In general, a method of applying to the tray with a brush, a spatula, a brush, a roller, or the like, or spraying the tray can be employed.

  After applying or spraying the adhesive onto the tray, it is preferably dried to volatilize excess solvent. As a drying method, for example, natural drying, heat drying, air drying, reduced pressure drying, or hot air drying combining heat drying and air drying is preferably employed.

  As the alginate impression material to which the adhesive according to the present embodiment is applied, known materials can be used without any limitation. Alginate impression materials stored in paste type (hereinafter referred to as paste type alginate impression materials) and alginate impression materials in which powder and water are mixed before use (hereinafter referred to as powder type alginate impression materials) Can be used for both. As a paste type alginate impression material, for example, there is a type in which a base paste mainly composed of an alginate and a hardener paste mainly composed of calcium sulfate are mixed. Specific examples of the powder type alginate impression material include a type in which water is mixed with a powder mainly composed of alginate and calcium sulfate.

  More specifically, in the powder type alginate impression material, the powder is composed of potassium alginate, silica powder, zinc oxide, magnesium oxide, trisodium phosphate, potassium fluoride titanate, calcium sulfate or the like.

  On the other hand, the base paste used for the alginate impression material of the type used by mixing the paste is composed of potassium alginate, silica powder, potassium hydroxide, polyacrylic acid, water and the like. Similarly, the hardener paste is composed of granular silica, liquid paraffin, zinc oxide, magnesium oxide, trisodium phosphate, potassium fluoride titanate, ultrafine silica, surfactant, calcium sulfate, and the like. In such a paste type alginate impression material, for example, in order to prevent the solvent from volatilizing and curing during storage, liquid paraffin or a surfactant is used than the powder type alginate impression material. Many are also included. For example, the paste type alginate impression material contains 10 to 200 parts by mass of a poorly water-soluble liquid compound such as liquid paraffin and 0.1 to 10 parts by mass of a surfactant with respect to 100 parts by mass of calcium sulfate.

  The paste type alginate impression material has a feature that it easily peels from the tray surface because it contains a larger amount of liquid paraffin or the like. However, the adhesive according to the present embodiment can improve the adhesive force between the paste type alginate impression material and the tray, and can provide a stable adhesive force. Therefore, it is necessary to measure and mix each of the powdery component and the liquid component when using the alginate impression agent by using a kit including the adhesive according to the present embodiment and the paste type alginate impression material. In addition to the above, it is possible to obtain a kit that can obtain an impression that is uniform, has a smooth surface and has high accuracy.

  EXAMPLES Hereinafter, although an Example demonstrates this invention concretely, this invention is not restrict | limited to these Examples.

  First, an adhesion test was performed using an adhesive containing a polyamine compound and a solvent and not containing an organic peroxide and an aryl borate compound. The evaluation results are shown in Table 1. The adhesion test method is shown in (1), the type of tray used is shown in (2), and the evaluation method is shown in (3).

(1) Adhesion test method The adhesive prepared beforehand was apply | coated to each tray described in (2) with a brush, and the excess solvent was volatilized by the air blow. Then, after the kneaded alginate impression material was placed on the tray, it was allowed to stand at 37 ° C. for 3 minutes under a load of 300 g. Thereafter, the cured impression material was peeled off from the tray.

  Next, according to the evaluation criteria described in (3), the adhesive performance was evaluated based on the ratio of the area causing cohesive failure at the interface between the impression material and the tray. In all adhesion tests, paste type alginate impression material “AP-1 paste” (manufactured by Tokuyama Dental Co., Ltd.) kneaded with AP mixer II (manufactured by Tokuyama Dental Co., Ltd.) was used.

(2) Tray type X: As a metal tray, a brass plated “COE104” (made by GC Corporation) plated with nickel was used.
Y: As the resin tray, “Ostron II” (manufactured by GC Corporation) cured in a plate shape was used.
Z: “Modeling compound neutrality” (manufactured by GC Corporation) was used as a modeling compound tray.

