JP4646264B1 - Dental curable composition - Google Patents

Abstract

【Task】
Provided is a dental curable composition which does not require refrigerated storage and has no long-term storage stability even when stored at room temperature for a long period of time, and has excellent long-term storage stability.
[Solution]
An agent A containing an acidic compound (a) and one or more selected from group IIa elements, tin, lead, or bismuth compounds, or salts thereof, or glass containing them (b) , An organic peroxide obtained by mixing a polymerizable monomer (c) having no acidic group, an aromatic sulfinate (d), and a B agent containing a tertiary amine (e) Curable compositions for dental use such as cement for cement, temporary cement, bonding agent, sealer for filling root canal, and composite resin for building and filling abutment.
[Selection figure] None

Description

The present invention relates to a dental curable composition having excellent storage stability used for tooth restoration, correction, and root canal filling.
More specifically, a cement for cementing, which is based on a chemical polymerization and dual cure type adhesive resin, which does not use organic peroxides, and therefore does not cause a delay in curing time even after long-term storage at room temperature. The present invention relates to a cement, a bonding agent, a root canal sealer, and a composite resin for abutment construction and filling.

(1) Cementing cement In the restoration treatment for caries with defects in the tooth structure, the cementing cement is a restoration material (for example, composite resin, metal, ceramics) that fills the defect and restores it aesthetically and functionally. And other orthodontic restoration materials (metal brackets and ceramic brackets) are used in daily clinical practice to adhere to the tooth. Adhesive resin cement is widely used as a material capable of firmly adhering a metal or ceramic prosthesis to a tooth. Resin cement using a chemical polymerization initiator is used to bond a prosthesis or orthodontic bracket that does not transmit light like metal. These are collectively referred to as a chemical polymerization type because of their polymerization modes, and those that also use a photopolymerization initiator are referred to as a dual cure type.
(2) Temporary cement Also, for the purpose of confirming whether the patient can be satisfied with the periodontal tissue, occlusion, aesthetics, etc., for the final prosthesis (crown or bridge), only for a temporary period. There are temporary cements used for Since the temporary cement is assumed to be removed, the adhesive strength is low or may not be bonded.

(3) Bonding agent Further, a bonding agent (liquid agent) having a composition in which the filler (filler) component is reduced or eliminated from the above composition may be used in order to firmly bond the composite resin or resin cement to the teeth.
(4) Sealer for root canal filling Furthermore, in dental treatment when bacteria reach the pulp and apical periodontal tissues, the root canal after pulp extraction is filled with a material that is materially stable. Root canal treatment is widely performed to block the gap between the root canal and periodontium, and to block the infection route between the root canal and the oral cavity. The most commonly used method at the time of performing this procedure is to fill the root canal after extraction with a thin needle-like root canal filling material called gutta percha point mainly composed of gutta percha and zinc oxide. It is a method of blocking with. In the root canal filling method using the gutta-percha points, a method called a lateral pressure filling method in which a plurality of gutta-percha points are sequentially filled in the root canal is generally performed.
However, since the gutta-percha point has insufficient adhesion to the root canal wall, a material called a root canal filling sealer is applied to the gutta-percha point and then filled into the root canal, and the gap between the root canal wall and the gutta-percha point It has been done to improve the blockade by filling.
A widely used sealer for root canal filling is zinc oxide / eugenol cement mainly composed of zinc oxide and eugenol. However, since there is no adhesion to the root canal wall, there is a drawback that the sealing ability of the root canal is not sufficient in clinical practice. Recently, in order to improve the sealing property, a product in which the above adhesive resin cement is applied to a sealer for filling a root canal is known. A chemical polymerization type is used as a root canal filling sealer that hardly transmits light to the apex, but there is also a dual cure type.
(5) Composite resin for abutment construction As a restoration treatment after root canal filling, if there is a substantial loss of the remaining teeth in the crown, and only the root remains, construct the abutment tooth form. Work to reinforce the holding force, that is, abutment construction is performed. As one method, a post is inserted into the root canal and planted, and the abutment construction is performed by a composite resin. The composite resin that has been built and hardened is cut into a shape suitable for crown bonding by a turbine to form an abutment tooth and used as an abutment tooth. When this planting post is made of metal, a part of the root canal or the bottom of the fossa where light does not reach is generated. Therefore, the composite resin for abutment construction is preferably a dual cure type.
(6) Filling and Restoring Material As a filling and restorative material for the cavity, composite resin is used not only for the front teeth but also for the molars. However, materials having no hardening delay are also useful.
Since a part of the root canal and the bottom of the fossa where light does not reach is generated, it is desirable that the composite resin for filling and repairing and for abutment construction be a dual cure type.

Adhesive resin cements and root canal filling sealers are basically composed of a polymerizable monomer (monomer) component having an acidic group, a polymerizable monomer (monomer) component having no acidic group, and a filler (filler). ) Component, and a polymerization initiator, powder, liquid, and paste-paste agent, and various material properties are expressed by polymerization of the polymerizable monomer.
In a dental material, in order to express various intended material properties, it is necessary that the polymerizable monomer is sufficiently polymerized in the oral cavity.

As these dental materials, various (meth) acrylic acid esters and derivatives thereof are generally used, and for the polymerization and curing, a redox chemical polymerization initiator composed of an organic peroxide and a reducing agent is used. In addition, a photopolymerization initiator that generates radicals by light irradiation is used.
These are generally divided into two agents, A agent and B agent. Agent A is a powder containing an organic peroxide or a paste (or liquid) in which an organic peroxide is mixed with a polymerizable monomer, and Agent B is a powder containing a tertiary amine as a reducing agent. Or a paste (or liquid) in which a polymerizable monomer is added thereto, and the agent A and the agent B are mixed at the time of use to obtain a curable paste (or liquid). However, benzoyl peroxide, which is typically used as an organic peroxide, gradually decomposes when mixed with (meth) acrylate monomers and other organic compounds, so in liquids or pastes containing organic peroxides It is cured (solidified) over time during storage at room temperature, or the polymerization initiation ability is lost and the curing time is delayed. Storage for two to three years, which is a general expiration date for dental curable materials, is not possible at room temperature, and a refrigerated environment is essential for long-term storage.

Furthermore, pastes (or liquids) containing organic peroxides are unavoidably decomposed over time even during refrigerated storage, and harden in a set time immediately after production. However, after long-term refrigerated storage, the curing time may be delayed due to a decrease in the organic peroxide concentration.
In order to eliminate the instability of these organic peroxides, there are also powder / liquid type compositions consisting of a powder containing an organic peroxide and a liquid containing a reducing agent. In addition, it is difficult to say that it is a simple method in the field of dental practice because it is necessary to measure the powder and mix with the liquid, and it takes time to prepare the mixture.
Moreover, the curable composition using an organic peroxide is subject to polymerization inhibition by oxygen in the air or dissolved oxygen in the mixture, and the polymerization rate may be remarkably lowered particularly on the surface that comes into contact with air. For example, when a crown restoration is bonded using an adhesive resin cement, a resin cement layer (cement line) of about 10 to 50 μm is formed in the gap between the restoration and the tooth. This cement line is exposed to air. Therefore, there is a concern that the polymerization rate is inevitably lowered and the cement line is not only discolored but also dissolved in saliva. In addition, since sufficient mechanical strength cannot be obtained, the adhesive strength is insufficient, and there is a risk that the restoration will fall off and secondary caries will be affected.

In order to solve the above problems, Patent Documents 1 and 2 describe a polymerization initiator system that does not use an organic peroxide.
Patent Document 1 exemplifies a curable composition comprising an aromatic carboxylic acid-containing methacrylate, a vinyl compound, an aromatic amine, and an aromatic sulfinate, and has an adhesion performance to a tooth or a metal, a curing performance and a color tone. It has improved. However, there is no description suggesting that a Group IIa element, tin, lead, or bismuth compound (or salt or glass containing) is added.
Patent Document 2 discloses a two-component dental adhesive containing an organic acid, an amine, and a sulfinate, and describes that it provides excellent adhesion to teeth. However, there is no description and specific meaning of blending a Group IIa element, tin, lead, or bismuth compound (or salt or glass containing). In addition, liquid B containing amine and sulfinate is prepared as an ethanol solution, and only an application method of air drying after applying the mixture with liquid A to the tooth surface is shown. There is no suggestion of combining the acid salt with the polymerizable monomer.

