JP6713819B2 - Dental adhesive set - Google Patents

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.

One aspect of the present invention aims to provide a dental adhesive set capable of improving 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 mass% of a compound having an acid group and a (meth)acryloyloxy group and contains water. 1 to 98% by mass, the adhesive contains 5 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% of water. To 60% by mass, does not have an acid group, and contains 10 to 90% by mass of a compound having a (meth)acryloyloxy group.

According to one aspect of the present invention, it is possible to provide a dental adhesive set capable of improving the adhesive strength.

Next, a mode for carrying out the present invention will be described.

The dental adhesive set has a primer and an adhesive.

Here, the dental adhesive set is used, for example, by sequentially applying the primer and the adhesive to the tooth structure, filling the 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 dental composite resin is filled and irradiated with light to cure the adhesive, which can be used. ..

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

In addition, in this specification and a claim, a (meth)acryloyloxy group means a methacryloyloxy group and/or an acryloyloxy group.

The content of the compound having the (a) acid group and the (meth)acryloyloxy group in the primer is 1 to 60% by mass, and preferably 5 to 30% by mass. When the content of the compound having the (a) acid group and the (meth)acryloyloxy group in the primer is less than 1% by mass or more than 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 more than 98% by mass, the adhesive strength is reduced.

The primer is, if necessary, (b) a water-soluble organic solvent, (d) a compound having no (meth)acryloyloxy group without an acid group, (e) a photopolymerization initiator, and (f) a photopolymerization accelerator. The agent, (g) a polymerization inhibitor and the like may be further contained.

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

The content of the compound having an (a) acid group and a (meth)acryloyloxy group in the adhesive is 1 to 40% by mass, and preferably 5 to 25% by mass. When the content of the compound having an (a) acid group and a (meth)acryloyloxy group in the adhesive is less than 1% by mass, or more than 40% by mass, the adhesive strength decreases.

The content of the water-soluble organic solvent (b) in the adhesive is 1 to 60% by mass, and preferably 25 to 55% by mass. When the content of the water-soluble organic solvent (b) in the adhesive is less than 1% by mass or more than 60% by mass, the adhesive strength decreases.

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 more than 60% by mass, the adhesive strength is lowered.

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. When the content of the compound having no (d) acid group and having a (meth)acryloyloxy group in the adhesive is less than 10% by mass or more than 90% by mass, the adhesive strength is decreased. To do.

It is preferable that the adhesive further contains (e) a photopolymerization initiator, (f) a photopolymerization accelerator, (g) a polymerization inhibitor, and (h) a filler.

The content of the (e) 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 exceeds 5% by mass, the adhesive strength is lowered.

The content of the (f) photopolymerization accelerator 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 (g) polymerization inhibitor 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 (g) polymerization inhibitor 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 mass%, more preferably 2.5 to 9 mass%. When the content of the (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, the materials contained in the primer and the adhesive will be described.

Examples of the acid group in the compound (a) having an acid group and a (meth)acryloyloxy group include a phosphoric acid group, a carboxyl group, and a sulfonic acid group.

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

Examples of the compound having a phosphoric acid group and a (meth)acryloyloxy group include 2-(meth)acryloyloxyethyl dihydrogen phosphate, bis[2-(meth)acryloyloxyethyl]hydrogen phosphate, and 2-(meth)acryloyl. Oxyethyl phenyl acid phosphate, 6-(meth)acryloyloxybutyl acid phosphate, 8-(meth)acryloyloxydecyl acid phosphate, 10-(meth)acryloyloxydecyl dihydrogen phosphate, 3-(meth)acryloyloxypropyl diphosphate Hydrogen phosphate, 4-(meth)acryloyloxybutyl dihydrogen phosphate, 5-(meth)acryloyloxypentyl dihydrogen phosphate, 6-(meth)acryloyloxyhexyl dihydrogen phosphate, 7-(meth)acryloyloxy Heptyl 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)acryloyloxyhexadecyl dihydrogen phosphate, 20-(meth)acryloyloxyicosyl dihydrogen phosphate, 2-(meth)acryloyloxyethyl phenyl hydrogen phosphate, 2-(meth)acryloyloxyethyl-2-bromoethyl hydrogen phosphate, 2-(meth)acryloyloxyethyl-(4-methoxyphenyl)hydrogen phosphate, 2-(meth)acryloyloxypropyl-(4-methoxyphenyl) ) Hydrogen phosphate and the like can be mentioned.

Examples of the compound having a carboxyl group and a (meth)acryloyloxy group include (meth)acrylic acid, 4-(meth)acryloyloxyethyltrimellitic 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)acryloyloxyethylphthalic acid, 2-(meth)acryloyloxyethylhexahydrophthalic 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 and the like can be mentioned.