(3) Evaluation Criteria A: When the impression material and the tray are peeled off by hand, the impression material is totally aggregated and broken.
○: When the impression material and the tray are peeled off by hand, most of the impression material causes cohesive failure, but a part is peeled off from the interface with the tray.
Δ: When the impression material and the tray are peeled off by hand, a part of the impression material causes cohesive failure, but most of the impression material is peeled off from the interface with the tray.
X: When the impression material and the tray are peeled off by hand, the impression material is easily peeled off at the interface of the tray.

Examples 1-4
Ethylenediamine and 1,7-heptanediamine as polyamine compounds having two amino groups in one molecule, 3,3′-diaminobenzidine as polyamine compounds having four amino groups in one molecule, and one molecule Each adhesive of Examples 1 to 4 having the composition shown in Table 1 was prepared using chitosan (molecular weight 984) as a polyamine compound having 6 amino groups therein.

  The metal trays to which the adhesives of Examples 1 to 4 were applied adhered firmly to the alginate impression material. Further, the adhesive of Example 4 using chitosan having 6 amino groups in one molecule has a relatively high adhesive force to each tray made of resin and modeling compound. It had a stronger adhesive force than the adhesives of Examples 1 to 3 for the tray made.

Examples 5 and 6
Using polyallylamine (molecular weight 1000) having 18 amino groups in one molecule as a polyamine compound, adhesives of Examples 5 and 6 having the compositions shown in Table 1 were produced.

Examples 7-10
Each of the adhesives of Examples 7 to 10 having the composition shown in Table 1 was prepared using polyallylamine (molecular weight 3000) having 53 amino groups in one molecule as a polyamine compound.

Examples 11-14
Each adhesive of Examples 11 to 14 having the composition shown in Table 1 was prepared using polyallylamine (molecular weight 15000) having 263 amino groups in one molecule as a polyamine compound.

Example 15
An adhesive of Example 15 having the composition shown in Table 1 was prepared using polylysine (molecular weight 3500) having 25 to 30 amino groups in one molecule as a polyamine compound.

  The adhesive strength of each adhesive of Examples 5 to 15 was improved without largely depending on the type of polyamine compound, the molecular weight, or the type of solvent. In particular, these adhesives had good adhesion to metal trays. Furthermore, the adhesives (Examples 6 and 10) containing 30 parts by mass of the polyamine compound had higher adhesion to the modeling compound. Conversely, each adhesive containing 5 parts by mass of polyallylamine (Example 7) had a relatively weak adhesive strength than that containing 10 parts by mass or more of each polyamine compound.

  Next, an adhesion test was performed using an adhesive containing an aryl borate compound. The evaluation results of Examples are shown in Table 2, and the evaluation results of Comparative Examples and Reference Examples are shown in Table 3. Since the evaluation method and the adhesion test method are the same as the adhesion test of an adhesive containing only a polyamine compound and a solvent, description thereof is omitted. The type of tray used is shown in (4), and the abbreviations of the compounds used in Examples, Reference Examples and Comparative Examples are shown in (5).

(4) Tray type X: As a metal tray, a brass plated “COE107” (made by GC Corporation) plated with nickel was used.
Y1: As the resin tray, a plate obtained by curing “Ostron II” (manufactured by GC Corporation) in a plate shape was used. "Ostron II" mixed with powder and liquid is placed on a PP film, and another PP film is placed on top of it and cured by pressure contact (contact surface roughness meter (Surfcom, manufactured by Tokyo Seimitsu Co., Ltd.) The surface roughness Ra measured in 1) was used.
Y2: The surface of Y1 was polished with P600 water-resistant abrasive paper under water injection to roughen the surface (surface roughness Ra 1.9 μm measured with a contact-type surface roughness meter (Surfcom, Tokyo Seimitsu Co., Ltd.)). It was.
Z: “Modeling compound neutrality” (manufactured by GC Corporation) was used as a modeling compound tray.

