JP5500988B2 - Total etching dental adhesive composition - Google Patents

Description

  The present invention relates to a dental adhesive. In particular, the present invention relates to sealants, orthodontic brackets, anterior composite resins, posterior composite resins, bonded dental silver amalgams; resin cementation using posts, all-metal restorations, ceramics The present invention relates to dental adhesives used in total etching adhesive techniques for the preservation of timber metal restorations, composite resin restorations and ceramic restorations, printing, core foundations, and damaged dentitions.

  The concept of total etching adhesion of enamel and dentin is known. Total etching technique uses phosphoric acid gel to simultaneously etch enamel and dentin to remove the smear layer and create a microcavity that can accept the subsequently applied dental adhesive composition Regarding technology. This acid is completely removed by subsequent air water jet spray cleaning. The capillary opening is sealed with a protective bonding material layer including a resin tag that is fixed to the capillary wall and the resin-impregnated dentin surface.

  However, the total etching technique has a problem that bonding characteristics may deteriorate due to excessive drying of the etched tooth surface (particularly dentin). Self-etching compositions have been proposed to avoid problems associated with separate etching steps and subsequent acid removal and drying. Self-etching compositions typically have an acidic pH of less than 2 and can pass through the smear layer. However, self-etching techniques pose additional problems even when self-curing activators are used for curing. Since dental cement is often inert at the interface with the dental adhesive, bonding and curing cannot occur efficiently.

  The object of the present invention is to avoid problems associated with excessive drying and to obtain improved adhesion to dentin and enamel expressed in terms of shear bond strength at a level of at least 15 MPa, where enamel expressed in terms of shear bond strength Adhesion to quality and adhesion to dentin is to provide a dental adhesive composition for use in total etching adhesion techniques having similar dimensions.

The present invention is a dental adhesive composition having a pH of at least 3,
(A) a polymerizable N-substituted alkylacrylic acid amide monomer or acrylic acid amide monomer;
(B) a water-soluble polymerizable carboxylic acid; and (c) a water-soluble organic solvent,
The dental adhesive composition characterized by including the aqueous solution containing this.

  The present invention is based on the recognition that extremely strong bonding can be achieved based on an aqueous solution that can regulate the moisture on the tooth surface. However, this composition contains a component that efficiently wets the tooth surface at pH 3 in order to form a polymerizable film. Assuming that water is present in the composition, there will be no ester linkages in the composition that undergo hydrolysis during storage.

FIG. 4 shows the adhesion between the composition according to Example 1 and a photocured composite (Spectrum TPH) compared to XP Bond and Prime & Bond NT polymerized in a Spectrum 800 curing unit in a total etching technique, where shear bonding Storage conditions before strength measurement are storage for 24 hours at 37 ° C., and thermocycling at 5 ° C. to 55 ° C. is performed 1800 times. The composition according to Example 1 and a self-curing composite in a total etching technique for photocuring the adhesive layer and self-curing the composite cement after storage for 24 hours / 37 ° C compared to XP Bond and Prime & Bond NT in the total etching technique It is a figure which shows adhesion | attachment with cement (Calibra). Composition according to Example 1 and commercially available self in total etching technique that self-cure the adhesive layer and self-cure the composite cement after storage for 24 hours / 37 ° C compared to XP Bond and Prime & Bond NT in the total etching technique It is a figure which shows adhesion | attachment with the mixture which consists of a hardening activator (Prime & Bond Self-cure Activator), and a self-hardening composite cement (Calibra).

  The dental adhesive composition according to the present invention comprises an aqueous solution. The aqueous solution brings moisture to the tooth structure when the tooth surface is excessively dried in the total etching technique.

  The aqueous solution contains an aqueous medium, a polymerizable component, and optionally an initiator, stabilizer and / or inhibitor. The dental adhesive composition has a pH of at least 3, preferably in the range of 3-9, more preferably at least 4, even more preferably at least 5.

  The aqueous medium includes water and optionally one or more water-miscible organic solvents. Preferably, water is present in an amount of at least 0.5% by weight, in particular 5% to 45% by weight, based on the dental adhesive composition. More preferably, water is present in an amount of 20% to 40% by weight relative to the dental adhesive composition. If the water content is less than 0.5% by weight, the dental adhesive may not be effective in moistening the tooth surface if the surface becomes excessively dry.

  The water-soluble organic solvent can be selected from alcohols and ketones. Specifically, the water-soluble organic solvent can be selected from ethanol, n-propanol, i-propanol, n-butanol, t-butanol, acetone and methyl ethyl ketone. t-Butanol is particularly preferred. The water-soluble organic solvent may be present in an amount of 5% to 45% by weight relative to the dental adhesive composition. More preferably, the water soluble organic solvent may be present in an amount of 8 wt% to 30 wt%.