Patent Document 3 is composed of a first component containing a (meth) acrylate polymerizable resin and an organic peroxide, and a second component containing a (meth) acrylate polymerizable resin and a reducing agent (amine compound), A polymerizable composition comprising a photopolymerization initiator and a filler in the first component and / or the second component, wherein the first component and / or the second component has an average particle size of 1 μm or less. A composite resin for building an abutment is disclosed, characterized in that a Group 2 element oxide powder is blended. However, the technique of this document basically uses an organic peroxide and a reducing agent (amine compound) as a catalyst, whereas the present invention is a polymerization initiator system that does not use an organic peroxide. Is different.
In addition, the same document describes the oxide powder of the Group 2 element “The oxide powder of the Group II element having an average particle size of 1 μm or less is an organic peroxide such as benzoyl peroxide and a reducing agent such as amine. In the redox-based chemical polymerization, the effect of silanol groups acting as acidity on the filler surface is suppressed (neutralized) and the polymerization is accelerated "(paragraph [0022]). That is, the group II element oxide in the same document only suggests an action as an alkali, and contains an acidic compound and a group IIa element or tin, lead, bismuth compound (or salt or containing glass). There is no description that suggests the significance of blending a Group IIa element, tin, lead, or bismuth compound (or salt, or glass containing) that the polymerization reaction (curing) can be performed without using an organic peroxide. .

JP 60-44508 A JP 61-176507 A JP 2008-247801 A

In the preliminary research stage of the present invention, a polymerization initiator system that does not use an organic peroxide, that is, an acidic compound (a), an aromatic sulfinate (d) and a tertiary amine (e), and having an acidic group A composition containing no polymerizable monomer (c) (Paste A [Comparative Example 1], Paste B [Comparative Example 2]) was prototyped and stored at room temperature. After about 6 months, the curing time was significantly delayed. However, there is a problem that it cannot be put to practical use for clinical purposes.
The present invention has been made with a focus on solving the above-mentioned problems, and its purpose is not to use an organic peroxide, it has excellent storage stability even at room temperature storage, and it has a curing time. The object is to provide a paste-paste (or liquid-liquid) dental curable composition that does not cause delayed changes.

The inventors of the present invention provide a composition containing an acidic compound (a), a polymerizable monomer having no acidic group (c), an aromatic sulfinate (d), and a tertiary amine (e). , Group IIa element, tin, lead, or bismuth compound (or salt, or glass containing glass) (b), which does not cause delayed changes in curing time even at room temperature storage, and has excellent storage stability- It was found that a paste (or liquid-liquid) dental curable composition was obtained, and the present invention was completed.
In addition, when (b) component itself is an acidic compound, since it will also serve as (a) component, it is not necessary to add (a) component separately.
That is, the present invention relates to an acidic compound (a), a Group IIa element, tin, lead, or a bismuth compound (salt or containing glass), or an A agent containing a mixture (b) thereof, an acidic agent A two-component packaged preparation of agent B containing a polymerizable monomer (c) having no group, an aromatic sulfinate (d), and a tertiary amine (e), and agents A and B The present invention relates to a curable composition obtained by mixing.

The two-packed preparation of the present invention does not need refrigerated storage because it does not contain an organic peroxide, and does not cause a delay in curing time even after long-term storage at room temperature, and has excellent long-term storage stability. Composition. The two-packed preparation of the present invention is polymerized (curable) without using an organic peroxide by mixing agent A and agent B at the time of use.
One of the acidic compound (a), group IIa element, tin, lead, or bismuth compound (salt or glass) of the present invention or a mixture thereof (b), a polymerizable monomer having no acidic group It is considered that the polymerization reaction that occurs by mixing (c), the aromatic sulfinate (d) and the tertiary amine (e) does not proceed by a radical mechanism frequently used in the polymerization reaction of vinyl compounds.
As an example, when (a), (b), (c), (d), (e) are mixed, even when diphenylpicrylhydrazyl and chloranil coexist as radical scavengers, they rapidly polymerize. Good curability. Therefore, it is considered that this polymerization reaction proceeds not by a radical polymerization mechanism but by an ionic polymerization mechanism.
Furthermore, it is suggested that ionic polymerization of methacrylic acid esters such as methyl methacrylate generally does not proceed by a cation (cation) polymerization mechanism but proceeds by an anion (anion) polymerization mechanism.
Accordingly, one of the acidic compound (a), Group IIa element, tin, lead, or bismuth compound (salt or glass) of the present invention or a mixture thereof (b), a polymerizable single group having no acidic group. The polymerization reaction that occurs by mixing the monomer (c), the aromatic sulfinate (d), and the tertiary amine (e) is presumed to proceed by an anionic polymerization mechanism.
This curable composition is used, for example, as cement for cement, temporary cement, a bonding agent, a sealer for filling a root canal, and a composite resin for building an abutment and filling. In the case where a polymerizable monomer having an acidic group is blended as the acidic compound, the bonding agent to the tooth substance can be exhibited alone without the need for a bonding agent.

The dental two-part package preparation of the present invention comprises an A agent and a B agent.
Agent A contains one or a mixture (b) of an acidic compound (a) and a Group IIa element, tin, lead, or bismuth compound (or salt or containing glass).
The agent A may further contain a polymerizable monomer (c) having no acidic group, an inorganic filler (f), an organic filler (g), and a photopolymerization initiator (h).
The agent B contains a polymerizable monomer (c) having no acidic group, an aromatic sulfinate (d), and a tertiary amine (e).
The B agent may further contain an inorganic filler (f), an organic filler (g), and a photopolymerization initiator (h).

  The acidic compound (a) used in the present invention is an essential component for curing the curable composition of the present invention, and reacts with a Group IIa element, tin, lead, or bismuth compound (b). A cation of a group IIa element, tin, lead or bismuth is generated, and a polymerization initiation catalyst function is exhibited in combination with the aromatic sulfinate (d) and the tertiary amine (e).

Examples of the acidic compound (a) include a polymerizable monomer (a1) having an acidic group and an acidic compound (a2) having no polymerizable group.
It is desirable to use a polymerizable monomer (a1) having an acidic group for applications requiring adhesiveness such as cement for cement, bonding agent, and root canal filling sealer.
Examples of the acidic group of the polymerizable monomer (a1) having an acidic group include a phosphoric acid group, a pyrophosphoric acid group, a phosphonic acid group, and a carboxylic acid group. For example, as the polymerizable monomer having a phosphate group, (meth) acryloyloxymethyl dihydrogen phosphate, 2- (meth) acryloyloxyethyl dihydrogen phosphate, 3- (meth) acryloyloxypropyl dihydrogen Phosphate, 4- (meth) acryloyloxybutyl dihydrogen phosphate, 5- (meth) acryloyloxypentyl dihydrogen phosphate, 6- (meth) acryloyloxyhexyl dihydrogen phosphate, 7- (meth) acryloyloxyheptyldi Hydrogen phosphate, 8- (meth) acryloyloxyoctyl dihydrogen phosphate, 9- (meth) acryloyloxynonyl dihydrogen phosphate, 10- (meth) acrylic Iroxydecyl dihydrogen phosphate, 11- (meth) acryloyloxyundecyl dihydrogen phosphate, 12- (meth) acryloyl oxide decyl dihydrogen phosphate, 16- (meth) acryloyloxyhexadecyl dihydrogen phosphate, 20 -(Meth) acryloyloxyeicosyl dihydrogen phosphate, di (meth) acryloyloxyethyl hydrogen phosphate, di (meth) acryloyloxybutyl hydrogen phosphate, di (meth) acryloyloxyhexyl hydrogen phosphate, di (meth) Acryloyloxyoctyl hydrogen phosphate, di (meth) acryloyloxynonyl hydrogen phosphate, di (meth) acrylic Iroxydecyl hydrogen phosphate, 1,3-di (meth) acryloyloxypropyl-2-dihydrogen phosphate, 2- (meth) acryloyloxyethyl phenyl hydrogen phosphate, 2- (meth) acryloyloxyethyl-2 ′ -Acid group-containing polymerizable monomers such as bromoethyl hydrogen phosphate, (meth) acryloyloxyethyl phenyl phosphonate, and the like, but are not limited thereto.