(5) Abbreviations of compounds used in Examples and Comparative Examples Polyamine compound PA1: 1,7-heptanediamine PA2: 3,3′-diaminobenzidine PA3: chitosan (number of amino groups in one molecule, molecular weight 984 )
PA4: polyallylamine (16 amino groups in one molecule, molecular weight 1000)
PA5: polyallylamine (53 amino groups in one molecule, molecular weight 3000)
PA6: polyallylamine (number of amino groups 263 in one molecule, molecular weight 15000)
Aryl borate compound AB1: Sodium tetraphenylborate AB2: Triethanolammonium tetraphenylborate AB3: Sodium tetrakis (p-fluorophenyl) borate AB4: Sodium butyltri (p-fluorophenyl) borate AB5: Sodium dibutyldiphenylborate Nitrogen-containing compound N1: n-butylamine N2: triethylamine N3: poly (4-vinylpyridine)
Boron-containing compound B1: Tributylborane (manufactured by Super Bond Catalyst Sun Medical)
Other compounds SPO: Stearyl peroxide

Example 16
1. 1.5 g of 1,7-heptanediamine which is a polyamine compound having two amino groups in one molecule, 1.0 g of sodium tetraphenylborate which is an aryl borate compound and 7.5 g of ethanol are weighed and mixed. A uniform solution adhesive was prepared. When an adhesion test was conducted using this adhesive, it showed a relatively good adhesion to all trays.

Examples 17 and 18
As in Example 16, using 3,3′-diaminobenzidine having 4 amino groups in one molecule and chitosan having 6 amino groups in one molecule (molecular weight 984) as polyamine compounds, respectively. Each adhesive having the composition shown in Table 2 was prepared and subjected to an adhesion test. As a result, the adhesive strength was better than that of Example 16 for all trays.

Examples 19-33
As polyamine compounds, polyallylamine having 18 amino tombs in one molecule (molecular weight 1000), polyallylamine having 53 amino groups in one molecule (molecular weight 3000), and 263 amino groups in one molecule Polyarylamine having a molecular weight of 15000, and as an aryl borate compound, sodium tetraphenylborate, triethanolammonium tetraphenylborate, sodium tetrakis (p-fluorophenyl) borate, butyltri (p-fluorophenyl) Each adhesive having the composition shown in Table 2 was prepared using sodium borate and sodium dibutyldiphenylborate. The results of the adhesion test are shown in Table 2, and were firmly or relatively strongly adhered to any tray.

Comparative Examples 1-4
As a system not containing a polyamine compound, a sample (Comparative Example 1) comprising an aryl borate compound and a solvent was prepared. In addition, n-butylamine having only one amino group in one molecule (Comparative Example 2), triethylamine as a tertiary amine (Comparative Example 3), and poly (4-vinylpyridine) as a heterocyclic amine compound (Comparison) Samples were prepared using the composition of Table 3 using Example 4). When the adhesion test was performed, the impression material was easily peeled off from all trays.

Reference Examples 1-3
In Example 16, a sample containing no aryl borate compound (Reference Example 1), a sample using a boron compound having no aryl group instead of the aryl borate compound (Reference Example 2), and replacing the aryl borate compound, Samples (Reference Example 3) using an organic peroxide were prepared and subjected to an adhesion test. As a result, all of them contained a polyamine compound, and the metal tray showed excellent adhesiveness. It was not a satisfactory result for trays made in particular, especially for trays with low surface roughness.

  Next, the adhesion test about the adhesive agent containing an organic peroxide was done. Since the adhesion test method and the conditions thereof are the same as the adhesion test of an adhesive not containing an organic peroxide and an aryl borate compound, description thereof is omitted.

  Tables 4, 5 and 6 show the compositions of the adhesives and the adhesive properties of the adhesives in each Example and each Comparative Example. First, the initial adhesive properties of each adhesive are shown, and then the adhesiveness after long-term storage of each adhesive is shown.