  The polymerizable component is a polymerizable N-substituted alkylacrylic acid amide monomer or acrylic acid amide monomer, and preferably has the following formula:

Wherein R ₁ and R ₂ independently represent a hydrogen atom or a C ₁ -C ₈ alkyl group; A is a divalent substituted or unsubstituted organic residue having 1 to 11 carbon atoms Wherein the organic residue may contain 1 to 3 oxygen and / or nitrogen atoms; Z is a saturated at least trivalent substituted or unsubstituted C _{1 to} C ₈ A polymerizable N, which may be selected from compounds characterized by one of the following: a hydrocarbon group, representing a saturated at least trivalent substituted or unsubstituted cyclic C ₃ -C ₈ hydrocarbon group; n is at least 3 -Containing substituted alkyl acrylamide monomers or acrylamide monomers.

  Preferably, the polymerizable monomer has the formula:

Wherein R ₁ , R ₂ and R ₄ independently represent a hydrogen atom or a C ₁ -C ₈ alkyl group, mono (meth) acrylamide, bis (meth) acrylamide or poly (meth) It can be acrylamide. Preferably, 1,3-bisacrylamide propane (BAP) or 1,3-bisacrylamide pentane (BAPEN) can be used.

  The water-soluble polymerizable N-substituted alkylacrylic acid amide monomer or acrylic acid amide monomer is present in an amount of 20% to 60% by weight, more preferably 30% to 50% by weight, based on the dental adhesive composition. Can do.

  Preferably, the polymerizable N-substituted alkylacrylic acid amide monomer or acrylic acid amide monomer has a molecular weight of up to 400, more preferably up to 300.

  The polymerizable component also includes a water-soluble polymerizable carboxylic acid that can be selected from the group of monocarboxylic acids or polycarboxylic acids. Specifically, the monocarboxylic acid or polycarboxylic acid is selected from the group of acrylic acid, methacrylic acid, fumaric acid, maleic acid, itaconic acid and mixtures thereof. The water-soluble organic acid may be present in an amount of 3 wt% to 20 wt%, more preferably 5 wt% to 15 wt%, based on the dental adhesive composition.

  Preferably, the water soluble polymerizable carboxylic acid has a molecular weight of up to 400, more preferably up to 300.

  Preferably, the water-soluble polymerizable N-substituted alkylacrylic acid amide monomer or acrylic acid amide monomer and the water-soluble polymerizable carboxylic acid are in a weight ratio of 7: 1 to 1: 1, preferably 5: 1 to 1: 1. Contains.

  The dental adhesive composition according to the present invention may further comprise a polymerization initiator, an inhibitor and / or a stabilizer. The polymerization initiator may be a thermal initiator, a redox initiator or a photoinitiator. The photoinitiator may be camphor quinine / amine and / or acyl phosphine oxide. The inhibitor and / or stabilizer can be selected from hydroquinone, hydroquinone monomethyl ether, di-t-butylcresol, t-butylhydroquinone.

  In certain embodiments, the dental adhesive composition may further comprise nanofillers having an average particle size in the range of 1 nm to 100 nm, preferably 1 nm to 10 nm.

  In other specific embodiments, the dental adhesive composition may further include a fluoride-containing compound.

In a preferred embodiment, the dental adhesive composition is basically:
(A) a polymerizable N-substituted alkylacrylic acid amide monomer or acrylic acid amide monomer;
(B) a water-soluble polymerizable carboxylic acid; and (c) a water-soluble organic solvent,
And optionally, fillers, fluoride-containing compounds, initiators, stabilizers and / or inhibitors.

  The dental adhesive composition provides adhesion to dentin and enamel expressed in terms of shear bond strength at a level of at least 15 MPa, wherein adhesion to dentin expressed in terms of shear bond strength is expressed in terms of shear bond strength. Preferably, the adhesion to the enamel is at least 50%, more preferably at least 70%.

  The invention will now be illustrated with reference to the following non-limiting examples.

[Example]
Preparation Example 1, Preparation Example 2 and Preparation Example 3
The following dental adhesive composition was prepared. The composition had a pH of 5.5-7.

  The mixture is a clear solution with low viscosity suitable for use in the total etching method. The composition provides excellent wetting properties of the tooth surface even when the tooth surface is excessively dried. Since no ester bond is present, the storage stability of the composition is excellent.

[Example 2]
Direct Restoration The compositions according to Examples 1, 2 and 3 were applied to the tooth surface and photocured. The tooth surface was either enamel or dentin. For Example 1, excessively dried dentin was also examined. Prior to application of the adhesive composition, the tooth surface was etched with a conventional phosphoric acid gel.

  A commercial photocured composite (Spectrum TPH, shade 2, Dentsply) was applied to the photocured surface of the adhesive.