  Examples of polymerizable monomers having a pyrophosphate group include di [2- (meth) acryloyloxyethyl pyrophosphate], di [3- (meth) acryloyloxypropyl pyrophosphate], and di [4- (meth) pyrophosphate. [Acryloyloxybutyl], di [5- (meth) acryloyloxypentyl] pyrophosphate, di [6- (meth) acryloyloxyhexyl] pyrophosphate, di [7- (meth) acryloyloxyheptyl] pyrophosphate, di pyrophosphate [8- (meth) acryloyloxyoctyl], di [9- (meth) acryloyloxynonyl] pyrophosphate, di [10- (meth) acryloyloxydecyl] pyrophosphate, di [12- (meth) acryloyloxy pyrophosphate Dodecyl], tetra [2- (meth) acryloyloxyethyl] pyrophosphate, pyrophosphate Li [2- (meth) acryloyloxyethyl] acid group-containing polymerizable monomer such as including but not limited to.

  Examples of polymerizable monomers having a phosphonic acid group include 5- (meth) acryloyloxypentyl-3-phosphonopropionate, 6- (meth) acryloyloxyhexyl-3-phosphonopropionate, 10- ( Acid group-containing polymerizability such as (meth) acryloyloxydecyl-3-phosphonopropionate, 6- (meth) acryloyloxyhexyl-3-phosphonoacetate, 10- (meth) acryloyloxydecyl-3-phosphonoacetate Although a monomer etc. are mentioned, it is not limited to these.

Examples of polymerizable monomers having a carboxylic acid group include (meth) acrylic acid, 2-chloro (meth) acrylic acid, 3-chloro (meth) acrylic acid, 2-cyano (meth) acrylic acid, aconitic acid, and mesacon. Acid, maleic acid, maleic anhydride, itaconic acid, itaconic anhydride, fumaric acid, glutaconic acid, citraconic acid, utraconic acid, 1,4-di (meth) acryloyloxyethyl pyromellitic acid, 6- (meth) acryloyloxy Naphthalene-1,2,6-tricarboxylic acid, 1-butene-1,2,4-tricarboxylic acid, 3-butene1,2,3-tricarboxylic acid, N- (meth) acryloyl-p-aminobenzoic acid, N -(Meth) acryloyl-5-aminosalicylic acid, 4- (meth) acryloyloxyethyl trimellitic acid and its anhydride, 4- (meth) a Liloyloxybutyl trimellitic acid and its anhydride, 2- (meth) acryloyloxybenzoic acid, β- (meth) acryloyloxyethyl hydrogen succinate, β- (meth) acryloyloxyethyl hydrogen maleate, 11- (Meth) acryloyloxy-1,1-undecanedicarboxylic acid, p-vinylbenzoic acid, 4- (meth) acryloyloxyethoxycarbonylphthalic acid, 4- (meth) acryloyloxybutyloxycarbonylphthalic acid, 4- (meth) Acryloyloxyhexyloxycarbonylphthalic acid, 4- (meth) acryloyloxyoctyloxycarbonylphthalic acid, 4- (meth) acryloyloxydecyloxycarbonylphthalic acid and their anhydrides, 5- (meth) acryloylaminopen Carboxylic acid, 6- (meth) acryloyloxy-1,1-hexanedicarboxylic acid, 8- (meth) acryloyloxy-1,1-octanedicarboxylic acid, 10- (meth) acryloyloxy-1,1-decanedicarboxylic acid 11- (meth) acryloyloxy-1,1-undecanedicarboxylic acid and other acidic group-containing polymerizable monomers, and the like, but are not limited thereto.
You may mix | blend the polymerizable monomer which has these acidic groups 1 type or in combination of several types. Among these, a polymerizable monomer having a phosphoric acid group or a carboxylic acid group is preferable, and particularly preferable is 10- (meth) acryloyloxydecyl dihydrogen phosphate, 4- (meth) acryloyloxyethyl trimellitic acid, and Its anhydride, 4- (meth) acryloyloxyethoxycarbonylphthalic acid.
As the acidic compound (a2) having no polymerizable group, a general mineral acid, organic acid, phosphate ester, or the like can be used.
Specifically, inorganic acids such as hydrofluoric acid, hydrochloric acid, hydrobromic acid, sulfuric acid, nitric acid, boric acid, phosphoric acid, pyrophosphoric acid, formic acid, acetic acid, propionic acid, butyric acid, valeric acid, caproic acid, lauric acid , Myristic acid, palmitic acid, stearic acid, oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, sebacic acid, phthalic acid, isophthalic acid, benzoic acid, terephthalic acid, fumaric acid, maleic acid, glycolic acid, lactic acid , Carboxylic acids such as hydroxybutyric acid, malic acid, tartaric acid, citric acid, ascorbic acid, sulfonic acids such as methanesulfonic acid, benzenesulfonic acid, p-toluenesulfonic acid, phosphoric acid monomethyl ester, phosphoric acid monoethyl ester, phosphoric acid Monopropyl ester, phosphoric acid monobutyl ester, phosphoric acid dimethyl ester, phosphoric acid diethyl ester, Phosphate esters such as dipropyl ester, dibutyl phosphate, monomethyl pyrophosphate, monoethyl pyrophosphate, monopropyl pyrophosphate, monobutyl pyrophosphate, dimethyl pyrophosphate, diethyl pyrophosphate, Pyrophosphoric acid esters such as dipropyl pyrophosphate and dibutyl pyrophosphate, monomethyl phosphonate, monoethyl phosphonate, monopropyl phosphonate, monobutyl phosphonate, dimethyl phosphonate, diethyl phosphonate, Acidic organic phosphorus compounds such as phosphonic acid esters such as phosphonic acid dipropyl ester and phosphonic acid dibutyl ester.
Among these, organic acids and phosphoric acids are preferable, and acetic acid, lactic acid, maleic acid, benzoic acid, phthalic acid, and phosphoric acid are more preferable.

The polymerizable monomer (c) that is an optional component of the agent A and has no acidic group, which is an essential component of the agent B, may be either a hydrophilic monomer or a hydrophobic monomer. Either functional or polyfunctional (crosslinkable) may be used. Also, several types can be used in combination.
Specific examples of the polymerizable monomer having no acidic group include methyl (meth) acrylate, ethyl (meth) acrylate, glycidyl (meth) acrylate, 2-cyanomethyl (meth) acrylate, benzyl (meth) acrylate, Polyethylene glycol mono (meth) acrylate, allyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, glycidyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, glyceryl mono (meth) acrylate, ethylene glycol di (meta ) Acrylate, diethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, nonaethylene glycol di (meth) acrylate, propylene glycol di (meth) acrylate, dipropiate Glycol di (meth) acrylate, 2,2′-bis [4- (meth) acryloyloxyethoxyphenyl] propane, 2,2′-bis [4- (meth) acryloyloxyethoxyethoxyphenyl] propane, 2,2 '-Bis {4- [3- (meth) acryloyloxy-2-hydroxypropoxy] phenyl} propane, neopentyl glycol di (meth) acrylate, 1,3-butanediol di (meth) acrylate, 1,4-butane Diol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, 1,10-decanediol di (meth) acrylate, trimethylolpropane tri (meth) acrylate, trimethylolethane tri (meth) acrylate, tetra Methylol methane tri (meth) acrylate, Examples include, but are not limited to, letane (meth) acrylate, epoxy (meth) acrylate, penta (methacryloxyethyloxy) cyclophosphazene monofluoride and di (trifluoroethoxy) hexamethacryloxycyclophosphazene. .
Of these, methyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, triethylene glycol di (meth) acrylate, 2,2′-bis [4- (meth) acryloyloxyethoxyphenyl] propane, 2,2'-bis {4- [3- (meth) acryloyloxy-2-hydroxypropoxy] phenyl} propane, 1,3-butanediol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate , Urethane (meth) acrylate.