Example 34
Adhesives having the compositions shown in Table 4 were prepared using benzoyl peroxide (benzoyl peroxide) as the organic peroxide and 3,3′-diaminobenzidine as the polyamine compound. The adhesive of Example 34 had a higher adhesive strength, particularly to the trays made of resin and modeling compound, than the adhesive (Example 3) to which no organic peroxide was added.

Example 35
Adhesives having the compositions shown in Table 4 were prepared using benzoyl peroxide as the organic peroxide and chitosan (molecular weight 984) as the polyamine compound. The adhesive of Example 35 had a higher adhesive strength, particularly to the trays made of resin and modeling compound, than the adhesive (Example 4) to which no organic peroxide was added. Further, the adhesive containing chitosan (Example 35) had higher adhesive force than the adhesive containing 3,3′-diaminobenzidine (Example 34).

Example 36
Adhesives having the compositions shown in Table 4 were prepared using benzoyl peroxide as the organic peroxide and polyallylamine (molecular weight 1000) as the polyamine compound. The adhesive of Example 36 had high adhesion to all trays.

Examples 37-41
Using benzoyl peroxide as the organic peroxide and polyallylamine (molecular weight 3000) as the polyamine compound, the content of benzoyl peroxide and the like was changed as shown in Table 4 to prepare an adhesive.

Examples 42-46
Using benzoyl peroxide as the organic peroxide and polyallylamine (molecular weight 3000) as the polyamine compound, the mass ratio of polyallylamine, the type of solvent and the mass ratio were changed as shown in Table 4, and the adhesive was changed. Produced.

Examples 47, 48
Compositions shown in Table 4 using stearoyl peroxide and 1,1-bis (t-butylperoxy) 3,3,5-trimethylcyclohexane as the organic peroxide and polyallylamine (molecular weight 3000) as the polyamine compound, respectively. An adhesive consisting of Each adhesive of Example 46 or Example 47 containing benzoyl peroxide or stearoyl peroxide of diacyl peroxides and 1,1-bis (t-butylperoxy) 3,3,5 of peroxyketals -When compared with the adhesive of Example 48 containing trimethylcyclohexane, each of the adhesives of Example 46 or Example 47, especially those made of resin and modeling compound, than the adhesive of Example 48, It had a high adhesion to the tray.

Example 49
Adhesives having the compositions shown in Table 4 were prepared using benzoyl peroxide as the organic peroxide and polyallylamine (molecular weight 3000) and polyallylamine (molecular weight 15000) as the polyamine compound.

Examples 50 and 51
Adhesives having the compositions shown in Table 4 were prepared using benzoyl peroxide as the organic peroxide and polyallylamine (molecular weight: 15000) as the polyamine compound.

Example 52
An adhesive having the composition shown in Table 4 was prepared using benzoyl peroxide as the organic peroxide and polylysine (molecular weight 3500) as the polyamine compound.

  An adhesive having a benzoyl peroxide content of 3 parts by mass or more and 10 parts by mass or less and a polyamine compound content of 10 parts by mass or more had extremely high adhesive strength to all trays. The adhesives (Examples 37 and 41) containing 1 part by weight and 20 parts by weight of benzoyl peroxide respectively (Examples 37 and 41) were made of resin compared to the adhesives containing no benzoyl peroxide (Examples 8 and 9). High adhesion to trays and modeling compound trays. However, each adhesive of Example 37 and Example 41 had lower adhesive strength than an adhesive containing 3 parts by mass or more and 10 parts by mass or more of benzoyl peroxide and a polyamine compound, respectively. .

Comparative Examples 5-12
As a system not containing a polyamine compound, a sample consisting only of ethanol (Comparative Example 5) and a sample obtained by adding an organic peroxide in the composition of Table 5 in ethanol (Comparative Example 6) were prepared. Each tray coated with the samples of Comparative Examples 5 and 6 was not adhered to the impression material. N-butylamine having only one amino group in one molecule, triethylamine as a tertiary amine, poly (4-vinylpyridine) as a heterocyclic amine compound, and quaternary poly (2-methacryloyloxyethylphosphorylcholine). The samples of Comparative Examples 7 to 12 were prepared using the compositions shown in Table 5. When the impression material was peeled off from all the trays coated with the samples in Comparative Examples 7 to 12, the impression material was easily peeled from the tray.

