JPH08143415A - Bonding composition for dental use - Google Patents

Abstract

PURPOSE: To obtain a bonding composition for dental use, containing a potassium salt having desensitizing actions and a polymerizable monomer in combination, capable of moderating the pain caused during and after treatment of teeth and having the adhesiveness. CONSTITUTION: This bonding composition for dental use is obtained by combining a potassium salt having desensitizing actions with a polymerizable monomer or further with an aqueous medium or a polymerization initiator. A potassium salt selected from potassium chloride, potassium fluoride, potassium nitrate, potassium sulfate, potassium carbonate, potassium benzoate and potassium oxalate is preferred as the potassium salt. An acrylic or a methacrylic ester is preferred as the polymerizable monomer. When an aqueous medium is added to a system comprising the potassium salt and polymerizable monomer, a dentinal bonding primer composition is obtained. When the polymerization initiator is added to the system, a curable composition is obtained. The restoring treatment of teeth and treatment of pain in dental pulp or hyperethesia can integrally be carried out.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a composition having a blunting action and an adhesive property, which is used for dental treatment.

[0002]

BACKGROUND OF THE INVENTION In the field of dental treatment, hypersensitivity and pulpal pain are clinically problematic stimuli for teeth. Hypersensitivity is a disease that causes transient pain caused by the action of cold air, cold water, or scratching stimuli on the surface of gingival recession or worn dentin, and pulpal pain is caused by cavity formation or composite resin. Pain that occurs intermittently or continuously after amalgam filling and its operation, and is considered to be caused by compression irritation caused by irritation of the dental pulp by the restorative material or by mating. For the treatment of such hypersensitivity, a method of applying silver nitrate, zinc chloride, sodium fluoride, silver fluoride diamine, formaldehyde, strontium chloride, steroid, etc. is adopted, and a treatment method for dental pulp pain is If it is still established, and if symptoms occur or there is a possibility of that, there is a lining material for protecting the pulp such as calcium hydroxide preparation, zinc oxide eugenol cement, glass aionmer cement, and carboxylate cement. in use.

However, these methods have a problem that the pulp is strongly irritated, gingival corrosion and dentin blackening are likely to occur, and the effect is uncertain and the effect is not long-lasting. There is.

Further, since these methods are performed separately from the restoration treatment of the dentine or the adhesion to the dentin is insufficient, the treatment operation is troublesome and reliable adhesion restoration is performed by such a method. There is also a problem that treatment cannot be performed.

In addition to the above method, as a method for desensitizing hypersensitive dentin, for example, Japanese Patent Publication No. 61-501.
Japanese Patent No. 389 discloses applying potassium bicarbonate or potassium chloride to hypersensitive teeth in order to reduce sensory nerve activity of the hypersensitive teeth of a subject. It has been shown that such a potassium salt is used as an aqueous solution or is mixed with a toothpaste, chewing gum or the like. However, the use of such potassium salts for desensitizing hypersensitive toothache during dental treatment is not disclosed.

Further, in Japanese Patent Laid-Open No. 5-255029, an aqueous solution A containing a phosphate and a fluoride and a water-soluble calcium salt such as calcium chloride are contained so that fluoroapatite is produced by mixing. A composition for treating a tooth surface, which is used by mixing with an aqueous solution B, is disclosed. That is, in this composition, phosphate ions, fluorine ions, and calcium ions are reacted on the tooth surface to generate fluoroapatite, and the apical pores of the narrow canals or root canals are blocked. Therefore, the component used here is a component capable of forming fluoroapatite by mixing, and the component used here is limited to a component capable of supplying fluorine ion, phosphate ion and calcium ion. .

JP-A 1-279815 discloses a tooth surface treating agent for treating a dentin surface containing an organic carboxylic acid, a metal chloride and water. Here, it is disclosed that potassium chloride, calcium chloride or the like is used as the metal chloride. However, this tooth surface treatment agent is used when treating dental caries using a filling / restoring material, etc.
It is a pretreatment agent used for improving the adhesive strength between the tooth substance and the filler, and there is no description about such a tooth substance treating agent desensitizing toothache.