The Group IIa element, tin, lead, or bismuth compound (b) component in the agent A may be a group IIa element, tin, lead, or bismuth cation produced by reaction with the component (a). Anything can be used, and the polymerization initiation catalyst function is exhibited in the present catalyst system.
The component (b) is blended in the agent A and exhibits its function. When blended in the agent B, the agent B is cured (solidified) and cannot be used.
Examples of Group IIa element, tin, lead, or bismuth compound (b) include oxides and hydroxides. Examples of Group IIa element, tin, lead, or bismuth salts include halides and sulfates. , Nitrates, organic acid salts and the like.

Specific examples of Group IIa elements, tin, lead, or bismuth compounds (b) include oxides of Group IIa elements, tin, lead, or bismuth as beryllium oxide, magnesium oxide, power lucium oxide, and barium oxide. , Strontium oxide, tin oxide, lead oxide, bismuth oxide, Group IIa elements, tin, lead, or bismuth hydroxide include beryllium hydroxide, magnesium hydroxide, power hydroxide lucium, barium hydroxide, strontium hydroxide , Tin hydroxide, lead hydroxide, bismuth hydroxide. Group IIa elements, tin, lead, or bismuth salts include beryllium chloride, magnesium chloride, strong lucium chloride, barium chloride, strontium chloride, tin chloride, lead chloride, bismuth chloride, beryllium chloride chloride, magnesium hydroxide hydroxide , Calcium chloride hydroxide, strontium chloride chloride, barium chloride hydroxide, beryllium bromide, magnesium bromide, lucium bromide, barium bromide, tin bromide, lead bromide, bismuth bromide, beryllium fluoride, fluoride Halides such as magnesium fluoride, lucium fluoride, barium fluoride, strontium fluoride, tin fluoride, lead fluoride, bismuth fluoride, beryllium phosphate, magnesium phosphate, calcium phosphate, barium phosphate, strontium phosphate, Phosphoric acids such as tin phosphate, lead phosphate, bismuth phosphate Beryllium hydrogen phosphate, magnesium hydrogen phosphate, calcium hydrogen phosphate, barium hydrogen phosphate, strontium hydrogen phosphate, tin hydrogen phosphate, lead hydrogen phosphate, bismuth hydrogen phosphate, beryllium dihydrogen phosphate, diphosphoric acid phosphate Magnesium hydrogen, calcium dihydrogen phosphate, barium dihydrogen phosphate, hydrogen phosphate such as strontium dihydrogen phosphate, beryllium citrate, magnesium citrate, calcium citrate, barium citrate, strontium citrate, tin citrate Citrates such as lead citrate and bismuth citrate, acrylates such as beryllium acrylate, magnesium acrylate, calcium acrylate, barium acrylate, strontium acrylate, tin acrylate, lead acrylate and bismuth acrylate , Magne methacrylate Sium, calcium methacrylate, barium methacrylate, strontium methacrylate, tin methacrylate, lead methacrylate, methacrylates such as bismuth methacrylate, calcium acid salts such as calcium lactate and calcium gluconate, calcium glycerophosphate, glucose-1 -Organic phosphate ester calcium salts such as calcium phosphate. Other organic acid salts of Group IIa elements, tin, lead or bismuth include acetate, benzoate, formate, fumarate, butyrate, isobutyrate, malate, maleate, propion And salts such as acid salts. Other inorganic compounds include all Group IIa elements, tin, lead, or bismuth salts, such as Group IIa elements, tin, lead, or bismuth carbonates, nitrates, sulfates. The Group IIa element, tin, lead, or bismuth compound (b) that can be used in the present invention is not limited to these, and may be used alone or in combination. In particular, an oxide or chloride of magnesium, calcium is preferable because it contributes to stabilization of the curing time over a long period of time.
More preferred are magnesium oxide, magnesium hydroxide, calcium oxide, calcium hydroxide, calcium chloride, and calcium lactate.
Among the above examples, the component (b) itself is an acidic compound, and those that also serve as the component (a) include tin chloride, barium chloride, calcium dihydrogen phosphate, magnesium chloride hydroxide and the like.

  Furthermore, specific examples of Group IIa elements, tin, lead, or bismuth-containing glass include calcium-containing aluminosilicate glass, magnesium-containing aluminosilicate glass, barium-containing glass, and strontium-containing glass. It may be a glass containing a plurality of Group IIa elements, tin, lead, or bismuth.

Aromatic sulfinates (d) include sodium p-toluenesulfinate, potassium p-toluenesulfinate, lithium p-toluenesulfinate, calcium p-toluenesulfinate, magnesium p-toluenesulfinate, sodium benzenesulfinate , Potassium benzenesulfinate, lithium benzenesulfinate, calcium benzenesulfinate, magnesium benzenesulfinate, sodium 2,4,6-trimethylbenzenesulfinate, potassium 2,4,6-trimethylbenzenesulfate, 2,4,6 -Lithium trimethylbenzenesulfinate, calcium 2,4,6-trimethylbenzenesulfinate, magnesium 2,4,6-trimethylbenzenesulfinate, 2,4,6-triethylben Sodium sulfinate, potassium 2,4,6-triethylbenzenesulfinate, lithium 2,4,6-triethylbenzenesulfinate, calcium 2,4,6-triethylbenzenesulfinate, 2,4,6-triethylbenzenesulfinate Magnesium, sodium 2,4,6-i-propylbenzenesulfinate, potassium 2,4,6-i-propylbenzenesulfinate, lithium 2,4,6-i-propylbenzenesulfinate, 2,4,6- Examples thereof include calcium i-propylbenzenesulfinate, magnesium 2,4,6-i-propylbenzenesulfinate, and the like, but are not limited thereto, and may be used alone or in combination.
Of the aromatic sulfinates (d), sodium salts are preferable, and sodium p-toluenesulfinate, sodium benzenesulfinate, and sodium 2,4,6-trimethylbenzenesulfinate are particularly preferable.

As the tertiary amine (e), both aromatic amines and aliphatic amines are effective. Examples of aromatic amines include p-tolyldiethanolamine, N, N-dimethylaniline, N, N-dimethyl-p-toluidine, N, N-dimethyl-m-toluidine, N, N-diethyl-p-toluidine, N, N-dimethyl-3,5-dimethylaniline, N, N-dimethyl-3,4-dimethylaniline, N, N-dimethyl-4-ethylaniline, N, N-dimethyl-4-isopropylaniline, N, N-dimethyl-4-t-butylaniline, N, N-bis (2-hydroxyethyl) -p-toluidine, ethyl N, N-dimethylaminobenzoate, butoxyethyl N, N-dimethylaminobenzoate, N, N-dimethylaminobenzoic acid (2-methacryloyloxy) ethyl and the like.
Examples of aliphatic amines include trimethylamine, triethylamine, N-methyldiethanolamine, N-ethyldiethanolamine, Nn-butyldiethanolamine, N-lauryldiethanolamine, triethanolamine, (2-dimethylamino) ethyl methacrylate, and N-methyl. Examples include, but are not limited to, diethanolamine dimethacrylate, N-ethyldiethanolamine dimethacrylate, triethanolamine monomethacrylate, triethanolamine dimethacrylate, and triethanolamine trimethacrylate. Moreover, the said amine compound can also be used individually or in combination of several types.
Particularly preferred as the tertiary amine (e) is p-tolyldiethanolamine, N, N-dimethyl-p-toluidine, ethyl N, N-dimethylaminobenzoate, N-methyldiethanolamine, triethanolamine, triethanolamine Monomethacrylate, triethanolamine dimethacrylate, triethanolamine trimethacrylate.

