JP2017200881A - Dental adhesive set - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a dental adhesive set with improved adhesion strength.SOLUTION: A dental adhesive set has a primer, and an adhesive. The primer contains a compound having an acid radical and a (meth) acryloyloxy group of 1-60 mass%, and water of 1-98 mass%. The adhesive contains a compound having an acid radical and a (meth) acryloyloxy group of 1-40 mass%, a water-soluble organic solvent of 1-60 mass%, water of 1-60 mass%, and a compound having no acid radical but having a (meth) acryloyloxy group of 10-90 mass%.SELECTED DRAWING: None

Description

  The present invention relates to a dental adhesive set.

  Conventionally, as a bonding system in dental treatment, a three-step bonding system including etching with an etching agent, priming with a primer, and bonding with a bonding agent has been used.

  In recent years, a one-step adhesive system using a one-component dental adhesive has been developed (see, for example, Patent Documents 1 and 2).

JP 2006-176488 A JP 2011-126830 A

  However, it is desired to improve the adhesive strength.

  An object of one embodiment of the present invention is to provide a dental adhesive set capable of improving the adhesive strength.

  One aspect of the present invention is a dental adhesive set having a primer and an adhesive, wherein the primer contains 1 to 60% by mass of a compound having an acid group and a (meth) acryloyloxy group, and water. 1 to 98% by mass, the adhesive contains 1 to 40% by mass of a compound having an acid group and a (meth) acryloyloxy group, 1 to 60% by mass of a water-soluble organic solvent, and 1 water. It contains ˜60% by mass, contains no acid group, and contains 10 to 90% by mass of a compound having a (meth) acryloyloxy group.

  According to one embodiment of the present invention, a dental adhesive set capable of improving adhesive strength can be provided.

  Next, the form for implementing this invention is demonstrated.

  The dental adhesive set has a primer and an adhesive.

  Here, the dental adhesive set is used, for example, by sequentially applying a primer and an adhesive to a tooth, filling a dental composite resin, and irradiating light to cure the primer and the adhesive. .

  In addition, when it is not necessary to improve the adhesive strength, for example, after applying only the adhesive, the adhesive can be cured by filling the dental composite resin and irradiating light. .

[Primer]
The primer contains (a) a compound having an acid group and a (meth) acryloyloxy group, and (c) water.

  In the present specification and claims, the (meth) acryloyloxy group means a methacryloyloxy group and / or an acryloyloxy group.

  Content of the compound which has (a) acid group and (meth) acryloyloxy group in a primer is 1-60 mass%, and it is preferable that it is 5-30 mass%. When the content of the compound having (a) acid group and (meth) acryloyloxy group in the primer is less than 1% by mass or exceeds 60% by mass, the adhesive strength is lowered.

  The content of (c) water in the primer is 1 to 98% by mass, and preferably 20 to 70% by mass. When the content of (c) water in the primer is less than 1% by mass or exceeds 98% by mass, the adhesive strength is lowered.

  The primer is optionally (b) a water-soluble organic solvent, (d) a compound having no acid group and having a (meth) acryloyloxy group, (e) a photopolymerization initiator, and (f) photopolymerization acceleration. May further contain an agent, (g) a polymerization inhibitor, and the like.

[adhesive]
The adhesive comprises (a) a compound having an acid group and (meth) acryloyloxy group, (b) a water-soluble organic solvent, (c) water, (d) having no acid group, and having a (meth) acryloyloxy group. The compound which has.

  Content of the compound which has (a) acid group and (meth) acryloyloxy group in an adhesive agent is 1-40 mass%, and it is preferable that it is 5-25 mass%. When the content of the compound having (a) acid group and (meth) acryloyloxy group in the adhesive is less than 1% by mass or exceeds 40% by mass, the adhesive strength is lowered.

  Content of (b) water-soluble organic solvent in an adhesive agent is 1-60 mass%, and it is preferable that it is 25-55 mass%. When the content of the water-soluble organic solvent (b) in the adhesive is less than 1% by mass or exceeds 60% by mass, the adhesive strength is lowered.

  The content of (c) water in the adhesive is 1 to 60% by mass, and preferably 5 to 30% by mass. When the content of (c) water in the adhesive is less than 1% by mass or exceeds 60% by mass, the adhesive strength decreases.

  The content of the compound having no (d) acid group and having a (meth) acryloyloxy group in the adhesive is 10 to 90% by mass, and preferably 15 to 30% by mass. In the case where the content of the compound having (d) an acid group and having a (meth) acryloyloxy group in the adhesive is less than 10% by mass or exceeds 90% by mass, the adhesive strength is lowered. To do.

  The adhesive preferably further contains (e) a photopolymerization initiator, (f) a photopolymerization accelerator, (g) a polymerization inhibitor, and (h) a filler.