Further, JP-A-62-249620 and JP-A-4-24-2
1618 and Japanese Patent Publication No. 5-39995 disclose a dental adhesive or a tooth pain sedative using N-methacryloylaminosalicylic acid as a polymerizable monomer having a pain suppressing effect. Although the pain control effect in this proposal has the advantage that it is performed at the same time as dental restoration, the pain control effect is still insufficient. It is presumed that these pain suppressors are polymerizable monomers, so that after the polymerization effect thereof, the effect is drastically reduced and the pain continuing after the operation cannot be sedated sufficiently.

Further, Japanese Patent Application Laid-Open No. 4-273805 discloses an adhesive containing salicylic acid or a salicylic acid derivative having no polymerizability. However, the sedative effects of salicylic acid and salicylic acid derivatives and their persistence were not sufficient.

[0010]

OBJECT OF THE INVENTION It is an object of the present invention to provide a dental adhesive composition capable of blunting toothache.

A further object of the present invention is to provide an adhesive composition which can relieve the pain generated during and after the treatment of teeth.

[0012]

SUMMARY OF THE INVENTION The dental adhesive composition of the present invention comprises a potassium salt [A] having a desensitizing effect and a polymerizable monomer [B].
It is characterized by containing and.

As the potassium salt which is the compound [A] having the desensitizing action, potassium chloride, potassium fluoride, potassium nitrate, potassium sulfate, potassium carbonate, potassium hydrogen carbonate, potassium benzoate and potassium oxalate are preferable. .

Since the dental adhesive composition of the present invention contains the potassium salt [A] having a desensitizing effect and the polymerizable monomer [B], it can be used as a tooth filling material and tooth substance. It is possible to desensitize irritable toothache and the like while adhering.

Therefore, by using the dental adhesive composition of the present invention, dental pulp pain or hyperesthesia can be treated integrally with the dental restorative treatment during or after the restorative treatment of the tooth.

[0016]

DETAILED DESCRIPTION OF THE INVENTION First, the dental adhesive composition of the present invention will be specifically described. The dental adhesive composition of the present invention contains a potassium salt [A] having a desensitizing effect and a polymerizable monomer [B].

As the potassium salt [A] having a desensitizing effect used in the present invention, it is possible to use either organic or inorganic potassium salt. Further, among various potassium salts, preferable examples of the potassium salt used as the potassium salt [A] having a desensitizing effect in the present invention include potassium chloride, potassium fluoride, potassium nitrate, potassium sulfate, potassium carbonate, and carbonic acid. Mention may be made of potassium hydrogen, potassium benzoate and potassium oxalate. Such potassium salt is particularly excellent in desensitizing action. Such potassium salts can be used alone or in combination. As the potassium salt, a part or all of the acidic group-containing polymerizable monomer described in the polymerizable monomer [B] may be a potassium salt.

The potassium salt [A] having such a desensitizing effect is usually used by dissolving or dispersing in an aqueous medium [C]. As the aqueous medium [C] used here, water and a solvent having a specific boiling point can be used. Examples of such a solvent include a volatile organic solvent having a boiling point of 200 ° C. or less at room temperature and atmospheric pressure. Examples of such volatile organic solvents include:
Alcohols such as methanol, ethanol, allyl alcohol, isopropanol, 1-octanol; ketones such as acetone, methyl ethyl ketone and phorone;
Ethers such as ethyl ether, 1,4-dioxane and diethylene glycol; esters such as ethyl acetate, butyl acetate and 2-ethylhexyl acetate; and hexane, undecane, toluene, xylene, methylene chloride, 1,2-dichloroethane and 1 Examples include 1,1,2,2-tetrachloroethane and the like. Water or the above volatile organic solvent may be used alone or as a mixture, and further, a mixed solvent of water and the above volatile organic solvent may be used.

The volatile organic solvent is preferably alcohol, particularly preferably ethanol, and this ethanol is used alone or as a mixed solvent with water. Particularly, as the potassium salt [A] having the desensitizing effect,
When the potassium salt is used, water or a water-ethanol mixed solvent is preferable as the aqueous medium.