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

Here, two or more kinds of compounds having an acid group (a) 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.

The compounds having the (a) acid group and the (meth)acryloyloxy group contained in the primer and the adhesive may be the same or different.

(B) The water-soluble organic solvent is not particularly limited as long as it can dissolve the compound (a) having an acid group and a (meth)acryloyloxy group and can improve the wettability with the tooth structure. However, ethanol, acetone, etc. may be mentioned, but two or more kinds may be used in combination.

When the primer contains (b) the water-soluble organic solvent, the (b) water-soluble organic solvent contained in the primer and the adhesive may be the same or different.

The compound (d) having no acid group and having a (meth)acryloyloxy group is not particularly limited, but includes 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(meth)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 Acrylate, trimethylolmethane tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, 2-hydroxyethyl(meth)acrylate, 2-hydroxypropyl(meth)acrylate, 2-hydroxy-1,3-bis[(meth) Acryloyloxy]propane, 2,2-bis[4-(2-hydroxy-3-(meth)acryloyloxypropoxy)phenyl]propane, bis((meth)acryloyloxy)propanol, urethane-containing (meth)acrylate, etc. And two or more kinds may be used in combination.

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

In addition, when the primer does not have a (d) acid group and contains a compound having a (meth)acryloyloxy group, it does not have a (d) acid group or a hydroxyl group contained in the primer and the adhesive, and (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, compounds containing azide group, etc. And two or more kinds may be used in combination.

When the primer and the adhesive contain the (e) 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 is 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-butylbarbituric acid, 1-benzyl-5-phenylbarbituric acid, 1-cyclohexyl-5-ethylbarbituric acid, and two or more kinds thereof may be used in combination.

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

(G) The polymerization inhibitor is not particularly limited, and examples thereof include 2,6-di-t-butyl-p-cresol, 2,6-t-butyl-2,4-xylenol and the like, and two or more kinds thereof are used in combination. You may.

When the primer and the adhesive contain the (g) polymerization inhibitor, the (g) polymerization inhibitor contained in the primer and the adhesive may be the same or different.

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

The inorganic filler is not particularly limited, and examples thereof include silica powder, glass powder (for example, barium glass powder, fluoroaluminosilicate glass powder) and the like, and two or more kinds may be used in combination.

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

Hereinafter, the present invention will be described in detail with reference to Examples and Comparative Examples, but the present invention is not limited to the Examples.

[Preparation of primer and adhesive]
A primer and an adhesive were prepared by mixing the components in the formulations shown in Table 1 and Table 2.

The meanings of the abbreviations in Table 1 and Table 2 are 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: 4-dimethylaminoethyl benzoate 701: 1,3-bis(methacryloyloxy)-2-propanol (manufactured by Shin-Nakamura Chemical Co., Ltd.)
3G: Triethylene glycol dimethacrylate (made 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 fresh bovine front teeth was polished using water-resistant abrasive paper #320 to expose 5 enamel and 5 dentin each.

A primer was applied to the ground tooth material, 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. Further, light was irradiated in mode F5 from above the ULTRADENT mold having a diameter of 2.3798 mm using a light irradiator G-light primer (manufactured by GC Corporation). Next, as a composite resin, after being filled with Clearfil AP-X (manufactured by Kuraray Co., Ltd.), light was irradiated in mode 20 using a light irradiator G-Light Prima (manufactured by GC Co.) (primer and) The adhesive was cured. Furthermore, after immersing in water at 37° C. overnight, a shearing test was carried out at a crosshead speed of 1 mm/min, and the average value of the adhesive strength of 5 pieces was obtained.

From Tables 1 and 2, it can be seen that the primers and adhesives (adhesive set) of Examples 1 to 10 have excellent 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 no primer is used, the adhesive strength is lowered.

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 the 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 is reduced.

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

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

Claims (3)

A dental adhesive set having a primer and an adhesive,
The primer contains 1 to 60 mass% of a compound having an acid group and a (meth)acryloyloxy group, and contains 1 to 98 mass% of water,
The adhesive contains 5 to 40 mass% of a compound having an acid group and a (meth)acryloyloxy group, contains 1 to 60 mass% of a water-soluble organic solvent, contains 1 to 60 mass% of water, and contains an acid. A dental adhesive set containing no group and containing 10 to 90 mass% of a compound having a (meth)acryloyloxy group. The dental adhesive set according to claim 1, wherein the adhesive has a water content of 5 to 60% by mass. The dental adhesive set according to claim 1 or 2, wherein the adhesive has a content of the water-soluble organic solvent of 25 to 55% by mass.