The inorganic filler (f) is a filler that does not contain a Group IIa element, tin, lead, or bismuth. For example, zirconia, zirconia glass, lanthanum glass, fluoroaluminosilicate glass, lithium borosilicate glass, silica, crystalline quartz And alumina, titanium oxide, zinc oxide and the like.
Of these, zirconia, zirconia glass, lanthanum glass, and zinc oxide are suitable when X-ray contrast properties such as root canal sealers are required, and when strength is required such as adhesive resin cement and resin for building an abutment Zirconia, zirconia glass, silica, crystalline quartz, and alumina are preferred.
In the case of producing a temporary cement that does not require high physical properties and requires the elasticity of the cured product, an organic filler (g) may be blended. Organic fillers (g) include polyethylene, polypropylene, polymethyl methacrylate, polyethyl methacrylate, polypropyl methacrylate, polybutyl methacrylate, ethylene-vinyl acetate copolymer, vinyl chloride-vinyl acetate copolymer, polystyrene, polyester, polyamide Nitrile rubber, methacrylate copolymer and the like.
More preferable organic fillers (g) are polypropylene, polymethyl methacrylate, polyethyl methacrylate, ethylene-vinyl acetate copolymer, and vinyl chloride-vinyl acetate copolymer.
Moreover, you may use the composite filler etc. which mixed the inorganic filler and the organic filler.

The dental curable composition according to the present invention can be used as a dual cure type by adding the photopolymerization initiator (h) to the agent A and / or the agent B. Specific examples of the photopolymerization initiator include benzyl, camphorquinone, α-naphthyl, acetonaphthene, p, p′-dimethoxybenzyl, p, p′-dichlorobenzylacetyl, pentanedione, 1,2-phenanthrenequinone, 1 , 4-phenanthrenequinone, 3,4-phenanthrenequinone, 9,10-phenanthrenequinone, α-diketones such as naphthoquinone, benzoin alkyl ethers such as benzoin, benzoin methyl ether, benzoin ethyl ether, thioxanthone, 2-chlorothioxanthone Thioxanthones such as 2-methylthioxanthone, 2-isopropylthioxanthone, 2-methoxythioxanthone, 2-hydroxythioxanthone, 2,4-diethylthioxanthone, 2,4-diisopropylthioxanthone Benzophenones such as benzophenone, acetoin benzophenone, p-chlorobenzophenone, p-methoxybenzophenone, 2,4,6-trimethylbenzoyldiphenylphosphine oxide, bis (2,6-dimethoxybenzoyl) -2,4,4-trimethylpentyl Acylphosphine oxides such as phosphine oxide, 2-benzyl-dimethylamino-1- (4-morpholinophenyl) -butanone-1,2-benzyl-diethylamino-1- (4-morpholinophenyl) -propanone Α-aminoacetophenones such as 1; ketals such as benzyldimethyl ketal, benzyl diethyl ketal and benzyl (2-methoxyethyl ketal); bis (cyclopentadienyl) -bis [2,6-difluoro-3- (1 Pyrrolyl) phenyl] -titanium, bis (cyclopentadienyl) -bis (pentanefluorophenyl) -titanium, bis (cyclopentadienyl) -bis (2,3,5,6-tetrafluoro-4-disiloxyphenyl) ) -Titanocene such as titanium.
Among the photopolymerization initiators (h), α-diketones and acylphosphine oxides are preferable, and benzyl, camphorquinone, 2,4,6-trimethylbenzoyldiphenylphosphine oxide, bis (2 , 6-dimethoxybenzoyl) -2,4,4-trimethylpentylphosphine oxide, but is not limited thereto. Moreover, the said photoinitiator can also be used individually or in combination of several types.

In the case where the acidic compound (a) is a polymerizable monomer having an acidic group (a1), for example, when an equal amount of the A agent and the B agent are mixed, the amount of the (a1) component in 100% by mass of the A agent is: 5-60 mass%, Preferably, it is 5-50 mass%. When the blending amount of the component (a1) is less than 5% by mass, the curing rate and the adhesive strength of the curable composition are decreased, and when it exceeds 60% by mass, the acidity of the curable composition is increased. There is a risk of excessive demineralization and tissue corrosion of the gingival surface, and the polymerization reaction tends to decrease.
When the acidic compound (a) is an acidic compound (a2) having no polymerizable group such as a mineral acid or an organic acid, for example, when mixing an equal amount of the A agent and the B agent, The amount of the component (a2) is 0.1 to 50% by mass, preferably 0.5 to 30% by mass. When the amount of the component (a2) is less than 0.1% by mass, the amount of the curable composition is When the curing rate decreases and exceeds 50% by mass, the acidity of the curable composition increases, which may cause excessive decalcification of the tooth and tissue corrosion of the gingival surface, and the polymerization reaction tends to decrease. is there.
Moreover, it is important that the compounding amount of the acidic compound (a) is set so that the pH of the mixture when the agent A and the agent B are mixed is in an acidic region. Furthermore, when the Group IIa element, tin, lead, or bismuth compound (or salt) (b) is basic, the acidic compound (a) is also consumed in the neutralization reaction with the component (b), so the blending amount Can be many.

The compounding amount of the Group IIa element, tin, lead, or bismuth compound (or salt) (b) is, for example, 0.1 to 30 in 100% by mass of the A agent when the A agent and the B agent are mixed in an equal amount. It is mass%, and 1-10 mass% is preferable. The curing rate due to the function of the group IIa element, tin, lead, or bismuth compound (or salt) (b) as a polymerization initiator is determined by the combination of aromatic sulfinate (d) and tertiary amine (e). Although it is influenced by the amount, if it is less than 0.1% by mass, the effect as an initiator is inferior, and if it exceeds 30% by mass, the curing time tends to be greatly shortened.
Further, among the components (b), the Group IIa element, tin, lead, or bismuth-containing glass contains 10 to 80% by mass of the Group IIa element, tin, lead, or bismuth as an oxide. Since the Group IIa element, tin, lead, or bismuth-containing glass is less effective as a polymerization initiator than the compound itself, its blending amount is 0.1 to 50% by mass, preferably 2% in 100% by mass of the A agent. -40 mass%. If it is less than 0.1% by mass, the action as an initiator becomes small.

When the acidic compound (a) is an acidic compound (a2) having no polymerizable group such as a mineral acid or an organic acid, a polymerizable monomer (c) having no acidic group is added to the agent A. Is preferred. In this case, the amount of the polymerizable monomer (c) having no acidic group contained in 100% by mass of the A agent is in the range of 10 to 99% by mass, preferably 20 to 90% by mass.
Also when the acidic compound (a) is a polymerizable monomer (a1) having an acidic group, a polymerizable monomer (c) having no acidic group can be blended. In this case, the blending amount of the polymerizable monomer (c) having no acidic group is preferably about 20 to 80% by mass.
The quantity of the polymerizable monomer (c) which does not have an acidic group in B agent 100 mass% is 10-99 mass%, Preferably it is 20-90 mass%. In the curable composition formed by mixing the A agent and the B agent, the total amount of the polymerizable monomer (a1) having an acidic group and the polymerizable monomer (c) having no acidic group is a curable composition. The amount must be 10% by mass or more of the product, and if it is less than 10% by mass, the mixing operability and adhesive strength of the preparation tend to decrease.

As for aromatic sulfinate (d), 0.05-10 mass% is suitable in 100 mass% of B agents, More preferably, it is 0.1-5 mass%.
0.05-10 mass% is suitable for the compounding quantity of a tertiary amine (e) in 100 mass% of B agent, More preferably, it is 0.1-5 mass%.
The blending amount of the aromatic sulfinate (d) and the tertiary amine (e) is desirably 0.025 to 5% by mass based on the total mass of the curable composition, and when exceeding this range, Adhesive strength may be reduced.

The blending amount of the filler of component (f) and / or (g) in agent A and agent B is 0 to 90% by mass, preferably 0 in 100% by mass of the curable composition in which agent A and agent B are mixed. An appropriate amount is blended in the agent A and the agent B so that the amount becomes -80% by mass.
By adjusting the amount of filler, a curable composition suitable as a cement for cementing, temporary cement, a sealer for filling a root canal, a composite resin for building an abutment, and a filling restorative agent can be obtained.
A curable composition containing no filler or a very small amount is used as a bonding agent.
In addition to the above-described components, the dental curable composition according to the present invention may contain a polymerization inhibitor, an antioxidant, an ultraviolet absorber, a pigment, and a dye as necessary. In addition, for the purpose of forming a thin film such as a bonding material, an appropriate solvent or dispersion medium may be used, preferably water and a water-soluble organic solvent, such as methanol, ethanol, propyl alcohol, etc. Examples include alcohols and ketones such as acetone and methylacetone. Among these, ethanol or acetone is preferably used alone or as a mixture, and 1 to 50% by mass can be added to 100% by mass of the curable composition.