Test method for adhesion performance after long-term storage Various adhesives were prepared by mixing the materials shown in Table 6. After production, the adhesive was sealed and stored for 9 weeks at 37 ° C. in a thermostatic bath. Using the adhesive after the long-term storage, the adhesive performance was evaluated in the same manner as in the initial adhesive performance test described above. The alginate impression material, tray, and evaluation criteria are the same as the test method for the initial adhesive performance of the adhesive not containing the organic peroxide and aryl borate compound.

Abbreviation of α-alkylstyrene dimer used: DMP: 2,4-diphenyl-4-methyl-1-pentene DMH: 2,4-diphenyl-4-methyl-1-hexene DEH: 2,4-diphenyl-4-ethyl -1-hexene

Examples 53-62
The adhesives of Examples 53 to 57 were prepared by changing the content of DMP as an α-alkylstyrene dimer. Moreover, each adhesive agent of Examples 58 and 59 was produced using another (alpha) -alkyl styrene dimer. Moreover, the adhesive agent of Example 60 was produced by changing the content of benzoyl peroxide as a peroxide. Moreover, each adhesive agent of Example 62 which changed the kind of polyamine compound and Example 62 which changed the kind of organic peroxide was produced. Each of the adhesives of Examples 53 to 62 containing an α-alkylstyrene dimer had extremely high adhesive strength to all trays even after being stored at 37 ° C. for 9 weeks. Corresponding Reference Examples 4 to 8 (adhesive containing peroxide: Example 39, Example 41, Example 35 and Example 47), and Reference Example 8 (adhesive not containing peroxide: Example 9) ) And a high adhesion to resin trays and modeling compound trays even after long-term storage.

  INDUSTRIAL APPLICABILITY The present invention can be used in the field of dental treatment in which tooth shaping is performed using an alginate impression material.

Claims (7)

  (A) An adhesive between a dental alginate impression material and an impression tray, comprising a polyamine compound containing two or more amino groups in one molecule, and (B) a solvent.   The adhesive between a dental alginate impression material and an impression tray according to claim 1, further comprising at least one of (C) an arylborate compound and (D) an organic peroxide. In the case of containing (C) an aryl borate compound, (C) the aryl borate compound is represented by the general formula (1)

(In the above formula, R ₁ , R ₂ and R ₃ are each independently an alkyl group, an aryl group or an alkenyl group, and R ₄ and R ₅ are each independently a hydrogen atom, a halogen atom or a nitro group. , An alkyl group, an alkoxy group, or a phenyl group, and L ⁺ is a metal cation, a tertiary or quaternary ammonium ion, a quaternary pyridinium ion, a quaternary quinolinium ion, or a quaternary phosphonium. Indicates ions.)
The adhesive between a dental alginate impression material and an impression tray according to claim 2, wherein the adhesive is a compound represented by the formula: Furthermore (E) the following general formula (2)

(In the formula, R ₆ and R ₇ are each independently a hydrogen atom or an alkyl group having 1 to 3 carbon atoms.)
The adhesive of the dental alginate impression material and impression tray of Claim 2 or Claim 3 characterized by containing the compound shown by (D) with an organic peroxide.   The dental alginate impression material according to any one of claims 1 to 4, wherein the solvent (B) is at least one selected from alcohols, acetone, and acetates. And adhesive for impression tray.   The dental alginate impression material and impression according to any one of claims 1 to 5, wherein the (A) polyamine compound is a polyamine compound having 5 or more amino groups in one molecule. Adhesive for trays.   The kit containing the adhesive agent of the dental alginate impression material and impression tray of any one of Claims 1-6, and a paste type alginate impression material.

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