  The content of (e) the photopolymerization initiator in the adhesive is preferably 0.1 to 5% by mass, and more preferably 1 to 2.5% by mass. When the content of the (e) photopolymerization initiator in the adhesive is less than 0.1% by mass, or when it exceeds 5% by mass, the adhesive strength decreases.

  The content of the photopolymerization accelerator (f) in the adhesive is preferably 0.1 to 5% by mass, and more preferably 0.2 to 1% by mass. When the content of the (f) photopolymerization accelerator in the adhesive is 0.1% by mass or more, or 5% by mass or less, the adhesive strength is further improved.

  The content of the polymerization inhibitor (g) in the adhesive is preferably 0.1 to 5% by mass, and more preferably 0.2 to 1% by mass. When the content of the polymerization inhibitor (g) in the adhesive is 0.1% by mass or more, or 5% by mass or less, the storage stability is improved.

  The content of the (h) filler in the adhesive is preferably 0.5 to 20% by mass, and more preferably 2.5 to 9% by mass. When the content of (h) filler in the adhesive is 0.5% by mass or more, or 20% by mass or less, the adhesive strength is further improved.

  Next, materials contained in the primer and the adhesive will be described.

  (A) As an acid group in the compound which has an acid group and a (meth) acryloyloxy group, a phosphoric acid group, a carboxyl group, a sulfonic acid group etc. are mentioned, for example.

  (A) The compound having an acid group and a (meth) acryloyloxy group may have a plurality of (meth) acryloyloxy groups.

  Examples of the compound having a phosphate group and a (meth) acryloyloxy group include 2- (meth) acryloyloxyethyl dihydrogen phosphate, bis [2- (meth) acryloyloxyethyl] hydrogen phosphate, 2- (meth) acryloyl. Oxyethyl phenyl acid phosphate, 6- (meth) acryloyloxybutyl acid phosphate, 8- (meth) acryloyloxydecyl acid phosphate, 10- (meth) acryloyloxydecyl dihydrogen phosphate, 3- (meth) acryloyloxypropyldi Hydrogen phosphate, 4- (meth) acryloyloxybutyl dihydrogen phosphate, 5- (meth) acryloyloxypentyl dihydrogen phosphate, 6- (meth) Acryloyloxyhexyl dihydrogen phosphate, 7- (meth) acryloyloxyheptyl dihydrogen phosphate, 8- (meth) acryloyloxyoctyl dihydrogen phosphate, 9- (meth) acryloyloxynonyl dihydrogen phosphate, 11- (Meth) acryloyloxyundecyl dihydrogen phosphate, 12- (meth) acryloyl oxide decyl dihydrogen phosphate, 16- (meth) acryloyloxy hexadecyl dihydrogen phosphate, 20- (meth) acryloyloxyicosyl dihydro Gen phosphate, 2- (meth) acryloyloxyethyl phenyl hydrogen phosphate, 2- (meth) acryloyloxyethyl-2-bromoe Le hydrogen phosphate, 2- (meth) acryloyloxyethyl - (4-methoxyphenyl) hydrogen phosphate, 2- (meth) acryloyloxy propyl - (4-methoxyphenyl) hydrogen phosphate, and the like.

  Examples of the compound having a carboxyl group and a (meth) acryloyloxy group include (meth) acrylic acid, 4- (meth) acryloyloxyethyl trimellitic acid and its acid anhydride, 6- (meth) acryloyloxyethylnaphthalene-1, 2,6-tricarboxylic acid and its acid anhydride, 1,4-di (meth) acryloyloxyethyl pyromellitic acid, 2- (meth) acryloyloxyethyl succinic acid, 2- (meth) acryloyloxyethyl maleic acid, 2 -(Meth) acryloyloxyethyl phthalic acid, 2- (meth) acryloyloxyethyl hexahydrophthalic acid, 11- (meth) acryloyloxy-1,1-undecanedicarboxylic acid, N- (meth) acryloyl-p-aminobenzoic acid Acid, N- (meth) acryloyl-o-aminobenzoic acid, N (Meth) acryloyl-5-aminosalicylic acid.

  Examples of the compound having a sulfonic acid group and a (meth) acryloyloxy group include 2-sulfoethyl (meth) acrylate and 2- (meth) acrylamide-2-methylpropanesulfonic acid.

  Here, two or more compounds having (a) an acid group and a (meth) acryloyloxy group may be used in combination.

  Among these, bis [2- (meth) acryloyloxyethyl] hydrogen phosphate, 2- (meth) acryloyloxyethyl phenyl acid phosphate, 10- (meth) acryloyloxydecyl dihydrogen phosphate, 4- (meth) acryloyl Oxyethyl trimellitic acid and its acid anhydride, 6- (meth) acryloyloxyethylnaphthalene-1,2,6-tricarboxylic acid and its acid anhydride, 1,4-di (meth) acryloyloxyethyl pyromellitic acid, 2- (Meth) acrylamido-2-methylpropanesulfonic acid is preferred.