The agent A is a mixture of a predetermined amount of an acidic compound (a) and a polymerizable monomer (c) having no arbitrarily selected acidic group, and then a Group IIa element, tin, lead, Alternatively, a bismuth compound (or salt or glass containing glass) (b) is added, and an appropriate amount of filler is added to adjust the viscosity of the liquid agent.
Agent B is a mixture of a predetermined amount of a polymerizable monomer (c) having no acidic group, an aromatic sulfinate (d), and a tertiary amine (e), and then blending an appropriate amount of filler. Then, it is prepared by adjusting the viscosity of the liquid agent.
The curable composition of this invention is obtained by mixing the said A agent and B agent at the time of use. The mixing ratio of agent A and agent B is arbitrary, but an appropriate amount is mixed so that the pH value immediately after the mixing of both agents becomes acidic.

EXAMPLES Next, although an Example is given and this invention is demonstrated more concretely, this invention is not limited to this Example.
The names and abbreviated names of the components used in each example are listed below.
HEMA: 2-hydroxyethyl methacrylate 4-MET: 4-methacryloyloxyethoxycarbonylphthalic acid Bis-GMA: 2,2-bis [4- (3-methacryloyloxy-2-hydroxypropoxy) phenyl] propane Ca- G: Calcium-containing glass (average particle size 10 μm, containing 14.3% by mass of calcium atoms. Composition: SiO 2
40 mass%, Al2O3 40 mass%, CaO 20 mass%. )
CaO: Calcium oxide Ca (OH) 2: Calcium hydroxide CaCl2: Calcium chloride CaSO4: Calcium sulfate Ca (NO3) 2: Calcium nitrate CaHPO4: Calcium hydrogen phosphate MgO: Magnesium oxide SrO: Strontium oxide BaO: Barium oxide SnO: Oxidation Tin (II)
SnCl2: Tin (II) chloride
Pb (NO3) 2: Lead nitrate (II)
Bi (NO3) 2: Bismuth nitrate (II)
BPO: benzoyl peroxide 1,6-HX: 1,6-hexanediol dimethacrylate-to-TSNa: sodium p-toluenesulfinate p-TSCa: calcium p-toluenesulfinate p-TDEA: p-tolyl Diethanolamine filler: spherical silica

  The compounding composition of A agent and B agent of Examples 1-44 and Comparative Examples 1-15 is as having described in Tables 1-8.

[PH measurement of the mixture]
The mixture immediately after mixing agent A and agent B was brought into contact with pH test paper (MACHEREY-NAGEL wide area, pH = 1-14) moistened with distilled water, and the pH was measured.

[Measurement of curing time]
The agents A and B of Examples 1 to 27 and Comparative Examples 1 to 9 were kneaded after 1 day of production and stored at 60 ° C. for 1 month as a heat deterioration test, and the curing time was measured. It showed to Tables 1-4.
The measurement method was as follows. First, A and B agents were weighed in equal amounts, kneaded for 20 seconds, filled into a cylindrical mold having an inner diameter of 10 mm and a depth of 5 mm, and the surface was flattened.
One minute after the start of kneading, the mixture is transferred to a constant temperature and humidity chamber at 37 ± 2 ° C. and a relative humidity of 95 to 100%, and a bigger 300 g (needle cross-sectional area 1 mm 2) is gently dropped onto the surface of the test piece. At this time, the time when the trace of the bigger needle was not recognized on the surface of the test piece was defined as the curing time.
This test was performed three times and the average time was expressed in units of 10 seconds.

[Measurement of tensile adhesive strength]
Tables 1 to 5 show the tensile adhesive strengths of compositions obtained by mixing equal amounts of agents A and B of Examples 1 to 30 and Comparative Examples 1 to 10. For the measurement, the A agent and the B agent that were passed one day from the production were used. In Examples 27, 28, and 30 and Comparative Example 10, the A agent and the B agent stored at 60 ° C. for one month as a heat deterioration test were further used. Using. The test was conducted by the method described below.
The lip side surface of fresh bovine teeth is cut into a flat surface until the dentin is exposed, and finish-polished with # 600 water-resistant abrasive paper, then ultrasonically washed for 10 minutes and washed with running water for 5 minutes. The polished surface was dried with an air gun for 10 seconds, and a masking tape having an opening with a diameter of 3 mm was attached to the polished surface. Then, the curable composition which mixed A agent and B agent in equal amounts was apply | coated to the to-be-adhered surface (opening part of a masking tape), the polyester film was mounted on it, and it press-contacted with the slide glass. Next, the test piece (cow teeth) was placed in a constant temperature and humidity chamber having a temperature of 37 ± 2 ° C. and a relative humidity of 95 to 100%, and cured for 1 hour.
After the paste is cured, the polyester film is removed and applied to the bottom surface of a stainless steel pole with a diameter of 7 mm and a height of 25 mm using a resin adhesive (Kuraray Co., Ltd., Panavia F2.0). The curable composition mixed in an amount was planted on the masking tape opening applied and cured, and placed in a 37 ± 2 ° C. incubator and cured for 30 minutes.
After the resin adhesive was cured, the test piece was immersed in distilled water and stored in a 37 ± 2 ° C. incubator for 24 hours.
After 24 hours, EZ Graph (Shimadzu Corporation)
Was used to perform a tensile adhesion test at a crosshead speed of 1 mm / min. The tensile bond strength (MPa) was evaluated by an average value of five test pieces.

[Measurement of bending strength]
Table 4 shows the bending strength (MPa) of Example 28 and Comparative Examples 8 and 9. For the measurement, the A agent and the B agent which were passed one day from the production were used. The test is JIS
T6514: 2005 The test was performed according to the test method described in the composite resin for dental filling.
[Measurement of Brinell hardness at the contact interface with Eugenol sealer]
In order to confirm that the polymerization inhibition of the curable composition does not occur with a substance that inhibits radical polymerization, Examples 31 and 32 and Comparative Examples 11 and 12 in Table 6 include Eugenol sealers that are not completely cured and The measurement results of the Brinell hardness at the contact interface were shown. For the measurement, the A agent and the B agent which were passed one day from the production, and the A agent and the B agent stored at 60 ° C. for 1 month as a heat deterioration test were used. The test was conducted by the method described below.
A commercially available Eugenol-based sealer (Nishika Canal Sealer Quick: curing time at 37 ° C. and 100% RH for 10 minutes) was kneaded at a volume ratio of 1: 1, and placed on a glass plate with a diameter of 20 mm.
Poured into a 1.5 mm thick mold.
A mold having a diameter of 8 mm and a thickness of 1.5 mm is placed on the surface of an uncured sealer that has been kneaded and allowed to stand at room temperature for 10 minutes, and filled with a curable composition in which equal parts of A agent and B agent are mixed. Then, it was cured by being held for 1 hour in a thermostat having a temperature of 37 ° C. and a relative humidity of 100%.
The cured composition was peeled from the sealer, and the Brinell hardness (H) of the surface with which the sealer was in contact was measured. As a control, it was compared with a composition cured on the glass surface. The Brinell hardness was obtained by the following formula and evaluated by the average value of five test pieces.