The concentration of the potassium salt [A] having the desensitizing effect in the aqueous medium [C] is not particularly limited, but is usually 0.1 to 95% by weight, preferably 1 to 75%.
It is used in a concentration of% by weight, more preferably 3 to 50% by weight. When used at such a concentration, the potassium salt [A] having a desensitizing effect penetrates well into the tooth structure, so that toothache can be alleviated in a short time, and
The desensitizing effect that has developed persists.

The dental adhesive composition of the present invention contains a polymerizable monomer [B]. Examples of the polymerizable monomer [B] used in the present invention include (meth) acrylic acid ester,
Mention may be made of vinyl esters such as (meth) acrylic acid amide, maleic acid ester, fumaric acid ester and vinyl acetate, styrene and its derivatives, and vinyl compounds such as acrylonitrile and acrolein. Among these, (meth) acrylic acid ester is preferable.

Examples of the (meth) acrylic acid ester preferably used in the present invention include methyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, ethylene glycol di (meth) acrylate and triethylene glycol di (meth). ) Acrylate, neopentyl glycol di (meth) acrylate, 2,2-bis [4- (3-methacryloyloxy-2-hydroxypropoxy) phenyl] propane (Bis-GMA), trimethylolethane tri (meth) acrylate, penta Mention may be made of erythritol tetra (meth) acrylate, pentaerythritol tri (meth) acrylate and N, N-dimethylaminoethyl methacrylate.

These polymerizable monomers [B] can be used alone or in combination. Further, in the present invention, as the polymerizable monomer,

[0024]

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At least one polar group represented by:
An acidic polymerizable monomer having at least one olefinic double bond can also be used. Examples of such acidic polymerizable monomers include the compounds described below.

[0026]

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[0027]

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[0028]

[Chemical 4]

[0029]

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[0030]

[Chemical 6]

Further, as the polymerizable monomer [B], a hydroxyl group such as glyceryl mono (meth) acrylate, pentaerythritol mono (meth) acrylate, mesoerythritol mono (meth) acrylate and xylitol mono (meth) acrylate. An acrylate compound having a can be used.

The above acrylate compounds may be used alone or in combination. Such a polymerizable monomer [B] is the same as the potassium salt [A] having a desensitizing effect in the aqueous medium [C] in which the potassium salt [A] having a desensitizing effect is dissolved or dispersed. It can be used after being dissolved or dispersed in.

The concentration of the above polymerizable monomer [B] in the aqueous medium [C] is not particularly limited, but it is usually 1 to
It is used in a concentration of 99.9% by weight, preferably 3 to 75% by weight, more preferably 5 to 50% by weight. When used at such a concentration, the polymerizable monomer [B] is well dispersed on the tooth surface and at the same time, part of the polymerizable monomer [B] is well penetrated into the tooth structure. , The adhesiveness is improved, and the desensitizing effect that has been further developed lasts.

In the dental adhesive composition of the present invention, the compounding ratio of the above-mentioned potassium salt [A] having a desensitizing action and the polymerizable monomer [B] is 1: 1 to 1 by weight. : 10
Is more preferable, and it is particularly preferable that it is in the range of 1: 2 to 1: 8. By using the potassium salt [A] having a desensitizing effect and the polymerizable monomer [B] in an amount within the above range, the balance between the effects of adhesiveness and desensitizing is improved. .

The dental adhesive composition of the present invention is prepared by dissolving or dispersing the potassium salt [A] having a desensitizing effect and the polymerizable monomer [B] in the aqueous medium [C] as described above. It can be used as a dental adhesive primer composition, and also with or without an aqueous medium [C], a potassium salt [A] and a polymerizable monomer [A] having a desensitizing action. A polymerization initiator [D] may be blended with B] and used as a curable composition.

The polymerization initiator [D] used here is a mixture of benzoyl peroxide-aromatic tertiary amines and peroxides such as cumene hydroperoxide; tributylborane, aromatic sulfinic acid (or Examples thereof include salts thereof) -aromatic secondary or tertiary amine-acyl peroxide-based mixtures, and the like. Furthermore, α
-Diketones (e.g. camphorquinone, diacetyl,
Benzyl) -reducing agents (eg tertiary amines, aldehydes, mercaptans) and photopolymerization initiators such as benzoin methyl ether can be mentioned.