  In addition, the compound which has (a) acid group and (meth) acryloyloxy group contained in a primer and an adhesive agent may be the same, and may differ.

  (B) The water-soluble organic solvent is particularly limited as long as (a) a compound having an acid group and a (meth) acryloyloxy group can be dissolved and wettability with a tooth can be improved. Although not mentioned, ethanol, acetone and the like can be mentioned, and two or more kinds may be used in combination.

  In addition, when a primer contains (b) water-soluble organic solvent, (b) water-soluble organic solvent contained in a primer and an adhesive agent may be the same, and may differ.

  (D) The compound having no acid group and having a (meth) acryloyloxy group is not particularly limited, but methyl (meth) acrylate, ethyl (meth) acrylate, isopropyl (meth) acrylate, n-butyl (meth) ) Acrylate, isobutyl (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, glycidyl (meth) acrylate, 2-methoxyethyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, benzyl (meth) acrylate, 2,2- Bis ((meth) acryloyloxyphenyl) propane, 2,2-bis (4- (meth) acryloyloxydiethoxyphenyl) propane, 2,2-bis (4- (meth) acryloyloxypolyethoxyphenyl) propane, ethylene Glycol di (me ) Acrylate, diethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, butylene glycol di (meth) acrylate, neopentyl glycol di (meth) acrylate, 1,3-butanediol di (meth) acrylate, 1, 4-butanediol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, trimethylolpropane tri (meth) acrylate, trimethylolethane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, trimethylol Methanetri (meth) acrylate, pentaerythritol tetra (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2-hydro Ci-1,3-bis [(meth) acryloyloxy] propane, 2,2-bis [4- (2-hydroxy-3- (meth) acryloyloxypropoxy) phenyl] propane, bis ((meth) acryloyloxy) Examples include propanol, (meth) acrylate having a urethane bond, and two or more of them may be used in combination.

  Examples of the (meth) acrylate having a urethane bond include bis [2- (meth) acryloyloxyethyl] -2,2,4-trimethylhexamethylene dicarbamate.

  When the primer does not have (d) an acid group and contains a compound having a (meth) acryloyloxy group, (d) the acid group or hydroxyl group contained in the primer and the adhesive does not have (meth) The compounds having an acryloyloxy group may be the same or different.

  (E) The photopolymerization initiator is not particularly limited, but camphorquinone, benzyl ketal, diacetyl ketal, benzyl dimethyl ketal, benzyl diethyl ketal, benzyl bis (2-methoxyethyl) ketal, 4,4′-dimethyl (benzyl dimethyl) Ketal), anthraquinone, 1-chloroanthraquinone, 2-chloroanthraquinone, 1,2-benzanthraquinone, 1-hydroxyanthraquinone, 1-methylanthraquinone, 2-ethylanthraquinone, 1-bromoanthraquinone, thioxanthone, 2-isopropylthioxanthone, 2 -Nitrothioxanthone, 2-methylthioxanthone, 2,4-dimethylthioxanthone, 2,4-diethylthioxanthone, 2,4-diisopropylthioxanthone, 2-chloro- 7-trifluoromethylthioxanthone, thioxanthone-10,10-dioxide, thioxanthone-10-oxide, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin isobutyl ether, benzophenone, bis (4-dimethylaminophenyl) ketone, 4 , 4′-bis (diethylamino) benzophenone, a compound containing an azide group, and the like, and two or more of them may be used in combination.

  When the primer and the adhesive contain (e) a photopolymerization initiator, the (e) photopolymerization initiator contained in the primer and the adhesive may be the same or different.

  (F) The photopolymerization accelerator is not particularly limited, but N, N-dimethyl-p-toluidine, N, N-dimethylaminoethyl methacrylate, triethanolamine, methyl 4-dimethylaminobenzoate, 4-dimethylamino Tertiary amines such as ethyl benzoate and isoamyl 4-dimethylaminobenzoate, barbituric acid, 1,3-dimethylbarbituric acid, 1,3,5-trimethylbarbituric acid, 1,3,5-triethylbarbitur Examples thereof include barbituric acid derivatives such as acid, 5-butyl barbituric acid, 1-benzyl-5-phenylbarbituric acid, 1-cyclohexyl-5-ethylbarbituric acid, and two or more of them may be used in combination.

  When the primer and the adhesive contain (f) a photopolymerization accelerator, the (f) photopolymerization accelerator contained in the primer and the adhesive may be the same or different.

  (G) Although it does not specifically limit as a polymerization inhibitor, 2,6-di-t-butyl-p-cresol, 2,6-t-butyl-2,4-xylenol, etc. are mentioned, 2 or more types combined use May be.