P: Test force (N) <Implemented at 245N>
D: Diameter of a ball indenter (mm) <1.5 mm used>
t: Depth of depression (mm)

[Root apex test]
Using the A and B agents shown in Examples 33 to 36 and Comparative Examples 13 to 15 in Table 7, an apical blockage evaluation test was performed. The test method is as follows.
A root canal was formed according to the method of passing a human extracted single root tooth, followed by cleaning with a 10% sodium hypochlorite solution and a 3% EDTA solution (pH = 9). The curable composition obtained by mixing equal amounts of agent A and agent B is used in combination with a gutta-percha point to perform vertical pressure root canal filling, applying nail enamel to the three layers excluding the apex, It was immersed for 5 days in Indian ink. The ink was taken out from the ink liquor, washed with water and removed from the nail enamel, and then decalcified by dipping in a decalcification liquid (K-CX, Pharma) for 3 days. This was dehydrated with ethanol and replaced with xylene, and then immersed in silicone oil for storage to obtain a transparent specimen. For each tooth of the transparent specimen, the distance from the apical hole to the maximum invasion portion of the ink was measured from four directions of the mesial, centrifugal, buccal side, and lingual side, and the average value of each direction was determined. The apical sealability was evaluated by an average value of 10 teeth of a transparent specimen.

[Measurement of compressive strength]
The compressive strength measurements shown in Examples 37 to 44 in Table 8 were conducted using Agent A and Agent B one day after production, and the test method was JIS-T6610: 2005 for dental zinc oxide Eugenol cement and zinc oxide non-Eugenol cement. The test was performed according to the test method described. The required value as temporary cement is 35 MPa or less.

[Measurement of film thickness]
The film thickness measurements shown in Examples 37 to 44 in Table 8 are described for JIS-T6610: 2005 dental zinc oxide Eugenol cement and zinc oxide non-Eugenol cement using Agent A and Agent B one day after production. The test method was followed. The required value as temporary cement is 25 μm or less.

In all of Examples 1 to 44, the mixture immediately after mixing of the agent A and the agent B showed an acidity of pH = 1.
Examples 1 to 26 and Comparative Examples 1 to 7 in Tables 1 to 3 are composition examples of cements to be attached.
Since the tensile adhesive strength of commercially available adhesive resin cement to bovine dentin is about 5 MPa to 20 MPa, the tensile adhesive strength in this example is 8.8 to 22.8 MPa, which is sufficiently practical. It was determined to be a thing.
In Examples 1 to 26 and Comparative Examples 1 to 7, the amounts of HEMA, 4-MET and Bis-GMA blended with the agent A are the same, and the amounts of 1,6-HX blended with the agent B are both the same. Identical.

In Examples 1 to 7, the amount of Ca-G blended in the agent A was changed from 5% by mass to 45% by mass, and the filler was changed correspondingly. The values of the curing time and the tensile adhesive strength of a curable composition obtained from a composition in which the amount of TSNa and p-TDEA and the amount of filler added are changed are shown.
In Examples 1 to 4, the blending amount of p-TSNa and p-TDEA in the B agent was temporarily reduced to 3.0 to 1.0% by weight in 0.5% increments, and the blending amount of Ca-G The prescription was increased to 5 to 25% by mass in increments of 5% by mass. As a result, it became clear that the curing time was shortened and the tensile bond strength was improved as the Ca-G content was increased. Even if the amount of p-TSNa and p-TDEA in the agent B is further reduced, if the amount of Ca-G is further increased, the curing time is shortened and the tensile adhesive strength is further improved. 7 revealed.

Examples 8 and 9 contain 5 and 8% by mass of CaO in agent A,
The prescription was such that both p-TSNa and p-TDEA in the B agent were blended in the same amount, but the curing time of Example 9 with a larger amount of CaO was shorter than that of Example 8 and the tensile strength was higher. Adhesive strength also increased.
Examples 10 and 11 are formulations in which 5 and 8% by mass of Ca (OH) 2 is blended in agent A and p-TSNa and p-TDEA in agent B are both blended in the same amount. The curing time was shorter in Example 11 with a larger amount of (OH) 2 than in Example 10. The tensile bond strength was equivalent.

In Examples 15 to 24, 8 parts by mass of each of the other Group IIa elements, tin, lead, or bismuth compounds are mixed in the A agent, and both p-TSNa and p-TDEA in the B agent are the same. The amount of the cement formulation to be used in the same amount, and when any compound is blended, as in Examples 9 and 11, ISO
4049: 2000 Denstry-Polymer-based filling, restorative and luting materials meet the required setting time (maximum 10 minutes), and the tensile adhesive strength is 11.6 to 18.2 MPa, clinically practical. The value that can withstand.
Comparative Examples 1 and 2 are formulations in which the Group IIa element compound is not blended in the A agent, and the formulation of Comparative Example 1 has the same amounts of p-TSNa and p-TDEA in the B agent as in Example 3. However, the curing time and tensile bond strength are significantly inferior. Comparative Example 2 is a formulation in which the amounts of p-TSNa and p-TDEA in the B agent are both increased to 5% by mass, but compared with Example 3, there is no delay in curing time after 1 day of production. The tensile adhesive strength was small, and when both agent A and agent B were stored at 60 ° C. for 1 month, they did not cure at all even after 24 hours of mixing.

Example 25 uses agent A and agent B used in Comparative Example 2 (stored at 60 ° C. for 1 month and does not cure at all), and 8% by mass of CaO is added to agent A. When this is mixed, it indicates that the curing time and tensile adhesive strength have been recovered. Further, no delay in the curing time was observed after the A and B agents were further stored at 60 ° C. for 1 month.
Comparative Examples 3 and 4 show defects when CaO is not blended with the A agent as in the present embodiment, but is blended with the B agent. When CaO was blended in an amount of 10% by mass and 5% by mass respectively in the B agent, the B agent alone was cured after 1 day of production and was not resistant to use.
Example 26 is a formulation in which 8 parts by mass of CaO is blended with agent A and 0.5% by mass of p-TSCa and p-TDEA is blended with part B. Both curing time and tensile adhesive strength are practically used as cements for use. It was a numerical value equivalent to Example 9.
Comparative Example 5 is a formulation obtained by removing CaO from Agent A of Example 26, and the curing time and tensile adhesive strength after 1 day of manufacture are the same as those in Example 26. After storage for 1 month, there was no appearance of curing even after 24 hours had passed after mixing.
Comparative Examples 6 and 7 are formulations containing a BPO-sulfinate-amine ternary polymerization initiator. One day after production, both the curing time and the tensile adhesive strength are good values, but after storing at 60 ° C. for one month, in Comparative Example 6 with a small amount of BPO, 24 hours after mixing of the A agent and the B agent In Comparative Example 7 with a large amount of BPO, the agent A was cured alone during storage at 60 ° C.

Example 27 and Comparative Examples 8 and 9 in Table 4 are composition examples of composite resins for building an abutment.
The tensile adhesive strength to bovine dentin required for the resin for building an abutment having self-adhesiveness is about 5 MPa to 10 MPa equivalent to the adhesive resin cement, and the tensile adhesive strength in this example is 10 Since it is 2 MPa, it can be evaluated that there is sufficient practical strength as a resin for building an abutment having self-adhesiveness.
In Example 27, the blending amount of the filler was increased in order to increase the mechanical strength, and the numerical value (83.4 MPa) higher than the required bending strength (80 MPa or more) defined in JIS T6514: 2005. was gotten. Moreover, it met the required value (maximum 10 minutes) of the curing time defined in ISO 4049: 2000. Further, even after storage at 60 ° C. for 1 month, no significant changes in curing time, bending strength and tensile adhesive strength are observed.
The comparative example 8 is a case where CaO is not added to the agent A with respect to the example 27. One day after production, the curing time, bending strength, and tensile bond strength all showed values almost equivalent to those in Example 27. After storage at 60 ° C. for 1 month, the mixture of Agent A and Agent B was 24. There was no appearance of curing over time.
In Comparative Example 9, 4-MET, which is a monomer having an acidic group, was removed from the formulation of Example 27, and BPO was added to form a BPO-sulfinate-amine ternary polymerization initiator. It is an example (composition example corresponding to the Example of patent document 2) in which CaO which is a group element compound is contained. In this case, compared with Example 27, the curing time is short after the first day of manufacture and the bending strength is almost the same, but 4-MET which acts as a tooth adhesive monomer is not blended, so tensile adhesion is achieved. The strength is low. Further, after storage at 60 ° C. for one month, there was no appearance of curing even after 24 hours had elapsed after mixing of agent A and agent B due to decomposition of BPO as the polymerization initiator.