The blending amount of such a polymerization initiator varies depending on the kind thereof, but is usually 0.01 to 50 parts by weight, preferably 0.1, with respect to 100 parts by weight of the polymerizable monomer [B].
~ 40 parts by weight.

The dental adhesive composition of the present invention comprises a potassium salt [A] having a desensitizing effect as described above, a polymerizable monomer [B], and optionally an aqueous medium [C] or a polymerization initiator. Although it contains [D], the dental adhesive composition of the present invention may contain other components to be blended with a usual dental adhesive, in addition to the above components.

Examples of other components to be incorporated in the dental adhesive composition of the present invention include fillers,
Specific examples of this filler include glass, quartz, hydroxyapatite, calcium carbonate, barium sulfate,
Besides inorganic fillers such as aluminum oxide, titanium oxide and zirconium oxide, polymer powders such as polymethylmethacrylate powder, polystyrene powder and polyvinyl chloride powder can be mentioned.

The compounding amount of such a filler varies depending on the kind, but is usually 1 to 90 parts by weight, preferably 5 to 75 parts by weight with respect to 100 parts by weight of the polymerizable monomer [B].

The dental adhesive composition of the present invention comprises a potassium salt [A] having a desensitizing effect and a polymerizable monomer [B]. The dental adhesive composition is, for example, as follows. Can be used in various ways.

Potassium salt having a desensitizing effect [A]
And a polymerizable monomer [B] are dissolved or dispersed in an aqueous medium [C], the treatment liquid is applied to the tooth structure, and the surface of the tooth structure is dried by air blowing, and the excess treatment is performed. Remove the liquid. Next, a composite resin containing a reaction curing agent for the polymerization initiator [B] is built up on this treatment liquid to bond the composite resin and the tooth structure.

The dental adhesive composition used as described above is easy to handle because it is a one-pack type, and it can be used without any practical problem in storage stability.

Further, the dental adhesive composition of the present invention is prepared by adding a reaction initiator [D] to a mixture of a potassium salt [A] having a desensitizing action and a polymerizable monomer [B]. And apply to the surface of the tooth substance dried by air blow. Next, a composite resin is built up on this application surface to bond the tooth surface and the composite resin or amalgam. In this case, the package of the reaction initiator [D] and the package of the dental adhesive of the present invention are separately stored, and both are mixed immediately before use.

Further, the dental adhesive composition of the present invention containing such a reaction hardening agent is applied to a portion of the tooth surface where the tooth is worn, a portion where the gingiva is retracted, etc.
It can be used for the treatment of hyperesthesia, etc. in addition to the restoration of teeth with composite resin or amalgam.

As described above, by using the dental adhesive composition of the present invention, it is possible to treat teeth and at the same time treat hyperesthesia or pulpal pain.

[0047]

The dental adhesive composition of the present invention comprises a potassium salt [A] having a desensitizing effect and a polymerizable monomer [B].
Since it contains, it is possible to desensitize hypersensitive toothache and the like while adhering the tooth substance and the like to the tooth substance.

Therefore, by using the dental adhesive composition of the present invention, the tooth restoration treatment and the treatment of hyperesthesia or pulp pain, which have been conventionally performed individually, can be performed during or after tooth restoration treatment. It can be performed after the treatment together with the dental restoration treatment, which facilitates the treatment and reduces the pain of the patient. Furthermore, since the potassium salt [A] having a desensitizing effect is contained in the adhesive composition which is directly applied to the surface of the tooth when filling the composite resin or the like, this compound penetrates into the tooth. Since the tooth substance surface is covered with the post-polymerizable monomer, the potassium salt [A] having a desensitizing action is less likely to flow out, and the effect is permanent.

[0049]

The contents of the present invention will be described in more detail with reference to the following examples, but the present invention is not limited to these examples.