  In addition, when the primer and the adhesive contain (g) a polymerization inhibitor, the (g) polymerization inhibitor contained in the primer and the adhesive may be the same or different.

  (H) The filler may be either an organic filler or an inorganic filler, but is preferably an inorganic filler.

  Although it does not specifically limit as an inorganic filler, A silica powder, glass powder (for example, barium glass powder, fluoroaluminosilicate glass powder) etc. are mentioned, You may use 2 or more types together.

  The inorganic filler may be treated with a surface treatment agent such as a silane coupling agent as necessary.

  EXAMPLES Hereinafter, although an Example and a comparative example are given and this invention is demonstrated in detail, this invention is not limited to an Example.

[Preparation of primer and adhesive]
Primers and adhesives were prepared by mixing the components in the formulations shown in Tables 1 and 2.

  In addition, the meaning of the abbreviation in Table 1 and Table 2 is as follows.

MDP: 10-methacryloyloxydecyl dihydrogen phosphate MEP: 2-methacryloyloxyethyl dihydrogen phosphate MEPP: 2-methacryloyloxyethyl phenyl acid phosphate MENT: 6-methacryloyloxyethyl naphthalene-1,2,6-tricarboxylic acid MET : 4-methacryloyloxyethyl trimellitic acid HEMA: 2-hydroxyethyl methacrylate EDB: ethyl 4-dimethylaminobenzoate 701: 1,3-bis (methacryloyloxy) -2-propanol (manufactured by Shin-Nakamura Chemical Co., Ltd.)
3G: Triethylene glycol dimethacrylate (manufactured by Shin-Nakamura Chemical Co., Ltd.)
NPG: Neopentyl glycol dimethacrylate (manufactured by Shin-Nakamura Chemical Co., Ltd.)
Bis-GMA: 2,2-bis [4- (2-hydroxy-3-methacryloxypropoxy) phenyl] propane Lucillin TPO: Diphenyl (2,4,6-trimethoxybenzoyl) phosphine oxide (manufactured by BASF)
DC: 2,6-di-t-butyl-p-cresol Inorganic filler: R972 silica (manufactured by Nippon Aerosil Co., Ltd.)
Next, the adhesive strength of the (primer and) adhesive was evaluated.

[Adhesive strength]
Under water injection, the surface of the fresh front teeth of the cow was polished using water-resistant abrasive paper # 320 to expose 5 enamels and 5 dentins.

  A primer was applied to the polished tooth, and after 20 seconds, it was dried with medium pressure air for 5 seconds. Next, an adhesive was applied, and after 10 seconds, it was dried with strong air for 5 seconds. Furthermore, light was irradiated in mode F5 from above the mold of ULTRADENT having a diameter of 2.3798 mm using a light irradiator G-Light Prima (manufactured by GC Corporation). Next, after filling clear fill AP-X (manufactured by Kuraray Co., Ltd.) as a composite resin, light is irradiated in mode 20 using a light irradiator G-light prima (manufactured by GC Corporation). The adhesive was cured. Furthermore, after being immersed in water at 37 ° C. overnight, a shear test was performed with a crosshead speed of 1 mm / min, and the average value of the five bond strengths was obtained.

  From Table 1 and Table 2, it can be seen that the primers and adhesives (adhesive set) of Examples 1 to 10 are excellent in adhesive strength.

  On the other hand, since the adhesives of Comparative Examples 1 and 2 do not use a primer, the adhesive strength decreases.

  Since the adhesive of Comparative Example 3 does not contain water and does not use a primer, the adhesive strength decreases.

  Since the adhesive of Comparative Example 4 does not contain a water-soluble organic solvent, it does not mix uniformly and cannot be used as an adhesive.

  Since the primer and adhesive (adhesive set) of Comparative Example 5 do not contain a compound having an acid group and a (meth) acryloyloxy group in the primer, the adhesive strength decreases.

  Since the primer and adhesive (adhesive set) of Comparative Example 6 contain an excessive amount of a compound having an acid group and a (meth) acryloyloxy group in the primer, the adhesive strength decreases.

  Since the primer and adhesive (adhesive set) of Comparative Example 7 do not contain water in the primer, the adhesive strength decreases.

Claims (1)

A dental adhesive set having a primer and an adhesive,
The primer contains 1 to 60% by mass of a compound having an acid group and a (meth) acryloyloxy group, and 1 to 98% by mass of water.
The adhesive contains 1 to 40% by mass of a compound having an acid group and a (meth) acryloyloxy group, 1 to 60% by mass of a water-soluble organic solvent, 1 to 60% by mass of water, and an acid. A dental adhesive set comprising 10 to 90% by mass of a compound having no (meth) acryloyloxy group and having no group.