Examples 28 to 32 and Comparative Examples 10 to 12 in Tables 5 and 6 are composition examples of a two-component type chemical polymerization bonding agent. Table 5 shows the measurement results of the tensile adhesive strength, and Table 6 shows the measurement results of the Brinell hardness at the contact interface with the Eugenol sealer.
The tensile bond strength of the commercially available bonding agent to bovine dentin is 15 to 30 MPa, and the tensile bond strength in this example is 22.1 to 27.1 MPa, which can be evaluated as having sufficient practical strength. .
In Example 28 containing CaO in the agent A, the tensile adhesive strength after 1 day of production was good, and there was almost no change even after 1 month of storage at 60 ° C. On the other hand, in Comparative Example 10 in which CaO was not contained in the agent A, the tensile adhesive strength after 1 day of production was slightly smaller than that in Example 28, but it was significantly lowered after 1 month of storage at 60 ° C.
However, in Example 29, the A agent and the B agent used in Comparative Example 10 (stored at 60 ° C. for 1 month and the tensile adhesive strength was significantly reduced) were added, and 5 mass% CaO was added to the A agent. When mixed with the B agent, the tensile adhesive strength was recovered. Further, even after the A agent and B agent were further stored at 60 ° C. for 1 month, no decrease in the tensile adhesive strength was observed.
Example 30 is a case where the component (b) itself is an acidic compound, SnCl2 which is an example of the component (a) is blended with the agent A, and the agent A does not contain a polymerizable monomer. . Also in this case, the tensile adhesive strength after one day of production is 22.1 MPa, and there is almost no change even after one month of storage at 60 ° C.

Table 6 shows that the curable composition of the present invention is completely cured even when contacted with a phenolic compound (eugenol) that inhibits radical polymerization, and that the polymerization does not proceed by a radical mechanism. is there.
In Example 31, since the surface brought into contact with the Eugenol sealer exhibits the same Brinell hardness as the surface brought into contact with the glass plate, it is considered that the polymerization is not inhibited by Eugenol.
Comparative Example 11 is a formulation of a two-component chemical polymerization bonding agent containing a BPO-amine polymerization initiator. Since this formulation is cured by a radical mechanism, the surface in contact with the glass plate is sufficiently cured, but the surface in contact with the Eugenol sealer is not cured due to inhibition of radical polymerization, and hardness measurement is impossible. there were. In addition, after the heat deterioration test, due to the deactivation of BPO, there was no appearance of curing even after 24 hours had elapsed after mixing the A agent and the B agent.
In Comparative Example 12 and Example 32, the A and B agents whose curability was remarkably lowered in the heat deterioration test were added with 5 mass% of CaO to the A agent and mixed with the B agent. Indicates that it has recovered.

In Examples 33 to 36 and Comparative Examples 14 and 15 in Table 7, composition examples of root canal filling sealers and results of apical sealing properties are shown. Comparative Example 14 is a result of apical capping test of a commercially available Eugenol root canal filling sealer (trade name: Nishika Canal Sealer).
Example 33 is a composition containing 30% by mass of Ca-G in the agent A, and Example 34 is a composition containing 8% by mass of CaO, both of which are resin-based compared to Comparative Example 14. It exhibits excellent apex-blocking properties, which are the characteristics of sealers, and has good storage stability by a heat deterioration test.
The prescription of Comparative Example 13 is a case where Ca-G and CaO are not included in the agent A, and after the heat deterioration test, a decrease in the apical sealability due to poor curing is observed.
In Example 35, the A and B agents whose curability was remarkably decreased in the heat deterioration test of Comparative Example 13 were added. When 8 mass% CaO was added to the A agent and mixed with the B agent, the curability was restored. This shows that the apical blockage is improved and the storage stability is restored.
In Example 36 and Comparative Example 15, the polymerizable monomer is not blended in the agent A, and the mixing ratio of the agent A and the agent B is set to 1/4. However, the agent A contains CaO. In the case of Comparative Example 15 that does not, after the heat deterioration test, a decrease in apical sealability due to poor curing is observed.

Examples 37 to 44 in Table 8 show composition examples of temporary cement and test results of compressive strength and film thickness.
Examples 37 to 41 are composition examples in which a non-polymerizable organic acid was added in place of 4-MET, which is a dental adhesive monomer, so as not to have adhesiveness to the tooth. In Examples 42 and 43, a polymerizable monomer was not blended with the A agent, and only an acid and CaO were mixed, and the mixing ratio of the A agent and the B agent was set to 1/4. In Example 44, a polymerizable monomer was not added to the agent A, SnCl2 [(b) component itself is an acidic compound, and (a) an example that also serves as the component] was added. The mixing ratio is 1/4.
The values of compressive strength and film thickness satisfy the required values for JIS-T6610: 2005 dental zinc oxide Eugenol cement and zinc oxide non-eugenol cement (temporary wear: compressive strength 35 MPa or less, film thickness 25 μm or less) The results are practical as temporary cement.

Claims (15)

An agent A containing an acidic compound (a) and one or more selected from group IIa elements, tin, lead, or bismuth compounds, or salts thereof, or glass containing them (b) , An organic peroxide used by mixing a polymerizable monomer having no acidic group (c), an aromatic sulfinate (d), and a B agent containing a tertiary amine (e) Two-part dental curable composition containing no The two-component dental curable composition according to claim 1, wherein the acidic compound (a) is a polymerizable monomer (a1) having an acidic group. The two-component dental curable composition according to claim 1, wherein the acidic compound (a) is an acidic compound (a2) having no polymerizable group. The two-component dental curable composition according to claim 2, wherein the acidic compound (a2) having no polymerizable group is a mineral acid, an organic acid, or a phosphate ester. The agent A further contains at least one of a polymerizable monomer having no acidic group (c), an inorganic filler (f), an organic filler (g), or a photopolymerization initiator (h). Item 2. The two-part dental curable composition according to any one of Items 1 to 3. The 2 agent type | mold of any one of Claims 1-4 which further contains 1 or more types of an inorganic filler (f), an organic filler (g), or a photoinitiator (h) in B agent. Dental curable composition. In 100 mass% of agent A, 0.1 to 50 mass% of acidic compound (a) and one or more selected from Group IIa elements, tin, lead, bismuth compounds, or salts thereof ( 0.1 to 30% by mass of b), or glass (b) containing one or more selected from Group IIa elements, tin, lead, or bismuth compounds, or salts thereof The two-part dental curable composition according to any one of claims 1 to 5, which is contained in an amount of 50% by mass. In 100% by mass of agent A, 5 to 60% by mass of the polymerizable monomer (a1) having an acidic group, or 0.1 to 50% by mass of the acidic compound (a2) having no polymerizable group, and 0.1 to 30% by mass of one or more selected from Group IIa elements, tin, lead, or bismuth compounds, or salts thereof, or Group IIa elements, tin, lead, or bismuth The two-part dental system according to any one of claims 1 to 5, comprising 0.1 to 50% by mass of glass (b) containing one or more compounds selected from compounds or salts thereof. Curable composition. In 100% by mass of agent B, 10 to 99% by mass of polymerizable monomer (c) having no acidic group, 0.05 to 10% by mass of aromatic sulfinate (d), tertiary amine The two-part dental curable composition according to any one of claims 1 to 7, comprising 0.05 to 10% by mass of (e). The cement for attachment containing the 2 agent type dental curable composition of any one of Claims 1-9. The bonding agent containing the 2 agent type dental curable composition of any one of Claims 1-9. A sealer for filling a root canal containing the two-part dental curable composition according to any one of claims 1 to 9. A temporary-wearing cement containing the two-part dental curable composition according to any one of claims 1 to 9. A composite resin for building an abutment containing the two-part dental curable composition according to any one of claims 1 to 9. An agent A containing an acidic compound (a) and one or more selected from group IIa elements, tin, lead, or bismuth compounds, or salts thereof, or glass containing them (b) , A polymerizable monomer (c) having no acidic group, an aromatic sulfinate (d), and a B agent containing a tertiary amine (e), and containing no organic peroxide 2 A packaged preparation for obtaining a dosage-form dental curable composition.