[0050]

Examples 1 to 3 As a primer of the present invention, for cavity dentin of a patient having pain after cavity formation of vital teeth,
2.5% potassium nitrate (KNO ₃ ), potassium chloride (K
Cl) or potassium sulfate (K ₂ SO ₄ ), 2.5% sodium p-toluenesulfonate, 5%
Ethylene glycol dimethacrylate (n = 23,2
3G) A solution consisting of 10% 4-methacryloyloxyethyl trimellitic acid (4-META), 45% distilled water and 35% methanol was prepared and applied immediately before use (applied amount about 25 mg). Dry with an air syringe until the surface lightly shines, apply the bonding material shown in Table 1 and blow with air, and then use a commercially available composite resin (SILUX PLU
S). The composite resin was irradiated with visible light for 30 seconds to cure. Through the series of treatments, the pain disappeared and did not occur even after the operation.

[0051]

[Examples 4 to 6] The labial surface of the bovine front tooth was rotated by a rotary polishing machine (BUEH
Water was applied using ECOMET III) manufactured by LER, and polished with water-resistant emery paper No. 600 under finger pressure to obtain a smooth surface of dentin.

After drying the surface with an air syringe, the adhesion surface area was defined and the primer of the present invention shown in Table 1 was applied. Dry with an air syringe until the surface lightly shines and then Table 1
After applying the bonding material described in 1 above and blowing air, the bonding material was cured by irradiating with a visible light irradiator for 20 seconds. Commercially available composite resin (SILUX PLUS) by placing an acrylic ring with a diameter of 6 mm on this treated part
Was filled. The composite resin was irradiated with visible light for 30 seconds to cure. After soaking in 37 ° C water for 24 hours,
2 mm / min using an autograph (Shimadzu Corporation)
The tensile test was performed at the crosshead speed of.

As a result, the adhesive strength was 12 in both cases.
It showed a high value of MPa or more.

[0054]

[Examples 7 to 9] 10% containing 3% ferric chloride to cavity dentin of a patient having pain after cavity formation of vital tooth
It was treated with an aqueous citric acid solution for 10 seconds and washed with water for 15 seconds. After thoroughly drying with an air syringe, 3% potassium carbonate (K ₂ CO ₃ ), potassium hydrogen carbonate (KHCO ₃ ).
Alternatively, any one kind of KCl, 35% 2-hydroxyethyl methacrylate (HEMA) and 62% distilled water was applied to the primer composition of the present invention (applied amount about 25 mg). The surface was dried with an air syringe until the surface lightly shined, the bonding material shown in Table 1 was applied, and air blowing was performed, and then a commercially available composite resin (SILUX PLUS) was filled. The composite resin was irradiated with visible light for 30 seconds to cure. After a series of treatments, the pain disappeared and did not occur even after the operation.

[0055]

[Examples 10 to 12] The labial surface of bovine anterior teeth was water-polished with a rotary polishing machine (BUEHLER, ECOMET III), and was ground under water pressure using a water-resistant emery paper No. 600 to obtain a smooth surface of dentin. Obtained. 10% of this dentin surface containing 3% ferric chloride
It was treated with an aqueous citric acid solution for 10 seconds and then washed with water for 15 seconds. After sufficiently dried with an air syringe, the primer of the present invention shown in Table 1 was applied. The surface was dried with an air syringe until the surface lightly shines, the bonding material shown in Table 1 was applied to this surface, and air blowing was performed, and then a commercially available composite resin (SILUX PLUS) was filled. The composite resin was irradiated with visible light for 30 seconds to cure. The sample thus prepared was immersed in water at 37 ° C. for 24 hours, and then, using an autograph (manufactured by Shimadzu Corporation), 2 mm /
A tensile test was performed at a crosshead speed of min.

As a result, the adhesive strength was 15 in both cases.
An extremely high value of MPa or more was shown.

[0057]

Examples 13 to 15 According to the above-mentioned Examples 1 to 3, the cavity dentin of a patient was filled with the composite resin. However,
The compound (A) having a desensitizing effect of the present invention was incorporated into the bonding material without being incorporated into the primer. After a series of treatments, the pain disappeared and did not occur even after the operation.

[0058]

Examples 16 to 18 Adhesion tests of the composite resins used in Examples 13 to 15 were conducted according to Examples 4 to 6 above. As a result, the adhesive strength was a high value of 10 MPa or more.