  Shear bond strength was measured. The results were compared to the shear bond strength obtained using commercially available adhesive compositions XP Bond and Prime & Bond NT. The results are shown in FIGS.

[Example 3]
Indirect restoration The composition according to Example 1 was applied to the tooth surface and photocured. The tooth surface was either enamel or dentin. Prior to application of the adhesive composition, the tooth surface was etched with a conventional phosphoric acid gel.

  A commercially available self-curing composite (Calibra) was applied to the photocured surface of the adhesive.

  Shear bond strength was measured. The results were compared to the shear bond strength obtained using commercially available adhesive compositions XP Bond and Prime & Bond NT. The results are shown in FIG.

  A mixture of the composition of Example 1 and Prime & Bond NT self-cure activator (SCA) was applied to the tooth surface and allowed to self cure. The tooth surface was enamel or dentin. Prior to application of the adhesive composition, the tooth surface was etched with a conventional phosphoric acid gel.

  A commercially available self-curing composite (Calibra) was applied to the self-curing surface of the adhesive.

  Shear bond strength was measured. The results were compared to the shear bond strength obtained using commercial Prime & Bond NT in conjunction with Prime & Bond NT's Self-Cure Activator (SCA). The results are shown in FIG.

Claims (17)

A dental adhesive composition having a pH of at least 3 used in a total etching adhesion technique,
(A) a polymerizable N-substituted alkylacrylic acid amide monomer or acrylic acid amide monomer;
(B) a water-soluble polymerizable carboxylic acid selected from the group consisting of acrylic acid, methacrylic acid, itaconic acid and mixtures thereof ; and (c) an aqueous solution containing a water-soluble organic solvent. Adhesive composition. The polymerizable N-substituted alkylacrylic acid amide monomer or acrylic acid amide monomer has the following formula:

Wherein R ₁ and R ₂ independently represent a hydrogen atom or a C ₁ -C ₈ alkyl group; A represents a divalent substituted or unsubstituted organic residue having 1 to 11 carbon atoms. Wherein the organic residue may contain 1 to 3 oxygen and / or nitrogen atoms; Z is a saturated at least trivalent substituted or unsubstituted C _{1 to} C ₈ hydrocarbon A group or a saturated at least trivalent substituted or unsubstituted cyclic C _{3 to} C ₈ hydrocarbon group; n is at least 3)
The dental adhesive composition according to claim 1, characterized by one of the following: The dental adhesive composition according to claim 1 or 2 , wherein the water-soluble organic solvent is selected from alcohols and ketones. The dental adhesive composition according to claim 3 , wherein the water-soluble organic solvent is selected from ethanol, n-propanol, i-propanol, n-butanol, t-butanol, acetone and methyl ethyl ketone. The dental adhesive composition according to any one of claims 1 to 4 , wherein the water-soluble polymerizable N-substituted alkylacrylic acid amide monomer or acrylic acid amide monomer is present in an amount of 20 wt% to 60 wt%. . The dental adhesive composition according to any one of claims 1 to 5 , wherein the water-soluble organic acid is present in an amount of 3 wt% to 20 wt%. The dental adhesive composition according to any one of claims 1 to 6 , wherein the water-soluble organic solvent is present in an amount of 5 wt% to 45 wt%. The dental adhesive composition according to any one of claims 1 to 7 , wherein water is present in an amount of 0.5% to 45% by weight. The dental adhesive composition according to any one of claims 1 to 8 , wherein the component (a) and the component (b) are contained in a weight ratio of 7: 1 to 1: 1. The polymerizable monomer has the following formula:

(Wherein R ₁ , R ₂ and R ₄ independently represent a hydrogen atom or a C ₁ -C ₈ alkyl group) mono (meth) acrylamide, bis (meth) acrylamide or poly (meth) acrylamide The dental adhesive composition according to any one of claims 1 to 9 . The dental adhesive composition according to any one of claims 1 to 10 , wherein the polymerizable N-substituted alkylacrylic acid amide monomer or acrylic acid amide monomer has a molecular weight of at most 400. The dental adhesive composition according to any one of claims 1 to 11 , wherein the water-soluble polymerizable carboxylic acid has a molecular weight of at most 400. The dental adhesive composition according to any one of claims 1 to 12 , further comprising a polymerization initiator, an inhibitor and / or a stabilizer. The dental adhesive composition according to any one of claims 1 to 13 , wherein the polymerization initiator is a thermal initiator, a redox initiator, or a photoinitiator. The dental adhesive composition according to claim 14 , wherein the photoinitiator is acylphosphine oxide and / or camphorquinone / amine. The dental adhesive composition according to any one of claims 1 to 15 , further comprising a nanofiller. The dental adhesive composition according to any one of claims 1 to 16 , further comprising a fluoride compound.

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