[0059]

Examples 19 to 20 According to the above Examples 7 to 9, the cavity dentin of the patient was filled with the composite resin. However,
The compound (A) having a desensitizing effect of the present invention was incorporated into the bonding material without being incorporated into the primer. After a series of treatments, the pain disappeared and did not occur even after the operation.

[0060]

Examples 21 to 22 Adhesion tests of the composite resins used in Examples 13 to 15 were conducted according to Examples 10 to 12 above. As a result, the adhesive strength was a high value of 10 MPa or more.

[0061]

Comparative Example 1 The cavity dentin of a patient was filled with the composite resin according to the method of Examples 1 to 3. However, the compound (A) having the desensitizing effect of the present invention was not mixed in the primer and the bonding material. Pain remained immediately after the series of treatments. However, the pain disappeared after a few days.

[0062]

[Comparative Example 2] An adhesion test was conducted according to Examples 4 to 6 above. As a result, the adhesive strength was a high value of 10 MPa or more. Therefore, Examples 1 to 3 or Examples 13 to 15
As is clear from a comparison with the effect of the present invention in the present invention, according to the present invention, the decrease in adhesive strength due to the addition of the potassium salt is not seen, it is possible to suppress the pain immediately after the treatment by adding the potassium salt. Suggested.

[0063]

Comparative Example 3 According to the method of Examples 7 to 9, the cavity dentin of a patient was filled with the composite resin. However, the compound (A) having the desensitizing effect of the present invention was not mixed in the primer and the bonding material. Pain remained immediately after the series of treatments. However, the pain disappeared after a few days.

[0064]

[Comparative Example 4] An adhesion test was performed according to Examples 10 to 12 above. However, the compound (A) having the desensitizing effect of the present invention was not mixed in the primer and the bonding material. As a result, the adhesive strength was a high value of 10 MPa or more. Therefore, as is clear from the comparison with the effects of the present invention in Examples 7 to 9 or Examples 19 and 20, according to the present invention, the decrease in adhesive strength due to the addition of the potassium salt was not observed, and It was suggested that the combination could reduce the pain immediately after the treatment.

The compositions of the primers and bonding materials used in the above Examples and Comparative Examples, and the presence or absence of pain and the measured adhesive strength to bovine teeth are summarized in Tables 1 (A) and (B).

[0066]

[Table 1]

[0067]

[Table 2]

Meanings of symbols other than the chemical symbols used in the above Tables 1 (A) and (B) are as follows. 3G: triethylene glycol dimethacrylate.

23G: Polyethylene glycol dimethacrylate (average addition amount of ethylene glycol is 23). 2.6E: Dimethacrylate of ethylene oxide adduct of bisphenol (average value of total addition amount of ethylene oxide 2.6).

VR90: Bisphenol A type epoxy acrylate represented by the following formula;

[0071]

[Chemical 7]

4-META: 4-methacryloyloxyethyl trimellitic anhydride. CQ: d, l-camphaquinone. DEABA: N, N-diethylaminobenzoic acid.

TBB: tri-n-butylborane (partial oxide, manufactured by Sun Medical Co., Ltd.) p-TSNa: sodium paratoluenesulfinate.

Claims (5)

[Claims] 1. A potassium salt [A] having a desensitizing effect.
And a polymerizable monomer [B]. 2. A potassium salt [A] having a desensitizing effect.
Is at least one kind of potassium salt selected from the group consisting of potassium chloride, potassium fluoride, potassium nitrate, potassium sulfate, potassium carbonate, potassium benzoate and potassium oxalate. Dental adhesive composition. 3. The dental adhesive composition according to claim 1, wherein the polymerizable monomer [B] contains a (meth) acrylic acid ester. 4. A dental adhesive composition is a dentin adhesive primer composition containing a potassium salt [A] having a desensitizing action, a polymerizable monomer [B] and an aqueous medium [C]. The dental adhesive composition according to any one of claims 1 to 3, wherein: 5. A dental adhesive composition comprising a potassium salt [A] having a desensitizing effect and a polymerizable monomer [B].
The dental adhesive composition according to any one of claims 1 to 3, which is a curable composition having a polymerization initiator [D].